WO2010061819A1 - Composition thermochrome et microcapsule thermochrome - Google Patents

Composition thermochrome et microcapsule thermochrome Download PDF

Info

Publication number
WO2010061819A1
WO2010061819A1 PCT/JP2009/069799 JP2009069799W WO2010061819A1 WO 2010061819 A1 WO2010061819 A1 WO 2010061819A1 JP 2009069799 W JP2009069799 W JP 2009069799W WO 2010061819 A1 WO2010061819 A1 WO 2010061819A1
Authority
WO
WIPO (PCT)
Prior art keywords
electron
thermochromic
thermochromic composition
color
compound
Prior art date
Application number
PCT/JP2009/069799
Other languages
English (en)
Japanese (ja)
Inventor
盛作 大城
Original Assignee
株式会社サクラクレパス
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社サクラクレパス filed Critical 株式会社サクラクレパス
Publication of WO2010061819A1 publication Critical patent/WO2010061819A1/fr

Links

Classifications

    • 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
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B

Definitions

  • the present invention relates to a thermochromic composition having reversibility and a thermochromic microcapsule containing the thermochromic composition.
  • thermochromic composition containing an electron-donating color-forming organic compound, an electron-accepting compound, and a desensitizer has already been proposed and put to practical use. Recently, in order to obtain a higher quality thermochromic composition, it has been proposed to use any one or more components as a specific compound.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6-88070
  • a thermochromic composition that is excellent in terms of color density, background color development, and color change an electron-donating color-forming organic compound, electron-accepting property is disclosed.
  • thermochromic composition containing a compound and at least one desensitizer selected from carbazole derivatives represented by a specific general formula is disclosed.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2000-297277
  • a reversible thermochromic composition having improved fastness, particularly water resistance, high color density at the time of color development and low toxicity
  • a composition comprising a developer having a specific general formula has been proposed.
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-29483 discloses a reversible thermochromic UV curable ink that exhibits permanent reversible thermochromic properties without impairing the color change sensitivity and has an efficient UV curable property.
  • a reversible thermochromic composition and a microcapsule pigment encapsulating a light fastness-imparting agent represented by a specific general formula are dispersed in a photopolymerizable composition containing an ultraviolet absorber and a photopolymerization initiator. Inks have been proposed.
  • Patent Document 4 Japanese Patent Laid-Open No.
  • JP-A-6-88070 JP 2000-297277 A Japanese Patent Laid-Open No. 2001-294783 JP 2001-31884 A JP 2003-119309 A
  • thermochromic composition not only has the property of developing / decoloring at a predetermined temperature, but also has the property that its density (color density) does not easily change over time after color development, that is, the color density. It is sometimes required to have stability over time. For example, in applications where the thermochromic composition is colored for a long period of time (for example, decoration of tableware such as cups and mugs), the color density of the thermochromic composition is low and the stability over time is predetermined. It is not preferable because the appearance and the characters are difficult to see. Accordingly, the thermochromic composition used in the above applications is required to have high color density stability over time.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a thermochromic composition having excellent color density stability over time.
  • the present invention includes an electron-donating color-forming organic compound, an electron-accepting compound, and a desensitizer.
  • the electron-accepting compound is represented by any one of the following general formulas (1) to (3) and has a melting point
  • a thermochromic composition comprising one or more compounds having a temperature of 150 ° C. or lower is provided.
  • R1 and R2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a cyclohexyl group, and X, Y And Z are each independently a halogen, an OH group, an alkoxy group, an alkoxyallyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cyclohexyl group, and C is A C5-C8 cycloalkane which may have a substituent or a fluorene ring which may have a substituent.
  • thermochromic composition of the present invention is an electron-accepting compound, that is, a compound represented by a specific chemical formula and having a melting point of 150 ° C. or lower (hereinafter referred to as “low-melting color developer for convenience”). Is used).
