WO2012115121A1 - Composition thermochromique - Google Patents

Composition thermochromique Download PDF

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Publication number
WO2012115121A1
WO2012115121A1 PCT/JP2012/054180 JP2012054180W WO2012115121A1 WO 2012115121 A1 WO2012115121 A1 WO 2012115121A1 JP 2012054180 W JP2012054180 W JP 2012054180W WO 2012115121 A1 WO2012115121 A1 WO 2012115121A1
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WIPO (PCT)
Prior art keywords
color
temperature
composition
compound
weight
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PCT/JP2012/054180
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English (en)
Japanese (ja)
Inventor
徳正 栗原
鉄太郎 荒木
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株式会社サクラクレパス
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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
Priority to CN201280010292.6A priority Critical patent/CN103391984B/zh
Publication of WO2012115121A1 publication Critical patent/WO2012115121A1/fr

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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
    • 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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or 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
    • 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 and relates to a thermochromic composition using a specific discoloration temperature adjusting agent. .
  • Patent Documents 1 to 5 disclose an electron-donating color-forming organic compound, an electron-accepting compound, a temperature-sensitive color-changing color memory microcapsule pigment employing various compounds as a reaction medium for controlling the color-changing reaction, reversible heat Color-changing microcapsule pigments, reversible temperature-sensitive color-changing hysteresis compositions and temperature-sensitive color-changing color memory liquid compositions are described. Specifically, according to the microcapsule pigment described in Patent Document 1, the hysteresis width obtained is 56 ° C. at most, and according to the microcapsule pigment described in Patent Document 2, the hysteresis obtained is as narrow as 14.5 ° C. or less. Hysteresis width.
  • the reversible temperature-sensitive color-changing hysteresis composition described in Patent Document 3 has a hysteresis width of 52 to 95 ° C., but the color-change temperature adjusting agent used in the composition is 4,4- (hexafluoroisopropyl acetate. Redene) is a diester composed of bisphenol and a saturated or unsaturated fatty acid having 9 to 19 carbon atoms.
  • the temperature-sensitive color-changing color memory liquid composition described in Patent Document 4 uses a benzyloxyphenylethanol ester compound and has a hysteresis width of 40 to 70 ° C.
  • the temperature-sensitive color-changing composition not only has the property of developing / decoloring at a predetermined temperature as a boundary, but, for example, even if the temperature decreases after heating to develop color, the coloring / decoloring may occur when the temperature decreases slightly. There is a case that it is necessary to have a property that cannot be restored. In such a case, as described in Patent Documents 1 and 2, in the prior art, a composition having a narrow hysteresis width is known, and such a composition could not cope with the above-described necessity. .
  • compositions described in Patent Documents 3 and 4 have a wide hysteresis width, but these are formed by using a specific color change temperature adjusting agent, and other color change temperature adjusting agents are used. Furthermore, a reversible thermosensitive color-changing composition having a wide hysteresis width and its microcapsules have not been known. In view of such circumstances, an object of the present invention is to obtain a temperature-sensitive color-changing composition having a wide hysteresis width and a microcapsule thereof by employing a new color-change temperature adjusting agent.
  • a temperature-sensitive color-changing composition comprising a leuco dye, a color developing substance, and a color-change temperature adjusting agent, wherein the color-change temperature adjusting agent is one or more of the following compounds a to e. 1.
  • each R represents a C4-22 aliphatic hydrocarbon group.
  • a temperature-sensitive color-changing composition having a wide hysteresis width can be obtained using a novel color-change temperature adjusting agent.
  • FIG. 1 is a discoloration temperature curve.
  • thermosensitive color-changing composition and the microcapsules of the present invention impart reversible thermochromic properties to resin molded articles such as polyolefin, printing inks, inks, paints, packaging materials, fibers, recording materials, and the like.
  • resin molded articles such as polyolefin, printing inks, inks, paints, packaging materials, fibers, recording materials, and the like.
  • the thermochromic composition of the present invention may be used as a coloring agent for drawing materials such as writing instruments and crayons. In that case, the handwriting and the painted part by the coloring agent can be made temperature-sensitive discoloration.
  • the temperature-sensitive color-changing composition of the present invention may be provided in a form encapsulated in microcapsules. Even when microencapsulated, it is possible to impart temperature-sensitive discoloration to the article.
  • the microencapsulated thermosensitive color-changing composition imparts thermochromic properties to aqueous emulsion inks, solvent volatile drying inks, two-part curable epoxy resin inks, printing pastes, and ultraviolet curable inks. Is preferably used.
