WO2012115121A1 - Thermochromic composition - Google Patents
Thermochromic composition Download PDFInfo
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- 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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- 0 *C(OCc(cc1)ccc1-c1ccccc1)=O Chemical compound *C(OCc(cc1)ccc1-c1ccccc1)=O 0.000 description 1
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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
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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
- 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
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- 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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Abstract
[Problem] To obtain: a thermochromic composition in which a novel color change temperature regulator is employed and which is provided with a broad hysteresis width; and microcapsules thereof. [Solution] The problem has been resolved by a composition which comprises a leuco dye, a color developer and a color change temperature regulator, wherein the color change temperature regulator is at least one of compounds (a) to (e). [Effect] According to the present invention, a thermochromic composition having a broad hysteresis width can be obtained using a novel color change temperature regulator.
Description
本発明は感温変色性組成物に関するものであり、特定の変色温度調整剤を使用してなる感温変色性組成物に関する。
The present invention relates to a thermochromic composition and relates to a thermochromic composition using a specific discoloration temperature adjusting agent. .
特許文献１～５には、電子供与性呈色性有機化合物、電子受容性化合物、変色反応をコントロールする反応媒体として各種化合物を採用してなる感温変色性色彩記憶性マイクロカプセル顔料、可逆熱変色性マイクロカプセル顔料、可逆感温変色性ヒステリシス組成物及び感温変色性色彩記憶性液状組成物が記載されている。
具体的には、特許文献１記載のマイクロカプセル顔料によれば、得られるヒステリシス幅がせいぜい５６℃であり、特許文献２記載のマイクロカプセル顔料によれば得られるヒステリシスが１４．５℃以下と狭いヒステリシス幅である。
また、特許文献３記載の可逆感温変色性ヒステリシス組成物は、そのヒステリシスの幅が５２～９５℃ではあるが、その組成物にて使用する変色温度調整剤は４，４－（ヘキサフルオロイソプロピリデン）ビスフェノールと炭素数９～１９の飽和又は不飽和脂肪酸からなるジエステルである。
特許文献４記載の感温変色性色彩記憶性液状組成物は、ベンジルオキシフェニルエタノールのエステル化合物を使用してヒステリシス幅が４０～７０℃である。 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.
具体的には、特許文献１記載のマイクロカプセル顔料によれば、得られるヒステリシス幅がせいぜい５６℃であり、特許文献２記載のマイクロカプセル顔料によれば得られるヒステリシスが１４．５℃以下と狭いヒステリシス幅である。
また、特許文献３記載の可逆感温変色性ヒステリシス組成物は、そのヒステリシスの幅が５２～９５℃ではあるが、その組成物にて使用する変色温度調整剤は４，４－（ヘキサフルオロイソプロピリデン）ビスフェノールと炭素数９～１９の飽和又は不飽和脂肪酸からなるジエステルである。
特許文献４記載の感温変色性色彩記憶性液状組成物は、ベンジルオキシフェニルエタノールのエステル化合物を使用してヒステリシス幅が４０～７０℃である。 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.
感温変色性組成物は、所定の温度を境に発色／消色する性質を有するだけではなく、例えば加熱して発色した後に温度が低下しても、多少の温度低下では発色／消色が元に戻らないような性質を必要とする場合がある。
このような場合には、特許文献１及び２に記載したように、先行技術においてはヒステリシス幅が狭い組成物が知られており、そのような組成物では上記の必要な場合に対応できなかった。
このため、特許文献３や４に記載された組成物であれば広いヒステリシス幅を有するが、これらは特定の変色温度調整剤を採用してなるものであり、その他の変色温度調整剤を使用し、かつ広いヒステリシス幅を備えた可逆感温変色性組成物およびそのマイクロカプセルまでは知られていなかった。
このような事情に鑑みて、本発明は新たな変色温度調整剤を採用して、広いヒステリシス幅を備えた感温変色性組成物及びそのマイクロカプセルを得ることを課題とした。 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. .
For this reason, the 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.
このような場合には、特許文献１及び２に記載したように、先行技術においてはヒステリシス幅が狭い組成物が知られており、そのような組成物では上記の必要な場合に対応できなかった。
このため、特許文献３や４に記載された組成物であれば広いヒステリシス幅を有するが、これらは特定の変色温度調整剤を採用してなるものであり、その他の変色温度調整剤を使用し、かつ広いヒステリシス幅を備えた可逆感温変色性組成物およびそのマイクロカプセルまでは知られていなかった。
このような事情に鑑みて、本発明は新たな変色温度調整剤を採用して、広いヒステリシス幅を備えた感温変色性組成物及びそのマイクロカプセルを得ることを課題とした。 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. .