  • low-melting color developer a compound represented by a specific chemical formula and having a melting point of 150 ° C. or lower
  • a low melting point developer By using a low melting point developer, a reversible thermochromic composition having excellent color developability and decoloring property and excellent color density stability with time can be obtained.
  • thermochromic composition is a compound represented by any one of the above general formulas (1) to (3) as a developer and having a melting point higher than 150 ° C. (hereinafter, for convenience) There is provided a thermochromic composition further comprising a “high melting point developer”. One or more high melting point developers may be included.
  • thermochromic composition of the present invention shows excellent color density stability over time as long as a low melting point developer is contained, even when a high melting point developer is contained.
  • a high melting point developer it is possible to utilize the characteristics (for example, high color developability or high decoloring property) and to improve the color density stability over time by using the low melting point developer. .
  • the present invention also provides a thermochromic microcapsule in which the thermochromic composition of the present invention is encapsulated.
  • the thermochromic composition is encapsulated in the microcapsules, the microcapsules are less susceptible to the influence of substances present in the surroundings.
  • thermochromic composition of the present invention exhibits excellent color density concentration stability over time by using a compound represented by the above specific formula and having a melting point of 150 ° C. or less as a developer. Therefore, the thermochromic composition of the present invention is suitable for applications in which a colored state is maintained for a long time. For example, textile products, inks, paints, pottery, glass products, plastic moldings, packaging materials, recording materials And as a colorant for imparting reversible thermochromic properties to printed matter.
  • thermochromic composition of the present invention includes an electron-donating color-forming organic compound, an electron-accepting compound, and a desensitizer, It contains at least one compound represented by a specific general formula and having a melting point of 150 ° C. or lower. Below, the component which comprises the thermochromic composition of this invention is demonstrated.
  • the electron-donating color-forming organic compound is also called a color former and reacts with the electron-accepting compound to give a color.
  • a known compound may be arbitrarily used as the electron-donating color-forming organic compound.
  • the electron donating color-forming organic compound is preferably 2- (2-chloroanilino) -6-dibutylaminofluorane or 3,6-bis (diphenylamino) fluorane.
  • the content of the electron-donating color-forming organic compound is preferably 0.1% by weight to 50% by weight, based on the weight of the entire composition, and 0.8% by weight to 15% by weight. More preferably.
  • the content of the electron-donating color-forming organic compound is small, the color density may be low.
  • the background color color density in the decolored state
  • the electron-accepting compound is also called a color developer, and is a compound that reacts with an electron-donating color-forming organic compound to develop a color.
  • a compound having pores Furthermore, in the present invention, a compound (low melting color developer) represented by any one of the following general formulas (1) to (3) and having a melting point of 150 ° C. or lower is used as the electron accepting compound.
  • R1 and R2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a cyclohexyl group, and X, Y and Z is independently halogen, OH group, alkoxy group, alkoxyallyl group, allyl group, straight or branched alkyl group having 1 to 4 carbon atoms, phenyl group, or cyclohexyl group, and C is substituted A cycloalkane having 5 to 8 carbon atoms which may have a group or a fluorene ring which may have a substituent.
  • an arc containing C means that the carbon atom bonded to the two aromatic rings is a carbon atom constituting a cycloalkane. Accordingly, in the general formula (2), when C is a cycloalkane having 6 carbon atoms (that is, cyclohexane), the general formula (2) is represented by the following formula.
  • p-cumylphenol bis (4-hydroxyphenyl) ethane, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-methoxydiphenylsulfone, 2,2′-diallyl -4,4'dihydroxydiphenylsulfone and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferably used as the electron-accepting compound.
  • 2,2′-diallyl-4,4′dihydroxydiphenylsulfone and 4-hydroxy-4′-isopropoxydiphenylsulfone are excellent in heat resistance.