  • Leuco dye The leuco dye (color former) is not limited as long as it reacts with an electron-accepting compound (developable substance) and develops color, and known or commercially available ones can be used.
  • the following compounds can be preferably used. These can be used alone or in combination of two or more.
  • At least one of fluorans can be suitably used.
  • 2 '-[(2-chlorophenyl) amino] -6'-(dibutylamino) -spiro [isobenzofuran-1 (3H), 9 '-(9H) xanthen] -3-one and 3,6-diphenyl More preferred is at least one aminofluorane.
  • the content of the leuco dye can be appropriately set according to the type of the compound and the like, but is generally about 0.1 to 50% by weight, particularly 0.8 to 15% by weight in the thermochromic composition of the present invention. % Is desirable. When the content is less than 0.1% by weight, the color density may be lowered. Moreover, when the said content exceeds 50 weight%, there exists a possibility that background coloring may become large.
  • developer is not limited, and a known or commercially available one can be used as appropriate.
  • the following compounds can be preferably used. These can be used alone or in combination of two or more.
  • Phenols bisphenol A or derivatives thereof, bisphenol S or derivatives thereof, p-phenylphenol, dodecylphenol, o-bromophenol, ethyl p-oxybenzoate, methyl gallate, phenol resin, etc .
  • Metal salts of phenols metal salts of phenols such as Na, K, Li, Ca, Zn, Al, Mg, Ni, Co, Sn, Cu, Fe, Ti, Pb, and Mo
  • C aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms: phthalic acid, benzoic acid, acetic acid, propionic acid, etc .
  • Acid phosphate esters butyl acid phosphate, 2-ethylhexyl acid phosphate, dodecyl acid phosphate, etc .
  • At least one selected from 1) bisphenol A and its derivatives and 2) bisphenol S and its derivatives is more preferred, most preferably 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis Examples include at least one of (4-hydroxyphenyl) propane and 1,1-bis (4′-hydroxyphenyl) -1-phenylethane.
  • the content of the color developing substance can be appropriately set according to the type of the compound and the like, but is generally about 0.05 to 98% by weight, particularly 0.5 to It is desirable that the content be 77% by weight.
  • the content is less than 0.05% by weight, the color density may be lowered.
  • the said content exceeds 98 weight%, there exists a possibility that background coloring may become large.
  • the leuco dye in relation to the leuco dye, it is preferable to use 0.1 to 100 parts by weight, particularly 0.5 to 20 parts by weight of the color developing substance with respect to 1 part by weight of the leuco dye.
  • each R represents a C4-22 aliphatic hydrocarbon group.
  • each R represents a C4-22 aliphatic hydrocarbon group, which may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. Furthermore, it may have a cyclic aliphatic hydrocarbon group or may have an aromatic ring. In particular, in view of easy adjustment of the color change temperature, a C7 to C13 linear or branched aliphatic hydrocarbon group is desirable.
  • the content (total amount) of such a color change temperature adjusting agent can be appropriately set according to the type of the compound and the like, but is generally about 1 to 99% by weight in the temperature-sensitive color change composition of the present invention, In particular, 19 to 99% by weight, more preferably 60 to 95% by weight is desirable. If the content is less than 1% by weight, the background color may increase. On the other hand, when the content exceeds 99% by weight, the color density may be lowered.
  • an ultraviolet absorber if necessary, an ultraviolet absorber, an infrared absorber, an antioxidant, a non-temperature-sensitive color-changing pigment, a non-temperature-sensitive color-changing dye, a fluorescent whitening agent, You may mix
  • the ultraviolet absorber may be any compound that effectively absorbs ultraviolet rays contained in sunlight or the like and prevents photodegradation caused by the excited state due to the photoreaction of the color former.
  • the ultraviolet absorber include benzophenone, benzotriazole, cyanoacrylate, triazine, salicylic acid, alinide oxalate, malonic ester, benzoic acid, cinnamic acid, and dibenzoylmethane.
  • a benzotriazole type ultraviolet absorber is preferable.
  • the content (total amount) of the ultraviolet absorber can be appropriately set according to the type of the compound and the like, but is generally about 0 to 96% by weight, particularly 0 to 61% in the thermochromic composition of the present invention. It is desirable to set the weight%.
  • the temperature-sensitive color-changing composition of the present invention is prepared by putting these components into a known mixer such as a stirrer, mixer, homogenizer and the like and mixing them uniformly. be able to. In this case, it is preferable to mix while heating.
  • the heating temperature is not limited, but is usually about 120 to 180 ° C.
  • thermochromic microcapsules obtained by encapsulating the thermochromic composition in the microcapsules.
