WO2020196073A1 - Pigment de microcapsule thermochromique réversible - Google Patents

Pigment de microcapsule thermochromique réversible Download PDF

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Publication number
WO2020196073A1
WO2020196073A1 PCT/JP2020/011594 JP2020011594W WO2020196073A1 WO 2020196073 A1 WO2020196073 A1 WO 2020196073A1 JP 2020011594 W JP2020011594 W JP 2020011594W WO 2020196073 A1 WO2020196073 A1 WO 2020196073A1
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WIPO (PCT)
Prior art keywords
microcapsule pigment
reversible thermochromic
compound
color
pigment according
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PCT/JP2020/011594
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English (en)
Japanese (ja)
Inventor
藤田　勝幸
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Pilot Ink Co Ltd
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Pilot Ink Co Ltd
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Priority to JP2021509112A priority Critical patent/JP7443335B2/ja
Priority to CN202080025196.3A priority patent/CN113767159B/zh
Publication of WO2020196073A1 publication Critical patent/WO2020196073A1/fr
Anticipated expiration legal-status Critical
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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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • 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 lossless thermochromic microcapsule pigment. More specifically, the present invention relates to a lossless thermochromic microcapsule pigment that develops a color by heating from a decolorized state.
  • thermochromic compositions by using hydroxybenzoic acid ester as the component (b), a reversible thermochromic composition exhibiting a discoloration behavior that changes to a color-developing state by heating from a decolorized state and returns to a discolored state by lowering the temperature.
  • hydroxybenzoic acid ester as the component (b)
  • a reversible thermochromic composition exhibiting a discoloration behavior that changes to a color-developing state by heating from a decolorized state and returns to a discolored state by lowering the temperature.
  • a substance and a microcapsule pigment containing the same are disclosed (see, for example, Patent Document 1).
  • thermochromic compositions show a color-developing state by heating, the temperature at which they develop color is high, and it is difficult to easily develop color at a temperature near daily life temperature or daily life temperature. Further, even if a reversible thermochromic composition that develops a color at a daily living temperature or a temperature close to the daily living temperature is obtained, the color density in the colored state is low, and the practicality is not satisfied.
  • the present inventor uses a specific hydroxyphenyl acetate compound as the component (b) and is specific as the component (d). By adding a compound, it exhibits a discoloration behavior that easily returns to the decolorized state by heating from the decolorized state at a temperature near the living environment temperature range or the daily living temperature, and also shows the color density at the time of color development.
  • the present invention has been completed by finding that a reversible thermochromic microcapsule pigment comprising a reversible thermochromic composition having a high temperature can be obtained.
  • thermochromic microcapsule pigment (A) Electron-donating color-forming organic compounds and (B) As an electron-accepting compound, a hydroxyphenylacetic acid ester compound represented by the following general formula (1) and (C)
  • the reaction medium that reversibly causes the electron transfer reaction by the components (a) and (b) is selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons.
  • Compounds and (D) A reversible thermochromic composition comprising a styrene compound having a softening point of 5 ° C. or higher and a mass average molecular weight of 2 to 100,000 is included.
  • R represents a linear or branched alkyl group having 12 to 22 carbon atoms.
  • X, Y, and Z are independently hydrogens or hydroxyl groups, two or three of which are hydroxyl groups and the rest are hydrogens)
  • the reversible thermochromic liquid composition according to the present invention comprises the above-mentioned lossless thermochromic microcapsule pigment and a vehicle.
  • the laminate according to the present invention comprises a support and a lossless thermal discoloration layer containing the above-mentioned microcapsule pigment.
  • the molded product according to the present invention contains the above-mentioned microcapsule pigment in the support.
  • the present invention exhibits a reversible discoloration behavior in which a color is easily developed by heating from a decolorized state in a living environment temperature range or a temperature close to the daily living temperature and returns to the decolored state, and the color density at the time of color development is increased. It is possible to provide a reversible thermochromic microcapsule pigment which is expensive and can be applied to various fields such as learning elements, toys, and decorations.
  • the component (a) of the present invention is a component that determines a color and is a compound that donates electrons to a component (b) that is a color developer to develop a color.
  • the electron-donating color-developing organic compound include a phthalide compound, a fluorene compound, a stirinoquinolin compound, a diazarodamine lactone compound, a pyridine compound, a quinazoline compound, and a bisquinazoline compound, and among these, a phthalide compound and a fluorine compound are preferable. ..