  • kneaded into a thermoplastic resin Is suitable.
  • thermochromic composition having better characteristics can be obtained utilizing the characteristics of each compound.
  • the compound represented by any one of the above three general formulas and having a melting point exceeding 150 ° C. Colorants may be used as electron accepting compounds.
  • High melting point compounds are generally excellent in heat resistance. Therefore, by using a combination of a low melting point compound and a high melting point compound, it is possible to obtain a composition having excellent color density stability over time and excellent heat resistance.
  • the high melting point compound examples include 4-hydroxy-4′-propoxydiphenyl sulfone, 1,1-bis (4-hydroxyphenyl) -1-isobutylethane, and 2,2-bis (4-hydroxyphenyl) propane. 4-hydroxy-4′-allyloxydiphenyl sulfone, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and biscresol fluorene are preferably used.
  • 1,1-bis (4-hydroxyphenyl) -1-phenylethane, biscresol fluorene, 4-hydroxy-4'-allyloxydiphenyl sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane and 4- Hydroxy-4'-propoxydiphenyl sulfone has excellent heat resistance, and is suitable for use in, for example, kneading into a thermoplastic resin.
  • the content of the electron-accepting compound is preferably 0.05% by weight to 98% by weight, more preferably 0.5% by weight to 77% by weight, based on the weight of the entire composition. preferable.
  • the electron-accepting compound is preferably contained in an amount of 0.1 to 100 parts by weight, preferably 0.5 to 20 parts by weight, with respect to 1 part by weight of the electron-donating color-forming organic compound. More preferably.
  • the weight ratio thereof is 1:99 to 99: 1 (low-melting color developer: high-melting color developer). It is preferable that they are mixed, and it is more preferable that they are mixed so as to be 10:90 to 90:10. If the proportion of the low melting point developer is too large, heat resistance by the high melting point developer may not be obtained. If the proportion of the low melting point developer is too small, good color density stability over time can be obtained. There may not be.
  • the desensitizer is a compound that can dissolve the electron-donating color-forming organic compound and the electron-accepting compound, and can control the color reaction by the solidification or melting characteristics thereof.
  • the color can be changed at ⁇ 10 ° C. to 60 ° C. by selecting a commonly used desensitizer.
  • a hardly volatile hydrophobic organic medium or solvent or solvent is used as a desensitizer.
  • examples of the desensitizer include aliphatic monohydric alcohols having 10 or more carbon atoms, fatty acids having 10 or more carbon atoms, fatty acid monoamides having 6 or more carbon atoms, and ester compounds having 13 or more carbon atoms in total. it can
  • the general-purpose desensitizer acid is a polybasic acid.
  • the general-purpose desensitizer alcohol is a polyhydric alcohol.
  • the general-purpose desensitizer acid is a polybasic acid and the alcohol is a polyhydric alcohol.
  • an aliphatic ketone compound having a total carbon number of 10 or more and an aliphatic ether compound having a total carbon number of 10 or more which are general-purpose desensitizers, can be used in the present invention.
  • the content of the desensitizer is preferably 1% by weight to 99% by weight, and more preferably 19% by weight to 99% by weight, based on the weight of the entire composition.
  • the desensitizer is preferably contained in an amount of 1 to 500 parts by weight, more preferably 5 to 100 parts by weight with respect to 1 part by weight of the electron donating color-forming organic compound. .
  • thermochromic composition of the present invention may contain other components contained in a normal thermochromic composition. Hereinafter, other components will be described.
  • the composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber selectively absorbs ultraviolet rays contained in sunlight. Ultraviolet rays cause the color former to deteriorate by photoreaction. UV absorbers are used to prevent this.
  • UV absorbers are broadly classified into benzophenone, benzotriazole, cyanoacrylate, triazine, salicylic acid, oxalic anilide, malonic ester, benzoic acid, cinnamic acid, and dibenzoylmethane.
  • benzotriazole-based Tinuvin 326, triazine-based Tinuvin 40 (both manufactured by Ciba Specialty Chemicals), and benzophenone-based Siasorb UV531 (manufactured by Cytec Industries) can be used.
  • the content of the ultraviolet absorber is preferably up to 96% by weight, and more preferably up to 61% by weight, based on the weight of the entire composition.
  • the content of the ultraviolet absorber is large, the color density may be lowered, discoloration may not be sharp, and / or discoloration temperature hysteresis may be increased.