  • a structure similar to that of a known microcapsule can be adopted except that the thermochromic composition of the present invention is used as the content.
  • the microcapsule which encloses the content containing a temperature-sensitive color-change composition with a wall film is mentioned.
  • the soot contents may contain a solvent (dissolution aid), an emulsifier, and the like, if necessary, in addition to the thermochromic composition.
  • a solvent dissolution aid
  • an emulsifier emulsifier
  • the content of the temperature-sensitive temperature-changing composition is not limited, but generally it is preferably about 6 to 98% by weight, particularly 50 to 95% by weight when the microcapsule is 100% by weight.
  • the soot solvent can be appropriately selected from known solvents as long as the temperature-sensitive color-changing composition and the wall film material can be uniformly dissolved and the temperature-sensitive color-changing performance is not impaired. In particular, those that can be removed in a later step are desirable.
  • ester solvents excluding the compounds a and d
  • ketone solvents excluding the compounds a and d
  • ether solvents excluding the compounds a and d
  • glycol ether solvents glycol ether solvents
  • hydrocarbon solvents hydrocarbon solvents
  • aromatic solvents nitrogen-containing solvents
  • silicon solvents Halogen-containing solvents
  • Halogen-containing solvents can be used. These can be used alone or in combination of two or more.
  • soot emulsifier an amphiphilic substance that is adsorbed on the surface of the oil droplet and stabilized when the contents are emulsified in water can be suitably used.
  • these can be employed from known emulsifiers.
  • water-soluble natural polymers, water-soluble synthetic polymers, surfactants, inorganic fine particles and the like can be mentioned. These can be used alone or in combination of two or more.
  • the emulsifier can be appropriately determined according to the type of the resin component constituting the wall film.
  • the resin component is an epoxy resin
  • proteins such as gelatin and casein can be suitably used in addition to polysaccharides such as gum arabic as emulsifiers.
  • a melamine formalin resin when used as a resin component, an ethylene maleic anhydride copolymer or the like can be suitably used as an emulsifier.
  • urethane isocyanate
  • gelatin polyvinyl alcohol, or the like can be used.
  • a resin-based wall film can be suitably used as the wall film.
  • the resin for example, various thermoplastic resins and thermosetting resins can be used. More specifically, epoxy resin, polyamide resin, acrylonitrile resin, polyurethane resin, polyurea resin, urea-formaldehyde resin, melamine-formaldehyde resin, benzoguanamine resin, butylated melamine resin, butylated urea resin, urea-melamine system Examples thereof include resins. These resin components can be used alone or in combination of two or more. When manufacturing microcapsules, these raw materials are used, and these can be polymerized suitably by polymerizing them.
  • thermochromic microcapsules of the present invention is in accordance with known microencapsulation except that the thermochromic composition of the present invention is used as the contents. Can be implemented.
  • the microencapsulation method include an interfacial polymerization method (polycondensation and addition polymerization), an in situ polymerization method, a coacervation method, a submerged drying method, and a spray drying method.
  • thermosensitive discoloration of main raw materials excluding the crosslinking agent
  • First step of preparing a solution by mixing or dissolving with a functional composition 2) Second step of adding the obtained solution to an aqueous emulsifier solution to prepare an O / W emulsion, 3) Crosslinking agent or solution thereof
  • a microcapsule can be suitably produced by a method including the third step of adding to the O / W emulsion.
  • each step will be described.
  • a solution is prepared by mixing or dissolving a main raw material (excluding a crosslinking agent) that can form a wall film with a temperature-sensitive color-changing composition in the presence or absence of a solvent. To do.
  • the amount of the temperature-sensitive color-changing composition used is usually preferably 5 to 50 parts by weight, particularly 10 to 40 parts by weight, based on 100 parts by weight of the emulsifier aqueous solution.
  • productivity may be reduced.
  • the said usage-amount exceeds 50 weight part, there exists a possibility that emulsification may become difficult.
  • the main raw material and the crosslinking agent those used as the components constituting the wall film described in the above (2) may be used.
  • the wall film is made of melamine resin, polyurea resin or the like, melamine, urea or the like may be used as the main raw material, and formalin may be used as the crosslinking agent.
  • an isocyanate compound when the wall film is a urethane resin or the like, an isocyanate compound may be used as a main raw material and a polyalcohol may be used as a crosslinking agent.
  • an epoxy compound may be used as a main raw material and a polyamine compound may be used as a crosslinking agent.
  • a polyamine compound may be used as a crosslinking agent.
  • an isocyanate compound is used as a main raw material, and a polyamine compound, polyalcohol, water, etc. are used as a crosslinking agent. Use it.