  • phthalide compound examples include diphenylmethanephthalide compound, phenylindrillphthalide compound, indolylphthalide compound, diphenylmethaneazaphthalide compound, phenylindrillazaphthalide compound, and derivatives thereof.
  • Phenylindrill azaphthalide compounds, and derivatives thereof are preferred.
  • fluorene compound examples include an aminofluorane compound, an alkoxyfluorane compound, and a derivative thereof. Examples of these compounds are given below.
  • a substituent on the phenyl group having the substituent on the phenyl group forming the xanthene ring and forming the lactone ring.
  • An alkyl group such as a methyl group, or a halogen atom such as a chloro group
  • a hydroxyphenylacetic acid ester compound represented by the general formula (1) is used as the electron-accepting compound (b).
  • R represents a linear or branched alkyl group having 12 to 22 carbon atoms.
  • X, Y, and Z are each independently hydrogen or hydroxyl group, of which two or three are hydroxyl groups.
  • X, Y, and Z two are hydroxyl groups and one is hydrogen.
  • X and Y are hydroxyl groups and Z is hydrogen.
  • the 3,4-dihydroxyphenylacetic acid ester compound represented by the general formula (2) is preferable, and this is preferably used because the color density at the time of color development is high.
  • R is the same as R in the formula (1).
  • the alkyl group of the hydroxyphenylacetic acid ester compound is a linear or branched alkyl group having 12 to 22 carbon atoms, preferably a linear or branched alkyl group having 14 to 22 carbon atoms.
  • Compounds having an alkyl group having less than 12 or more than 22 carbon atoms have low crystallinity and therefore do not satisfy practicality. Further, in consideration of practical performance such as excellent discoloration characteristics and color development density, a linear alkyl group having 12 to 22 carbon atoms is preferable, a linear alkyl group having 16 to 22 carbon atoms is more preferable, and a linear alkyl group having 16 to 22 carbon atoms is more preferable.
  • hydroxyphenylacetic acid ester compound examples include dodecyl 3,4-dihydroxyphenylacetate, tridecyl 3,4-dihydroxyphenylacetate, tetradecyl 3,4-dihydroxyphenylacetate, 2-methyltridecyl 3,4-dihydroxyphenylacetate, 3, 4-Dihydroxyphenyl acetate pentadecyl, 3,4-dihydroxyphenyl acetate hexadecyl, 3,4-dihydroxyphenyl acetate 2-ethyltetradecyl, 3,4-dihydroxyphenyl acetate heptadecyl, 3,4-dihydroxyphenyl acetate 2-methyl hexadecyl , Octadecyl 3,4-dihydroxyphenylacetate, 2-methylheptyldecyl of 3,4-dihydroxyphenylacetate, 2-eth
  • the reaction medium for reversibly causing the electron transfer reaction by the components (a) and (b) is selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons. Compounds are used.
  • the compound of the component (c) the desensitization to the color development property due to the reaction between the component (a) and the component (b) is small, and it effectively functions to improve the discoloration behavior and the color density of the color development due to heating.
  • the hydroxybenzoic acid ester of the component (b) tends to have higher crystallinity as the number of carbon atoms in the alkyl group increases, and the discoloration temperature of the hydroxybenzoic acid ester having high crystallinity in the low temperature region due to the addition of the component (c) It can be used with.
  • Chain hydrocarbons include saturated chain hydrocarbons such as pentadecane, hexadecane, heptadecane, octadecane, nonadecan, eikosan, heneikosan, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, etc.
  • alicyclic hydrocarbons examples include cyclooctane, cyclododecane, n-pentadecylcyclohexane, n-octadecylcyclohexane, n-nonadecilcyclohexane, and decahydronaphthalene.
  • halogenated hydrocarbons examples include 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-chlorotetradecane, 1-bromopentadecane, 1-bromohexadecane, 1- Chlorohexadecane, 1-iodohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-chlorooctadecane, 1-iodooctadecane, 1-bromoeicosan, 1-chloroeicosan, 1-bromodocosan, 1-chlorodocosan, etc. It can be exemplified.
  • a styrene-based compound having a softening point of 5 ° C. or higher and a mass average molecular weight of 2 to 100,000 is exemplified below.