For this reason, the 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.
ロイコ染料、顕色性物質、変色温度調整剤を含有する感温変色性組成物において、変色温度調整剤が下記化合物ａ～ｅのいずれか１種以上の化合物である組成物。
１．化合物ａ
化合物ｂ
化合物ｃ
化合物ｄ
化合物ｅ
式中ＲはそれぞれＣ４～２２の脂肪族炭化水素基を表す。
２．１記載の組成物を内包するマイクロカプセル。 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. Compound a
Compound b
Compound c
Compound d
Compound e
In the formula, each R represents a C4-22 aliphatic hydrocarbon group.
A microcapsule containing the composition according to 2.1.
１．化合物ａ
２．１記載の組成物を内包するマイクロカプセル。 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. Compound a
A microcapsule containing the composition according to 2.1.
本発明によれば、新規の変色温度調整剤を使用してヒステリシス幅が広い感温変色性組成物を得ることができる。
According to the present invention, a temperature-sensitive color-changing composition having a wide hysteresis width can be obtained using a novel color-change temperature adjusting agent.
本発明はヒステリシス幅が広い感温変色性組成物を得るために上記の特定の組成としたものであり、その組成に関しては以下に述べる。
また、本発明の感温変色性組成物及びそのマイクロカプセルは、ポリオレフィン等の樹脂成形体、印刷インキ、インキ、塗料、包装材料、繊維、記録材料等に可逆的な感温変色性を付与するために用いることが出来る。あるいは、本発明の感温変色性組成物は、筆記具およびクレヨン等の描画材の着色剤として用いてもよい。その場合、その着色剤による筆跡や塗りつぶし箇所を感温変色性とすることができる。 The present invention has the above-mentioned specific composition in order to obtain a temperature-sensitive color-changing composition having a wide hysteresis width, and the composition will be described below.
Further, the 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. Can be used for Alternatively, 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.
また、本発明の感温変色性組成物及びそのマイクロカプセルは、ポリオレフィン等の樹脂成形体、印刷インキ、インキ、塗料、包装材料、繊維、記録材料等に可逆的な感温変色性を付与するために用いることが出来る。あるいは、本発明の感温変色性組成物は、筆記具およびクレヨン等の描画材の着色剤として用いてもよい。その場合、その着色剤による筆跡や塗りつぶし箇所を感温変色性とすることができる。 The present invention has the above-mentioned specific composition in order to obtain a temperature-sensitive color-changing composition having a wide hysteresis width, and the composition will be described below.
Further, the 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. Can be used for Alternatively, 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.
本発明の感温変色性組成物は、マイクロカプセルに内包された形態で提供されてよい。マイクロカプセル化された場合も、上記の物品に感温変色性を付与することができる。特に、マイクロカプセル化された感温変色性組成物は、水性エマルジョンインキ、溶剤揮発性乾燥型インキ、二液硬化型エポキシ樹脂インキ、捺染糊および紫外線硬化型インキに感温変色性を付与するのに好ましく用いられる。
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. In particular, 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.
ロイコ染料
ロイコ染料（発色剤）としては、電子受容性化合物（顕色性物質）と反応して呈色するものであれば限定されず、公知又は市販のものを使用することができる。例えば、下記の化合物を好適に用いることができる。これらは１種又は２種以上で用いることができる。 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. For example, the following compounds can be preferably used. These can be used alone or in combination of two or more.
ロイコ染料（発色剤）としては、電子受容性化合物（顕色性物質）と反応して呈色するものであれば限定されず、公知又は市販のものを使用することができる。例えば、下記の化合物を好適に用いることができる。これらは１種又は２種以上で用いることができる。 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. For example, the following compounds can be preferably used. These can be used alone or in combination of two or more.