  • an ultraviolet absorber is contained in the quantity up to 50 weight part with respect to 1 weight part of electron-donating colorable organic compounds, and it is more preferable that it is contained in the quantity up to 10 weight part.
  • the composition of the present invention may contain an ultraviolet scattering agent.
  • the ultraviolet scattering agent physically reflects or scatters ultraviolet rays contained in sunlight. As a result, the action of ultraviolet rays on the color former is prevented.
  • the ultraviolet scattering agent is, for example, metal oxide fine particles such as zinc oxide, titanium oxide, ⁇ -iron oxide, and cerium oxide.
  • the composition of the present invention may contain a light stabilizer.
  • the light stabilizer prevents the coloring agent from deteriorating due to the reaction between the radicals generated by ultraviolet rays and the coloring agent.
  • hindered phenols or hindered amines may be used as light stabilizers.
  • antioxidants phenolic, phosphorous, and sulfur-based
  • infrared absorbers fluorescent brighteners
  • non-thermochromic dyes non-thermochromic pigments
  • non-thermochromic pigments one or more components may be included.
  • thermochromic composition of the present invention can be produced by heating and dissolving an electron-donating color-forming organic compound, an electron-accepting compound, a desensitizer, and, if necessary, other components.
  • the temperature at that time is selected so that the component having the highest melting point out of all the components is dissolved, and is generally in the range of 120 ° C. to 180 ° C.
  • thermochromic composition of the present invention may be encapsulated in microcapsules. Due to the microencapsulation, the problems that arise when the thermochromic composition is used as it is, for example, in ink or plastic moldings, ie, 1) the migration of components to repeat the solid-liquid state change during discoloration. 2) In particular, in the case of ink, vehicle components (resins, solvents, etc.) tend to affect the discoloration and may have an adverse effect. Is avoided or reduced. This is because the microencapsulation blocks the contact with the surrounding atmosphere during use, thereby preventing the influence of substances present in the vicinity.
  • thermochromic composition The microencapsulation of the thermochromic composition can be performed according to the following procedure.
  • the capsule wall raw material and the thermochromic composition are uniformly dissolved in the desensitizer using a dissolution aid as necessary.
  • the solubilizing agent can uniformly dissolve the thermochromic composition and the capsule wall raw material, and does not impair the thermochromic performance or needs to be removed in a subsequent process.
  • an ester solvent, a ketone solvent, an ether solvent, a glycol ether solvent, a hydrocarbon solvent, an aromatic solvent, a nitrogen-containing solvent, a silicon solvent, and a halogen-containing solvent are dissolved.
  • the capsule wall raw material contains a resin main agent and a crosslinking agent.
  • the resin main component is a compound that reacts with a crosslinking agent at the interface of an O / W emulsion having a capsule inclusion as a dispersed phase to form a capsule wall.
  • the crosslinking agent is a compound that reacts with the resin main component at the interface of the O / W emulsion having the capsule inclusion as a dispersed phase to form a capsule wall.
  • a solution containing the capsule wall raw material and the thermochromic composition is added to the aqueous emulsifier solution heated to 30 to 60 ° C. with medium shear stirring. After the addition, high shear stirring is performed to obtain an O / W emulsion having an average particle size of several ⁇ m.
  • An emulsifier is an amphiphilic substance that is adsorbed on the interface of an O / W emulsion having a capsule inclusion as a dispersed phase to stabilize the system.
  • the emulsifier is a natural water-soluble polymer, a synthetic water-soluble polymer, a low molecular surfactant, and inorganic fine particles.
  • the emulsifiers according to the combination of the resin main agent and the crosslinking agent are as follows.
  • the aqueous emulsifier solution is preferably an aqueous solution containing 0.1 to 15% by weight of an emulsifier, and more preferably an aqueous solution containing 0.5 to 8% by weight of an emulsifier. If the concentration of the emulsifier is too high, foaming may occur, and if it is too low, the particle size may increase or emulsification may not be possible.
  • Thermochromic composition 5-50 parts by weight (10-40 parts by weight)
  • Dissolving aid 0 to 100 parts by weight (0 to 40 parts by weight)
  • Emulsifier aqueous solution 100 parts by weight