  • a styrene compound having a mass average molecular weight of 200 to 6000 is preferably used.
  • the mass average molecular weight is measured by the GPC method (gel permeation chromatography).
  • the styrene compound include low molecular weight polystyrene, a styrene- ⁇ -methylstyrene copolymer, an ⁇ -methylstyrene polymer, and a copolymer of ⁇ -methylstyrene and vinyltoluene.
  • styrene- ⁇ -methylstyrene copolymer manufactured by Rika Hercules Co., Ltd., trade name: picorastic A5 (mass average molecular weight 317), picorastic A75 (mass average molecular weight 917), manufactured by Rika Hercules Co., Ltd., Product name: Picorastic D125 (mass average molecular weight 3000) or the like is used.
  • Examples of the ⁇ -methylstyrene polymer include Rika Hercules Co., Ltd., trade names: Crystalx 3085 (mass average molecular weight 664), Crystalx 3100 (mass average molecular weight 1020), Crystalex 1120 (mass average molecular weight 2420), and the like. Used.
  • As the copolymer of ⁇ -methylstyrene and vinyltoluene Rika Hercules Co., Ltd., trade name: Picotex LC (mass average molecular weight 950), Picotex 100 (mass average molecular weight 1740) and the like are used.
  • the styrene-based compound may be used alone, or two or more kinds may be used in combination.
  • thermochromic microcapsule pigment (hereinafter, simply referred to as microcapsule pigment) containing the reversible thermochromic composition cooled from the color-developed state to the decolorization induction temperature in the temperature lowering process is left unattended. Decolorize.
  • the microcapsule pigment according to the present invention is (e) a compound selected from the group consisting of alcohols, esters, ethers, ketones, acid amides, and aromatic hydrocarbons having a melting point of 50 ° C. or higher (hereinafter, It is preferable to further include (sometimes referred to as component (e)).
  • component (e) is illustrated below.
  • hexadecane 1-ol As alcohols, hexadecane 1-ol, heptadecane 1-ol, octadecane 1-ol, nonadecane 1-ol, icosane 1-all, henei cosan 1-all, docosane 1-ol, tetracosane 1-ol, hexacosane 1-ol, Examples thereof include octacosane 1-all and triacontane 1-all.
  • Esters include eicosyl laurate, behenyl laurate, tetracosyl laurate, hexacosyl laurate, octacosyl laurate, cetyl myristate, stearyl myristate, eicosyl myricitate, behenyl myristate, tetracosyl myristate, hexacocil myristate, myristin.
  • ethers examples include pentadecyl ether, dihexadecyl ether, dioctadecyl ether, dieicosyl ether, didocosyl ether and the like.
  • ketones examples include dioctyl ketone, dinonyl ketone, diundecyl ketone, ditridecyl ketone, dipentadecyl ketone, diheptadecyl ketone, dinonadecil ketone, phenyloctyl ketone, phenylundecyl ketone, phenyltridecyl ketone, and phenylpentadecyl.
  • ketones examples include ketones and phenylheptadecyl ketones.
  • Acid amides include hexyl amide, heptyl amide, octyl amide, nonyl amide, decyl amide, undecyl amide, lauryl amide, tridecyl amide, myristyl amide, palmityl amide, stearyl amide, eico syl amide, behenyl amide, hexacocil amide. Examples thereof include amides and octacosylamides.
  • aromatic hydrocarbons examples include biphenyl, orthoterphenyl, metaterphenyl, paraterphenyl, terthiophene and the like.
  • the compounds listed in the table below can also be used as the component (e).
  • the component (e) is preferably a compound selected from the group consisting of esters, ethers, and aromatic hydrocarbons, and is more preferably aromatic hydrocarbons.
  • the crystallization of the component (b) progresses due to the component (b) and the color is decolorized, but it may take time to completely decolorize, and by adding the component (e), Further, crystallization can be promoted and decolorization sensitivity can be improved.
  • the proportions of the components (a), (b), (c), and (d) depend on the color density, discoloration temperature, discoloration form, and type of each component, but generally, the component ratio at which the desired characteristics can be obtained.
  • component 1 component 1
  • component 0.1 to 50 preferably 0.5 to 20
  • component 1 to 200 preferably 5 to 100
  • component 0.1 It is in the range of ⁇ 10.0, preferably 0.5 to 5.0
  • component 0.1 to 5.0 preferably 0.1 to 3.0 (all of the above ratios are by mass). It is a department).