（ａ）フルオラン類…２’－[（２－クロロフェニル）アミノ]－６’－（ジブチルアミノ）－スピロ[イソベンゾフラン－１（３Ｈ），９’－（９Ｈ）キサンテン]－３－オン、３－ジエチルアミノ－６－メチル－７－クロロフルオラン、３－ジメチルアミノベンゾ（ａ）－フルオラン、３－アミノ－５－メチルフルオラン、２－メチル－３－アミノ－６，７－ジメチルフルオラン、２－ブロモ－６－シクロヘキシルアミノフルオラン、６’－（エチル（４－メチルフェニル）アミノ－２’－（Ｎ－メチルフェニルアミノ）－スピロ（イソベンゾフラン１（３Ｈ），９’－（９Ｈ）キサンテン）－３－オン、３，６－ジフェニルアミノフルオラン等；
（ｂ）フルオレン類…３，６－ビス（ジエチルアミノ）フルオレンスピロ（９，３’）－４’－アザフタリド、３，６－ビス（ジエチルアミノ）フルオレンスピロ（９，３’）－４’，７’－ジアザフタリド等；
（ｃ）ジフェニルメタンフタリド類…３，３－ビス－（ｐ－エトキシ－４－ジメチルアミノフェニル）フタリド等；
（ｄ）ジフェニルメタンアザフタリド類…３，３－ビス－（１－エトキシ－４－ジエチルアミノフェニル）－４－アザフタリド等；
（ｆ）インドリルフタリド類…３，３－ビス（ｎ－ブチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド等；
（ｇ）フェニルインドリルフタリド類…３－（１－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド等；
（ｈ）フェニルインドリルアザフタリド類…３－（２－エトキシ－４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド、３－［２－エトキシ－４－（Ｎ－エチルアニリノ）フェニル］－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド等；
（ｉ）スチリルキノリン類…２－（３－メトキシ－４－ドデコキシスチリル）キノリン等；
（ｊ）ピリジン類…２，６－ジフェニル－４－（６－ジメチルアミノフェニル）ピリジン、２，６－ジエトキシ－４－（４－ジエチルアミノフェニル）ピリジン等；
（ｋ）キナゾリン類…２－（４－Ｎ－メチルアニリノフェニル）－１－フェノキシキナゾリン、２－（４－ジメチルアミノフェニル）－４－（１－メトキシフェニルオキシ）キナゾリン等；
（ｌ）ビスキナゾリン類…４，４’－（エチレンジオキシ）－ビス［２－（１－ジエチルアミノフェニル）キナゾリン］、４，４’－（エチレンジオキシ）－ビス［２－（１－ジ－ｎ－ブチルアミノフェニル）キナゾリン］等；
（ｍ）エチレノフタリド類…３，３－ビス［１，１－ビス－（ｐ－ジメチルアミノフェニル）エチレノ－３］フタリド等；
（ｎ）エチレノアザフタリド類…３，３－ビス［１，１－ビス－（ｐ－ジメチルアミノフェニル）エチレノ－２］－４－アザフタリド、３，３－ビス［１，１－ビス－（ｐ－ジメチルアミノフェニル）エチレノ－２］－４，７－ジアザフタリド等；
（ｏ）トリフェニルメタンフタリド類…クリスタルバイオレットラクトン、マラカイトグリーンラクトン等；
（ｐ）ポリアリールカルビノール類…ミヒラーヒドロール、クリスタルバイオレットカルビノール、マラカイトグリーンカルビノール等；
（ｑ）ロイコオーラミン類…Ｎ－（２，３－ジクロロフェニル）ロイコオーラミン、Ｎ－ベンゾイルオーラミン、Ｎ－アセチルオーラミン等；
（ｒ）ローダミンラクタム類…ローダミンβラクタム等；
（ｓ）インドリン類…２－（フェニルイミノエチリデン）－３，３－ジメチルインドリン等；
（ｔ）スピロピラン類…Ｎ－３，３－トリメチルインドリノベンゾスピロピラン、８－メトキシ－Ｎ－３，３－トリメチルインドリノベンゾスピロピラン等；
また、本発明では、これらのほか、ジアザローダミンラクトン類、キサンテン類等も使用することができる。 (A) Fluoranes 2 ′-[(2-chlorophenyl) amino] -6 ′-(dibutylamino) -spiro [isobenzofuran-1 (3H), 9 ′-(9H) xanthen] -3-one, 3 -Diethylamino-6-methyl-7-chlorofluorane, 3-dimethylaminobenzo (a) -fluorane, 3-amino-5-methylfluorane, 2-methyl-3-amino-6,7-dimethylfluorane, 2-Bromo-6-cyclohexylaminofluorane, 6 '-(ethyl (4-methylphenyl) amino-2'-(N-methylphenylamino) -spiro (isobenzofuran 1 (3H), 9 '-(9H) Xanthene) -3-one, 3,6-diphenylaminofluorane, etc .;
(B) Fluorenes: 3,6-bis (diethylamino) fluorene spiro (9,3 ′)-4′-azaphthalide, 3,6-bis (diethylamino) fluorene spiro (9,3 ′)-4 ′, 7 ′ -Diazaphthalide etc .;
(C) Diphenylmethanephthalides: 3,3-bis- (p-ethoxy-4-dimethylaminophenyl) phthalide and the like;
(D) Diphenylmethane azaphthalides ... 3,3-bis- (1-ethoxy-4-diethylaminophenyl) -4-azaphthalide and the like;