  • Resin main ingredient 1-50 parts by weight (2-10 parts by weight)
  • Cross-linking agent 0.5 to 25 parts by weight (1 to 5 parts by weight)
  • thermochromic composition If the amount of the thermochromic composition is too large, emulsification may not be possible, and if it is too small, the productivity may deteriorate. If the amount of the solubilizing agent is too large, the productivity may be deteriorated, and if it is too small, the color density may be lowered. If the amount of the resin main component is too large or too small, the reaction may be insufficient and the capsule strength and heat resistance may be reduced. Similarly, if the amount of the crosslinking agent is too large or too small, the reaction may be insufficient and the strength and heat resistance of the capsule may be reduced.
  • thermochromic composition of the present invention can be used to impart reversible thermochromic properties to plastic molded articles such as polyethylene and polypropylene, printing inks, inks, paints, packaging materials, fibers, recording materials, and the like. it can. Or you may use the thermochromic composition of this invention as a coloring agent of a writing instrument and a drawing material (for example, crayon). In that case, the line drawing and painting written or drawn with them can be thermochromic.
  • thermochromic composition of the present invention may be provided in a form encapsulated in microcapsules. Even when microencapsulated, the above-mentioned article can be imparted with thermochromic properties.
  • the microencapsulated thermochromic composition is preferable for imparting thermochromic properties to aqueous emulsion inks, solvent volatile drying inks, two-component curable epoxy resin inks, printing pastes, and ultraviolet curable inks. Used.
  • thermochromic composition was prepared using an electron-donating color-forming organic compound (color former), an electron-accepting compound (developer) and a desensitizer shown in Tables 3-6. Specifically, these three components were heated and dissolved at a temperature in the range of 120 to 180 ° C.
  • thermochromic composition heated to 70-100 ° C.
  • a sample for measurement was prepared by dropping 0.05 g onto 5C filter paper and heating and impregnating at 70 ° C. for 10 minutes.
  • the impregnation condition was 100 ° C. for 10 minutes.
  • the white color proofing of the initial color development state and ground color development state of the obtained measurement sample and the color development state (color density) after storage Evaluation was made by determining the color difference from the plate.
  • the color difference is expressed by the following formula.
  • L * indicates a lightness index
  • a * and b * indicate a chromaticness index. Details are described in the instruction manual of the device (especially page 77). It can be said that the larger the ⁇ E *, the higher the color density or background color density.
  • the measurement of ⁇ E * in the colored state was performed in a ⁇ 5 ° C. cooler box, and the measurement of ⁇ E * in the ground colored (decolored) state was performed on a 100 ° C. hot plate.
  • the color development state after storage was evaluated by measuring ⁇ E * after storing at 32 ° C. for 4 days. From the ⁇ E * before and after storage, the rate of change in color density was calculated according to the following formula.
  • Tables 3 to 6 show the evaluation results of the measurement samples prepared with the discoloration compositions of each Example and each Comparative Example.
  • the melting point of the electron-accepting compound was measured using TG / DTA6220 manufactured by SII Nanotechnology. The measurement was performed at an N2 flow rate of 200 ml / min and a heating rate of 10 ° C./min, and the melting start temperature appearing on the DTA curve was taken as the melting point.
  • Examples 27 to 34 Microcapsules containing a composition selected from the thermochromic compositions prepared in Examples 1 to 26 and Comparative Examples 1 to 20 were produced.
  • the materials and amounts used for the production of the microcapsules are as follows.
  • thermochromic composition and the resin main agent are uniformly dissolved in the solubilizer, and then this solution is added to the aqueous emulsifier solution heated to 60 ° C. with medium shear stirring. did.
  • high shear stirring was performed to obtain an O / W emulsion having an average particle size of several ⁇ m.
  • low shear stirring was performed and the aqueous crosslinking agent solution was gradually added dropwise. After dropping, the mixture was reacted at 60 ° C. for 1 hour and 90 ° C. for 1 hour, cooled to room temperature, and a slurry in which microcapsules were dispersed was obtained.