  • the lossless thermochromic composition is used by being encapsulated in microcapsules. This is because even if it comes into contact with a chemically active substance such as an acidic substance, a basic substance, or a peroxide, or other solvent components, its function is not deteriorated and heat stability can be maintained. This is because the reversible thermochromic composition can be kept in the same composition under various conditions of use and can exert the same action and effect.
  • the microcapsule pigment containing the reversible thermochromic composition has a particle size of 0.1 to 100 ⁇ m, preferably 0.5 to 30 ⁇ m, and more preferably 1 to 20 ⁇ m.
  • the particle area is determined using the image analysis type particle size distribution measurement software "MacView” manufactured by Mountec, and the projected area circle equivalent diameter (Heywood) is determined from the area of the particle area. (Diameter) is calculated, and it is a value measured as the particle diameter and the average particle diameter of particles corresponding to equal volume spheres based on the values.
  • a particle size distribution measuring device manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e
  • Multisizer 4e is used by the Coulter method to form an isovolume sphere. It is also possible to measure as the particle size and average particle size of the corresponding particles.
  • a laser diffraction / scattering type particle size distribution measuring device (device name: LA-300, manufactured by Horiba Seisakusho Co., Ltd.) calibrated based on the numerical values measured using the measuring device by the Coulter method, volume-based.
  • the particle size and the average particle size (median size) of the above may be measured.
  • each component may be a mixture of two or more kinds of compounds, and a light stabilizer can be added within a range that does not interfere with the function.
  • the light stabilizer include an ultraviolet absorber that prevents photodeterioration caused by an excited state due to the photoreaction of component (a), a visible light absorber, an infrared absorber, an antioxidant, carotene, pigments, amines, and phenol.
  • Compounds that suppress the oxidation reaction such as singlet oxygen quenchers such as varieties, nickel complexes and sulfides, superoxide anion quenchers such as oxidosis and cobalt, and nickel complexes, and ozone quenchers.
  • a system in which an ultraviolet absorber and an antioxidant and / or a singlet oxygen quencher are used in combination is particularly effective in improving light resistance.
  • an antiaging agent, an antistatic agent, a polarity imparting agent, a rocking denaturing agent, an antifoaming agent and the like can be added as necessary to improve the function.
  • a general dye pigment non-thermally discoloring
  • a lossless thermochromic composition comprising the components (a), (b), (c), and (d), or the components (a), (b), (c), (d), and (e).
  • the discoloration characteristics of microcapsule pigments containing substances will be described.
  • the reversible thermochromic composition exhibiting a decolorized state starts to develop color from the temperature of the color development start temperature (T 1 ) in the heating process, becomes a complete color development state when it reaches the complete color development temperature (T 2 ), and disappears in the process of lowering the temperature.
  • T 1 is preferably 15 to 35 ° C, more preferably 15 to 27 ° C.
  • T 2 is preferably 25 to 50 ° C, more preferably 25 to 40 ° C.
  • Reversible thermochromic microcapsule pigments can be used for (i) screen printing, offset printing, process printing, gravure printing, coaters, tampo printing, etc. by dispersing them in vehicles containing additives as necessary to form liquid compositions.
  • Printing inks used (ii) brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dip coating, etc., (iii) marking pen, ball pen, perpetual brush, brush It can be used for reversible thermochromic liquid compositions such as inks for writing tools such as pens, inks for (iv) coating tools, (v) paints, (vi) cosmetics, and (vi) coloring liquids for fibers.
  • Additives include resins, cross-linking agents, hardeners, desiccants, plasticizers, viscosity regulators, dispersants, UV absorbers, infrared absorbers, antioxidants, light stabilizers, solubilizers, antisettling agents, Examples thereof include smoothing agents, gelling agents, antifoaming agents, matting agents, penetrants, pH adjusting agents, foaming agents, coupling agents, moisturizing agents, fungicides, preservatives and rust preventives.
  • Examples of the vehicle of the liquid composition according to the present invention include an oil-based vehicle containing an organic solvent, or a water-based vehicle containing water and, if necessary, an organic solvent.
  • organic solvent examples include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene.
  • Glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2 -Pyrrolidone and the like can be mentioned.
  • the liquid composition includes a shear thinning liquid composition containing a shear thinning agent in the vehicle, and a cohesive liquid composition containing a water-soluble polymer flocculant in the vehicle and suspending the pigment in a loosely aggregated state.
  • the liquid composition contains a shear thinning agent, for example, when it is used as an ink composition, it is possible to suppress the aggregation and precipitation of the pigment and also to suppress the bleeding of the handwriting, which is good. Can form handwriting.
  • the ballpoint pen when the ballpoint pen is filled with an ink composition containing a shear thinning agent, ink leakage from the gap between the ball and the tip when not in use is prevented, or the writing tip is left facing upward (upright). Backflow of the ink composition in the case can be prevented.
  • xanthan gum As the shear reducing viscosity imparting agent, xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million), which is an organic acid-modified heteropolysaccharide whose constituent monosaccharides are glucose and galactose, guar gum, locust bean gum and its derivatives. , Hydroxyethyl cellulose, alginate alkyl esters, methacrylic acid alkyl esters as main components, polymers with a molecular weight of 100,000 to 150,000, thickening polysaccharides with gelling ability extracted from seaweeds such as glucomannan, agar and caragenin.
  • water-soluble polymer flocculant examples include polyvinylpyrrolidone, polyethylene oxide, and water-soluble polysaccharides.
  • water-soluble polysaccharide examples include traganth gum, guar gum, pullulan, cyclodextrin, and water-soluble cellulose derivative
  • specific examples of the water-soluble cellulose derivative include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and the like. Can be mentioned.
  • a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, and tri-thiophosphite (alkoxy) are used.
  • Thio-phosphoric acid triesters such as carbonyl methyl ester) and thio-phosphate tri (alkoxycarbonylethyl ester), phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers or polyoxyethylene.
  • a phosphoric acid diester of an alkylaryl ether or a lubricant such as a metal salt, an ammonium salt, an amine salt or an alkanolamine salt thereof to prevent wear of the ball receiving seat.
  • acrylic resin styrene-maleic acid copolymer, cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, dextrin, and other resins that impart adhesiveness and viscosity to the paper surface
  • sodium carbonate Inorganic salts such as sodium phosphate and sodium acetate
  • pH adjusters such as organic basic compounds such as water-soluble amine compounds
  • benzotriazole tolyltriazole, dicyclohexylammonium nitrate, diisopropylammonium nitrate, saponin and the like.
  • Rust agent (iv) phenol, sodium salt of 1,2-benzthiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4 -Preservatives or antifungal agents such as (methylsulfonyl) pyridine, (v) urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin , Solbit, mannit, wetting agents such as sodium pyrophosphate, (vi) defoaming agents, (vii) dispersants, (viii) fluorosurfactants and nonionic surfactants that improve the permeability of ink compositions. Agents may be added.
  • the reversible thermochromic microcapsule pigment can be contained, preferably 5 to 40% by mass, more preferably 10 to 40% by mass, and further preferably 10 to 30% by mass with respect to the total mass of the liquid composition.
  • the content of the microcapsule pigment is in the above range, a desired color development density can be achieved, and when used as an ink composition, a decrease in the outflow property can be prevented.
  • the writing instrument comprises a barrel containing the ink composition and a pen body for drawing out the ink in the barrel.
  • the pen body include a marking pen body, a ballpoint pen body, and a brush pen body.
  • the marking pen body include marking chips such as fiber chips, felt chips, and plastic chips.
  • the ballpoint pen body include a ballpoint pen tip.
  • the microcapsule pigment according to the present invention can be combined with a support to form a laminate, and comprises a lossless thermochromic layer containing the microcapsule pigment and a support. Further, it may be a molded product in which the support contains a microcapsule pigment.
  • the microcapsule pigment is dispersed in a medium containing a binder, which is a film-forming material, and is applied as a reversible thermochromic material such as ink and paint, and is applied to conventionally known methods such as screen printing.
  • Paper, synthetic paper by means of offset printing, gravure printing, coater, tampo printing, transfer and other printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dip coating, etc.
  • a reversible thermal discoloration layer is formed on a support such as cloth, brushed or brushed cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, stone, etc. to obtain a laminate, or is dispersed in the support.
  • a molded product can be obtained.