  • an acid chloride compound may be used as a main raw material and a polyamine compound may be used as a crosslinking agent.
  • an acrylic compound when the wall film is an acrylic resin or the like, an acrylic compound may be used as a main raw material and a peroxy compound may be used as a crosslinking agent.
  • Use amounts of the main raw material and the crosslinking agent are not particularly limited.
  • the main raw material can be appropriately set in the range of usually 1 to 50 parts by weight, preferably 2 to 10 parts by weight with respect to 100 parts by weight of the emulsifier aqueous solution.
  • the crosslinking agent can be appropriately set within the range of usually 0.5 to 25 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the emulsifier aqueous solution. When the amount of the main raw material or the crosslinking agent used is too small or too large, the reaction becomes insufficient, and the strength, heat resistance, etc. of the capsule (wall film) may be lowered.
  • a solvent can be used as necessary.
  • the solvent those listed above can be used.
  • the amount of the soot solvent used is not limited, but it can usually be appropriately set within the range of 0 to 100 parts by weight, preferably within the range of 0 to 40 parts by weight with respect to 100 parts by weight of the emulsifier aqueous solution.
  • Second Step the obtained solution is added to an aqueous emulsifier solution to prepare an O / W emulsion.
  • the emulsifier aqueous solution can be an aqueous solution obtained by dissolving the above emulsifier in water.
  • the concentration of the emulsifier aqueous solution can be appropriately set according to the type of the emulsifier, but is generally 0.1 to 15% by weight, particularly preferably 0.5 to 8% by weight. If the concentration is less than 0.2% by weight, emulsification may be difficult. If the concentration exceeds 15% by weight, foaming may occur.
  • the O / W emulsion can be prepared according to a known method such as a stirring method or a membrane permeation method.
  • the droplet diameter of the O / W emulsion may be set as appropriate within a range of about 0.1 to 20 ⁇ m.
  • a crosslinking agent or a solution thereof is added to the O / W emulsion.
  • a crosslinking agent each crosslinking agent enumerated above can be used.
  • the solution of the crosslinking agent for example, an aqueous crosslinking agent solution obtained by dissolving the crosslinking agent in water can be suitably used.
  • the concentration of the aqueous solution in this case is not limited, but it may be appropriately set within the range of about 1 to 100% by weight.
  • the method for adding the cross-linking agent is not particularly limited, but it is preferable to add it by dropping.
  • an isocyanate compound when used as a wall film raw material, an amine compound generated by the reaction of water and an isocyanate in an aqueous emulsifier solution can be used as a crosslinking agent without newly adding a crosslinking agent.
  • the desired microcapsules can be obtained in the form of a slurry. Thereafter, if necessary, the microcapsules can be recovered as a solid content according to a known solid-liquid separation method such as filtration or centrifugation. In addition, the microcapsules can be washed as necessary.
  • thermochromic composition was prepared by uniformly mixing each component shown in Table 1 with a stirrer while heating at 120 to 180 ° C.
  • the obtained thermochromic composition was microencapsulated by the following method.
  • thermochromic composition obtained in 1 and 2 were uniformly mixed and dissolved to obtain a solution.
  • the solution was added to 71.4 parts of a 4% gelatin aqueous solution (emulsifier aqueous solution) heated to 30 to 60 ° C. with medium shear stirring.
  • O / W emulsion droplet particle size: about 5 ⁇ m was obtained from the solution by performing high shear stirring.
  • the stirring was switched to low shear stirring, and the aqueous crosslinking agent solution was dropped into the O / W emulsion.
  • the slurry was cooled to room temperature to obtain a slurry in which microcapsules were dispersed.
  • Leuco dye 2 '-[(2-chlorophenyl) amino] -6'-(dibutylamino) spiro [isobenzofluorane-1 (3H), 9 '-(9H) xanthene)]-3-one developer (Developer): 2,2-bis (4-hydroxyphenyl) hexafluoropropane color change temperature adjusting agent a: 4-hydroxymethylbiphenyl decanoic acid ester color change temperature adjusting agent b: benzoic acid phenyl-n-decyl ether color change Temperature adjusting agent c: 4-hydroxybenzophenone lauryl ether Color changing temperature adjusting agent d: 4-chloro-4'-hydroxybenzophenone lauric acid ester Color changing temperature adjusting agent e: Decyl ether of 4-hydroxymethylbiphenyl Color changing temperature adjusting agent f: Benzyl Phenylketone discoloration temperature regulator g: Stearyl palmitate
  • thermochromic compositions of Examples 1 to 5 using the compounds a to e in the present invention the complete color temperature T1 is ⁇ 5 ° C. or less, and the color development / decoloration branch temperature T2 is 40 ° C.