  • thermochromic composition obtained by cooling a sample for measurement to room temperature, One filter paper was coated with a doctor blade (200 ⁇ m) and dried at room temperature for 2 hours. Using this sample, ⁇ E * was measured in a colored state and a ground colored (decolored) state, and ⁇ E * was measured in a colored state after storage. These measurements were made by the method described in connection with Examples 1-26. Table 8 shows the initial color development and ground color development of each example and each comparative example, the rate of change in color density after storage, and the color density stability over time.
  • Examples and Comparative Examples are reversible thermochromic compositions that can develop a black color at a temperature lower than that at a color change temperature of about 30 ° C. and repeat the change of colorlessness at a higher temperature.
  • Examples 1 to 4 using an electron-accepting compound having a melting point ⁇ 150 ° C. all had an absolute value of the change rate after storage of 10 or less, and showed excellent color density stability over time.
  • Comparative Examples 1 to 6 using only an electron-accepting compound having a melting point> 150 ° C. the absolute value of the change rate of ⁇ E * after storage exceeded 10 in all cases, and the color density greatly changed over time. The stability was low.
  • Examples 9 to 15 in which two types of electron-accepting compounds having a melting point ⁇ 150 ° C. were combined or an electron-accepting compound having a melting point ⁇ 150 ° C. and an electron-accepting compound having a melting point> 150 ° C.
  • the absolute values of the rate of change were 10 or less, indicating excellent color density stability over time.
  • Comparative Examples 13 to 17 in which two kinds of electron accepting compounds having melting points> 150 ° C. were used in combination, the absolute value of the change rate of ⁇ E * after storage exceeded 10 in all cases, and the color density increased with time. Changed and less stable.
  • Example 20 to 22 and 24-26 in which a developer having a melting point ⁇ 150 ° C. was used alone or in combination of two, and an ultraviolet absorber was added, the absolute value of the change rate of ⁇ E * after storage was 10 or less. Yes, it showed excellent color density stability over time.
  • Comparative Example 20 using a developer having a melting point> 150 ° C. and adding an ultraviolet absorber the absolute value of the change rate of ⁇ E * after storage exceeds 10, and the color density increases with time. Changed and less stable.
  • Example 23 in which two kinds of electron-donating color-forming organic compounds were used in combination and an electron-accepting compound having a melting point ⁇ 150 ° C. was used, the absolute value of the change rate of ⁇ E * after storage was 10 or less.
  • thermochromic composition Examples 1, 3, 5, 7, 23 to 26
  • the change rate of ⁇ E * after storage The absolute values of these were all 10 or less, indicating excellent color density stability over time.
  • Comparative Examples 21 to 24 in which the thermochromic compositions of Comparative Examples 5, 11, 19, and 20 were microencapsulated, the absolute value of the change rate of ⁇ E * after storage exceeded 10 in all cases. As time passed, the color density changed greatly and the stability was low.
  • thermochromic composition of the present invention can be reversibly discolored and has excellent color density stability over time, so that it can be used for textiles, inks, paints, ceramics, glass products, plastic moldings, packaging materials, It can be used as a colorant for imparting reversible thermochromic properties to recording materials and printed matter.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une composition thermochrome réversible avec une excellente stabilité dans le temps de la densité des couleurs développées. La composition thermochrome contient un composé organique colorant donneur d'électrons, un composé accepteur d'électrons et un désensibilisateur. Un ou plusieurs composés représentés par une formule générale spécifique portant deux cycles aromatiques et ayant un point de fusion inférieur ou égal à 150 °C sont utilisés comme composés accepteurs d'électrons et permettent d'obtenir l'excellente stabilité précitée. La composition thermochrome convient pour les applications dans lesquelles une couleur développée doit durer longtemps, et peut être utilisée, par exemple, comme colorant pour des produits fibreux, des encres, des matériaux de revêtement, des poteries, des produits verriers, des corps moulés en plastique, des matériaux d'emballage, des matériaux d'enregistrement et des imprimés, avec un thermochromisme réversible.
PCT/JP2009/069799 2008-11-25 2009-11-24 Composition thermochrome et microcapsule thermochrome WO2010061819A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008299476A JP5595652B2 (ja) 2008-11-25 2008-11-25 熱変色性組成物および熱変色性マイクロカプセル
JP2008-299476 2008-11-25