  • a molded product can be obtained as a material that is kneaded and integrated in a molten thermoplastic.
  • compositions used in the lossless thermochromic composition of the present invention are shown in the table below.
  • the numbers in parentheses in the table indicate parts by mass, and the numbers indicating the following compounding amounts are all parts by mass.
  • picorastic A75 has a low molecular weight polystyrene resin and a softening point of 75 ° C.
  • picorastic D125 has a low molecular weight polystyrene resin and a softening point of 125 ° C.
  • picorastic A5 has a low molecular weight.
  • the compounds 1, 2 and 6 described in the component (e) in the table are the compounds described in the table exemplifying the component (e).
  • thermochromic composition After each reversible thermochromic composition was heated and melted to form a compatible compound, a microcapsule pigment in the form of microcapsules encapsulated in an epoxy resin film was obtained by an interfacial polymerization reaction with an epoxy resin and an amine curing agent. After preparing the following measurement samples for the microcapsule pigment, the discoloration temperature was measured by the following measurement method.
  • the discoloration characteristics of the microcapsule pigment are as follows: A printed matter printed on high-quality paper by screen printing using a reversible thermochromic ink in which 40 parts of the microcapsule pigment is dispersed in 60 parts of an ethylene-vinyl acetate emulsion is measured. And said.
  • Measurement method The measurement samples of Examples 1 to 14 are set in a predetermined place of a color difference meter [TC-3600 type color difference meter, manufactured by Tokyo Denshoku Co., Ltd.], and the speed is 10 ° C./min in a temperature range of 0 ° C. to 40 ° C. Heat at. After heating to 40 ° C., it was cooled to the decolorization induction temperature and left to be decolorized.
  • the table below shows the color change, color development start temperature (T 1 ), complete color development temperature (T 2 ), decolorization induction temperature, and color density (brightness value) at the time of color development in each example.
  • Comparative Examples 1 and 2 The composition used for the lossless thermochromic composition is shown in the table below.
  • the numbers in parentheses in the table indicate parts by mass, and the numbers indicating the following compounding amounts are all parts by mass.
  • thermochromic composition After each reversible thermochromic composition was heated and melted to form a compatible compound, a microcapsule pigment in the form of microcapsules encapsulated in an epoxy resin film was obtained by an interfacial polymerization reaction with an epoxy resin and an amine curing agent. After preparing the following measurement samples for the microcapsule pigment, the discoloration temperature was measured by the following measurement method.
  • the discoloration characteristics of the microcapsule pigment are as follows: A printed matter printed on high-quality paper by screen printing using a reversible thermochromic ink in which 40 parts of the microcapsule pigment is dispersed in 60 parts of an ethylene-vinyl acetate emulsion is measured. And said.
  • Application example 1 30.0 parts of microcapsule pigment containing the reversible thermochromic composition prepared in Example 1, 2.0 parts of fluorescent pigment (pink), 50.0 parts of acrylic resin emulsion, 3.0 parts of defoamer, A reversible thermochromic screen ink consisting of 15.0 parts of turpen emulsion was prepared. Printing was performed on polyester taffeta by screen printing using a reversible thermochromic screen ink to form a reversible thermochromic layer to obtain a reversible thermochromic sheet. The reversible thermochromic sheet turns purple when heated to 26 ° C. or higher. When the reversible thermochromic sheet is cooled to 18 ° C. and then left to stand, the reversible thermochromic sheet turns pink.
  • thermochromic offset ink 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition produced in Example 2 is uniformly dispersed and mixed in 50.0 parts of a linseed oil-based offset ink vehicle to obtain a reversible thermochromic offset ink.
  • Offset printing was performed on high-quality paper using the offset ink to form a reversible thermochromic layer to obtain a reversible thermochromic sheet.
  • the sheet turns blue when heated above 38 ° C.
  • the reversible thermochromic sheet is cooled to 26 ° C. and then left to stand, the reversible thermochromic sheet becomes colorless.
  • Application example 3 Obtained by uniformly dispersing and kneading 33.3 parts of a microcapsule pigment containing the reversible thermochromic composition prepared in Example 3, 66.4 parts of a hard type liquid epoxy resin, and 0.3 part of a defoaming agent. 20.0 parts of a room temperature curable aliphatic polyamide was added to the reversible thermochromic epoxy ink, and the mixture was stirred and mixed to prepare a reversible thermochromic epoxy ink. A curved screen is printed on the surface of a ceramic cup using a reversible thermal discoloration epoxy ink on a 100 mesh screen plate made of stainless steel, and heat-cured at 70 ° C. for 60 minutes to form a reversible thermal discoloration layer.