  • the result that the daily temperature environment is within the range of these T1 and T2 was obtained. This indicates that the color does not change in a normal temperature range, and the color is erased at a heated temperature exceeding the temperature range or colored at a cooled temperature.
  • the thermochromic composition in a decolored state and a colored state in some cases Can be used properly.
  • the complete color temperature T1 is particularly low, and there is an effect that the once-decolored composition is unlikely to be recolored even outdoors in a cold region.
  • thermochromic composition of Comparative Example 1 in which none of the compounds a to e in the present invention was used and benzyl phenyl ketone was used as the color change temperature adjusting agent, the complete color temperature T1 was just 24 ° C. It is room temperature and the width of hysteresis is narrow, and the width of hysteresis does not include room temperature, indicating that it will cause unintentional thermal discoloration under daily use conditions. Not suitable for applications that do not require discoloration under conditions.
  • the hysteresis width is wide, and the complete color temperature T1 is as high as 40 ° C.
  • the color developing / decoloring branching temperature T2 since it exhibits the property of being decolored at 61 ° C. or higher, which is the color developing / decoloring branching temperature T2, by heating, it is impossible to obtain two types of coloring and decoloring depending on the case at ordinary temperatures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

L'invention a pour but d'obtenir : une composition thermochromique dans laquelle un nouveau régulateur de température de changement de couleur est employé et qui comporte une grande largeur d'hystérésis ; et des microcapsules de celle-ci. A cet effet, selon l'invention, le problème a été résolu par une composition qui comprend un leucocolorant, un développeur de couleur et un régulateur de température de changement de couleur, le régulateur de température de changement de couleur étant au moins l'un des composés (a) à (e). Selon la présente invention, une composition thermochromique ayant une grande largeur d'hystérésis peut être obtenue à l'aide d'un nouveau régulateur de température de changement de couleur.
PCT/JP2012/054180 2011-02-24 2012-02-22 Composition thermochromique WO2012115121A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201280010292.6A CN103391984B (zh) 2011-02-24 2012-02-22 感温变色性组合物

Applications Claiming Priority (4)

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JP2011038329 2011-02-24
JP2011-038329 2011-02-24
JP2012-007683 2012-01-18
JP2012007683A JP5833457B2 (ja) 2011-02-24 2012-01-18 感温変色性組成物

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EP3109293A1 (fr) * 2015-06-26 2016-12-28 Dong-A Pencil Co., Ltd. Microparticules thermochromiques et composition d'encre thermochromique, appareil d'écriture et fenêtre intelligente l'utilisant
WO2017037284A1 (fr) * 2015-09-03 2017-03-09 Thermographic Measurements Ltd Composé à utiliser dans des compositions à changement de couleur
WO2018094630A1 (fr) * 2016-11-24 2018-05-31 The Gillette Company Llc Poignée pour dispositif de rasage comprenant un matériau thermochromique
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EP3009493B1 (fr) * 2013-06-14 2018-01-31 The Pilot Ink Co., Ltd. Composition thermochromique à mémoire de couleur et pigment de microcapsule thermochromique à mémoire de couleur l'encapsulant
CN103614043B (zh) * 2013-11-21 2016-02-10 天津翔盛粉末涂料有限公司 一种可逆示温粉末涂料及其制备方法和使用方法
US9855789B2 (en) * 2014-08-18 2018-01-02 The Pilot Ink Co., Ltd. Thermochromic color-memorizing composition and thermochromic color-memorizing microcapsule pigment encapsulating same
KR102562352B1 (ko) * 2015-06-26 2023-08-01 동아연필 주식회사 열변색성 미세 입자 및 이를 이용한 열변색성 잉크 조성물, 필기구 및 스마트 윈도우
CN104893421A (zh) * 2015-06-29 2015-09-09 蔡武军 一种可逆温敏变色固体墨组合物
US20180142141A1 (en) * 2016-11-24 2018-05-24 The Gillette Company Llc Handle for shaving device comprising a thermochromic material
EP3587534B1 (fr) * 2017-02-27 2021-10-06 The Pilot Ink Co., Ltd Pigment microcapsulaire thermochromique à mémoire de couleur renfermant composition thermochromique à mémoire de couleur
KR101988916B1 (ko) 2017-05-25 2019-06-13 주식회사 엑티브온 과열방지 비가역적 감온변색 성형체 및 그 제조방법
CN109575664B (zh) * 2018-12-21 2021-03-26 上海晨光文具股份有限公司 长期稳定变色油画棒及其制备方法

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