Publications (1)

Publication Number Publication Date
WO2010061819A1 true WO2010061819A1 (fr) 2010-06-03

Family

ID=42225693

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/069799 WO2010061819A1 (fr) 2008-11-25 2009-11-24 Composition thermochrome et microcapsule thermochrome

Country Status (2)

Country Link
JP (1) JP5595652B2 (fr)
WO (1) WO2010061819A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018123204A (ja) * 2017-01-30 2018-08-09 パイロットインキ株式会社 可逆熱変色性組成物及びそれを内包した可逆熱変色性マイクロカプセル顔料
CN111542736A (zh) * 2017-12-21 2020-08-14 株式会社日立产机系统 温度检测材料和使用其的温度偏离时间的推定系统

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6239933B2 (ja) * 2013-10-25 2017-11-29 三菱鉛筆株式会社 マイクロカプセル色材及び筆記具用インク組成物
JP6245511B2 (ja) * 2013-10-25 2017-12-13 三菱鉛筆株式会社 マイクロカプセル色材及び筆記具用インク組成物
KR101988916B1 (ko) * 2017-05-25 2019-06-13 주식회사 엑티브온 과열방지 비가역적 감온변색 성형체 및 그 제조방법
JPWO2022065230A1 (fr) * 2020-09-28 2022-03-31
US20230287259A1 (en) * 2020-09-28 2023-09-14 The Pilot Ink Co., Ltd. Reversibly thermochromic composition and reversibly thermochromic microcapsule pigment encapsulating the same
JPWO2022065229A1 (fr) * 2020-09-28 2022-03-31

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60149685A (ja) * 1984-01-17 1985-08-07 Matsui Shikiso Kagaku Kogyosho:Kk 熱可逆変色性組成物
JPH0688070A (ja) * 1992-09-08 1994-03-29 Sakura Color Prod Corp 熱変色性組成物
JPH0995633A (ja) * 1995-09-29 1997-04-08 Sakura Color Prod Corp 加熱履歴表示用インキ組成物
JPH09176628A (ja) * 1995-12-27 1997-07-08 Pilot Ink Co Ltd 可逆性熱変色組成物の発色時の耐光性を向上する方法
JPH09208850A (ja) * 1996-02-06 1997-08-12 Pilot Ink Co Ltd 可逆性熱変色組成物の消色時の耐光性を向上する方法
JP2000330321A (ja) * 1999-05-21 2000-11-30 Pilot Ink Co Ltd 感温変色性乾式トナー
JP2003136845A (ja) * 2001-10-30 2003-05-14 Pilot Ink Co Ltd 金属光沢調感温変色性印刷物
JP2004264830A (ja) * 2003-02-12 2004-09-24 Oji Paper Co Ltd インジケータ、ラベル及び温度／時間履歴検知方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3694795B2 (ja) * 1994-07-01 2005-09-14 パイロットインキ株式会社 熱変色性プロセス印刷物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60149685A (ja) * 1984-01-17 1985-08-07 Matsui Shikiso Kagaku Kogyosho:Kk 熱可逆変色性組成物
JPH0688070A (ja) * 1992-09-08 1994-03-29 Sakura Color Prod Corp 熱変色性組成物
JPH0995633A (ja) * 1995-09-29 1997-04-08 Sakura Color Prod Corp 加熱履歴表示用インキ組成物
JPH09176628A (ja) * 1995-12-27 1997-07-08 Pilot Ink Co Ltd 可逆性熱変色組成物の発色時の耐光性を向上する方法
JPH09208850A (ja) * 1996-02-06 1997-08-12 Pilot Ink Co Ltd 可逆性熱変色組成物の消色時の耐光性を向上する方法
JP2000330321A (ja) * 1999-05-21 2000-11-30 Pilot Ink Co Ltd 感温変色性乾式トナー
JP2003136845A (ja) * 2001-10-30 2003-05-14 Pilot Ink Co Ltd 金属光沢調感温変色性印刷物
JP2004264830A (ja) * 2003-02-12 2004-09-24 Oji Paper Co Ltd インジケータ、ラベル及び温度／時間履歴検知方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018123204A (ja) * 2017-01-30 2018-08-09 パイロットインキ株式会社 可逆熱変色性組成物及びそれを内包した可逆熱変色性マイクロカプセル顔料
CN111542736A (zh) * 2017-12-21 2020-08-14 株式会社日立产机系统 温度检测材料和使用其的温度偏离时间的推定系统
US11635335B2 (en) 2017-12-21 2023-04-25 Hitachi Industrial Equipment Systems Co., Ltd. Temperature sensing material, and temperature deviation time estimating system employing same