  • thermochromic cup turns blue when heated above 50 ° C.
  • the reversible thermochromic cup becomes colorless.
  • thermochromic spray paint was prepared by stirring and mixing in a vehicle consisting of 23.0 parts of methyl isobutyl ketone and 6.0 parts of a polyisocyanate-based curing agent.
  • a reversible thermochromic spray paint was spray-painted on the entire miniature train to form a reversible thermochromic layer to obtain a reversible thermochromic miniature train. Lossless thermochromic miniature trains turn purple when heated above 32 ° C. When the reversible thermochromic miniature train is cooled to 24 ° C. and then left to stand, the reversible thermochromic miniature train exhibits a pink color.
  • thermochromic spray coating material was prepared by stirring and mixing in a vehicle consisting of 23.0 parts of a ketone and 6.0 parts of a polyisocyanate-based curing agent.
  • a reversible thermochromic spray paint was spray-painted on the entire miniature train to form a reversible thermochromic layer to obtain a reversible thermochromic miniature car.
  • the reversible thermochromic miniature car turns purple when heated above 38 ° C.
  • the reversible thermochromic miniature car is cooled to 26 ° C. and then left to stand, the reversible thermochromic miniature car exhibits a blue color.
  • Application example 6 50.0 parts of microcapsule pigment containing the reversible thermochromic composition prepared in Example 5, 0.04 part of yellow pigment, 1000.0 parts of 12 nylon resin (melting point 178 ° C.), 10.0 parts of ultraviolet absorber was mixed and dispersed with a Henshell mixer, and then a reversible thermochromic 12 nylon resin pellet (reversible thermochromic molding resin composition) was obtained using an extrusion molding machine.
  • a resin composition for reversible thermochromic molding was used for melt spinning to obtain a reversible thermochromic filament as a molded product. Hair was transplanted to the head of the doll using a filament. When the filament is heated to 32 ° C. or higher, it exhibits a green color in which blue and yellow are mixed. When the filament is cooled to 10 ° C. and then left to stand, the filament turns yellow.
  • Application example 7 30.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 6 is composed of 45.0 parts of an acrylic acid ester resin emulsion, 1.0 part of an antifoaming agent, and 23.0 parts of diluted water. It was mixed in a vehicle and filtered through a 180 mesh screen to give a reversible thermochromic spray paint. A spray gun (diameter 0.6 mm) was filled with the spray paint, and the entire surface of the white cloth (support) was painted, and then dried to form a reversible thermochromic layer to obtain a reversible thermochromic cloth. The fabric was sewn to make a swimsuit. Swimwear turns blue when heated above 38 ° C. When the swimsuit is cooled to 20 ° C. and then left to stand, the swimsuit becomes white.
  • Application example 8 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 8 is uniformly dispersed and mixed in 50.0 parts of a linseed oil-based offset ink vehicle to obtain a reversible thermochromic offset ink. Prepared. Offset printing was performed on high-quality paper using the offset ink to form a reversible thermochromic layer to obtain a reversible thermochromic sheet. Friction heat is generated by rubbing the sheet with a friction tool made of SEBS, and when heated to 32 ° C. or higher, it turns blue. When the reversible thermochromic sheet is cooled to 5 ° C. and then left to stand, the reversible thermochromic sheet becomes white.
  • Application example 9 50.0 parts of the microcapsule pigment containing the reversible thermochromic composition prepared in Example 9 is uniformly dispersed and mixed in 50.0 parts of a linseed oil-based offset ink vehicle to obtain a reversible thermochromic offset ink. Prepared. Offset printing was performed on high-quality paper using offset ink to form a reversible thermochromic layer to obtain a reversible thermochromic sheet. When the sheet is heated to 32 ° C. or higher using an energizing heater, it turns blue. After cooling the reversible thermochromic sheet to 24 ° C. and leaving it for a while, the reversible thermochromic sheet turns white.

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

Abstract

La présente invention vise à fournir un pigment de microcapsule thermochromique réversible qui présente un comportement thermochromique réversible tel que le pigment passe facilement d'un état incolore à un état de développement de couleur lorsqu'il est chauffé dans une plage de température d'environnement vivant ou à la température, ou approximativement, de la vie courante, puis revient à l'état incolore, et présente également une densité de couleur élevée lorsque le pigment développe une couleur. L'invention concerne par conséquent un pigment de microcapsule thermochromique réversible qui comprend (a) un composé organique de développement de couleur donneur d'électrons, (b) un composé ester d'acide hydroxyphénylacétique représenté par la formule générale (1) et servant de composé accepteur d'électrons, (c) un composé sélectionné parmi des hydrocarbures à chaîne, des hydrocarbures alicycliques, et des hydrocarbures halogénés, en tant que médiateur de réaction qui provoque de manière réversible une réaction de transfert d'électrons entre le composant (a) et le composant (b), et (d) un composé à base de styrène ayant un point de ramollissement de 5 °C ou plus et un poids moléculaire moyen en masse de 200 à 100 000. (Dans La formule, R représente un groupe alkyle à chaîne droite ou ramifiée ayant 12 à 22 atomes de carbone, X, Y, et Z représentent chacun indépendamment un atome d'hydrogène ou un groupe hydroxy, et deux ou trois de X, Y et Z représentent chacun un groupe hydroxy)
PCT/JP2020/011594 2019-03-28 2020-03-17 Pigment de microcapsule thermochromique réversible Ceased WO2020196073A1 (fr)

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CN202080025196.3A CN113767159B (zh) 2019-03-28 2020-03-17 可逆热变色性微胶囊颜料

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WO2023100627A1 (fr) * 2021-11-30 2023-06-08 株式会社パイロットコーポレーション Pigment en microcapsule thermochromique réversible

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JPS5694361A (en) * 1979-12-27 1981-07-30 Ishihara Sangyo Kaisha Ltd Electrophotographic receptor
JP2000263947A (ja) * 1999-03-17 2000-09-26 Nippon Paper Industries Co Ltd 感熱記録体
US20150165806A1 (en) * 2013-12-18 2015-06-18 Appvion, Inc. Thermal recording materials
JP2017014328A (ja) * 2015-06-29 2017-01-19 パイロットインキ株式会社 可逆熱変色性マイクロカプセル顔料

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TW554027B (en) * 2001-10-18 2003-09-21 New Prismatic Entpr Co Ltd Reversible thermochromic composition
AU2011286681B2 (en) * 2010-08-06 2014-01-16 Tokuyama Corporation Photochromic composition
JP5937833B2 (ja) * 2012-02-06 2016-06-22 パイロットインキ株式会社 可逆熱変色性マイクロカプセル顔料
JP5819773B2 (ja) * 2012-04-30 2015-11-24 パイロットインキ株式会社 可逆熱変色性マイクロカプセル顔料
JP6216148B2 (ja) * 2012-10-11 2017-10-18 パイロットインキ株式会社 可逆熱変色性印刷物
JP5968755B2 (ja) * 2012-10-29 2016-08-10 パイロットインキ株式会社 可逆熱変色性マイクロカプセル顔料
FR3063082B1 (fr) * 2017-02-17 2019-04-05 Societe Bic Nouvelle composition de pigment thermochrome comprenant un compose de formule (i) en tant que milieu reactionnel

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Publication number Priority date Publication date Assignee Title
JPS5694361A (en) * 1979-12-27 1981-07-30 Ishihara Sangyo Kaisha Ltd Electrophotographic receptor
JP2000263947A (ja) * 1999-03-17 2000-09-26 Nippon Paper Industries Co Ltd 感熱記録体
US20150165806A1 (en) * 2013-12-18 2015-06-18 Appvion, Inc. Thermal recording materials
JP2017014328A (ja) * 2015-06-29 2017-01-19 パイロットインキ株式会社 可逆熱変色性マイクロカプセル顔料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023100627A1 (fr) * 2021-11-30 2023-06-08 株式会社パイロットコーポレーション Pigment en microcapsule thermochromique réversible
CN118339237A (zh) * 2021-11-30 2024-07-12 株式会社百乐 可逆热致变色微胶囊颜料

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CN113767159B (zh) 2024-12-06
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CN113767159A (zh) 2021-12-07

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