Also Published As

Publication number Publication date
JP2010126549A (ja) 2010-06-10
JP5595652B2 (ja) 2014-09-24

Similar Documents

Publication Publication Date Title
JP5595652B2 (ja) 熱変色性組成物および熱変色性マイクロカプセル
JP5833457B2 (ja) 感温変色性組成物
KR100753199B1 (ko) 탈색가능한 화상 형성 재료
JP6995753B2 (ja) 変色性組成物に用いられる化合物
JP5324128B2 (ja) 熱変色性組成物及び熱変色性マイクロカプセル
BR112015023622B1 (pt) Pigmentos microencapsulados em pequena escala e seus usos
JP3726217B2 (ja) 感温変色性色彩記憶性マイクロカプセル顔料
JP4568027B2 (ja) フォトクロミック材料
KR102215243B1 (ko) 감온 변색성 조성물 및 이를 포함하는 감온 변색성 마이크로캡슐
JP5819773B2 (ja) 可逆熱変色性マイクロカプセル顔料
US6770125B2 (en) Reversible thermochromic composition
JP5968755B2 (ja) 可逆熱変色性マイクロカプセル顔料
JP3833563B2 (ja) 耐光堅牢性に優れた感温変色性組成物
JP5937833B2 (ja) 可逆熱変色性マイクロカプセル顔料
KR102172624B1 (ko) 감온 변색성 조성물 및 이를 포함하는 감온 변색성 마이크로캡슐
JPS63308087A (ja) 温度依存性フォトクロミック組成物
JP2010127634A (ja) 再利用可能な経時インジケーター
JPH0781089B2 (ja) 熱可逆変色性微小カプセル並びにその製造方法
JP5840483B2 (ja) 可逆熱変色性固形筆記体の製造方法
JP2523350B2 (ja) 熱可逆変色性組成物及び熱可逆変色性粒状物
JP2008031313A (ja) 熱変色性組成物及び熱変色性マイクロカプセル
JP2022542696A (ja) 変色性組成物及び化合物
WO2019074008A1 (fr) Composition de développement de couleur ultraviolette irréversible et technologie associée à celle-ci
CA2133932C (fr) Pigment a microcapsules, memorisant la couleur et thermosensible
Khanjankhani et al. Preparation of Reversible Thermochromic Ink for Flexography Printing on Paper and Study its Colorimetric Properties

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09829067

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09829067

Country of ref document: EP

Kind code of ref document: A1