(F) Indolylphthalides: 3,3-bis (n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide etc;
(G) Phenylindolylphthalides: 3- (1-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide and the like;
(H) Phenylindolyl azaphthalides 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- [2- Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide and the like;
(I) styrylquinolines: 2- (3-methoxy-4-dodecoxystyryl) quinoline and the like;
(J) Pyridines: 2,6-diphenyl-4- (6-dimethylaminophenyl) pyridine, 2,6-diethoxy-4- (4-diethylaminophenyl) pyridine and the like;
(K) quinazolines: 2- (4-N-methylanilinophenyl) -1-phenoxyquinazoline, 2- (4-dimethylaminophenyl) -4- (1-methoxyphenyloxy) quinazoline and the like;
(L) Biskinazolines: 4,4 ′-(ethylenedioxy) -bis [2- (1-diethylaminophenyl) quinazoline], 4,4 ′-(ethylenedioxy) -bis [2- (1-di -N-butylaminophenyl) quinazoline] and the like;
(M) Ethylenophthalides: 3,3-bis [1,1-bis- (p-dimethylaminophenyl) ethyleno-3] phthalide and the like;
(N) Ethylene azaphthalides: 3,3-bis [1,1-bis- (p-dimethylaminophenyl) ethyleno-2] -4-azaphthalide, 3,3-bis [1,1-bis- (P-dimethylaminophenyl) ethyleno-2] -4,7-diazaphthalide and the like;
(O) Triphenylmethanephthalides: crystal violet lactone, malachite green lactone, etc .;
(P) Polyaryl carbinols: Michler hydrol, crystal violet carbinol, malachite green carbinol, etc .;
(Q) leucooramines: N- (2,3-dichlorophenyl) leucooramine, N-benzoyloramine, N-acetyloramine, etc .;
(R) Rhodamine lactams: Rhodamine β-lactam, etc .;
(S) Indolines: 2- (phenyliminoethylidene) -3,3-dimethylindoline and the like;
(T) Spiropyrans: N-3,3-trimethylindolinobenzospiropyran, 8-methoxy-N-3,3-trimethylindolinobenzospiropyran, etc .;
In addition to these, diazarhodamine lactones, xanthenes and the like can also be used in the present invention.
（ｂ）フルオレン類…３，６－ビス（ジエチルアミノ）フルオレンスピロ（９，３’）－４’－アザフタリド、３，６－ビス（ジエチルアミノ）フルオレンスピロ（９，３’）－４’，７’－ジアザフタリド等；
（ｃ）ジフェニルメタンフタリド類…３，３－ビス－（ｐ－エトキシ－４－ジメチルアミノフェニル）フタリド等；
（ｄ）ジフェニルメタンアザフタリド類…３，３－ビス－（１－エトキシ－４－ジエチルアミノフェニル）－４－アザフタリド等；
（ｆ）インドリルフタリド類…３，３－ビス（ｎ－ブチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド等；
（ｇ）フェニルインドリルフタリド類…３－（１－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド等；
（ｈ）フェニルインドリルアザフタリド類…３－（２－エトキシ－４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド、３－［２－エトキシ－４－（Ｎ－エチルアニリノ）フェニル］－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド等；
（ｉ）スチリルキノリン類…２－（３－メトキシ－４－ドデコキシスチリル）キノリン等；
（ｊ）ピリジン類…２，６－ジフェニル－４－（６－ジメチルアミノフェニル）ピリジン、２，６－ジエトキシ－４－（４－ジエチルアミノフェニル）ピリジン等；
（ｋ）キナゾリン類…２－（４－Ｎ－メチルアニリノフェニル）－１－フェノキシキナゾリン、２－（４－ジメチルアミノフェニル）－４－（１－メトキシフェニルオキシ）キナゾリン等；
（ｌ）ビスキナゾリン類…４，４’－（エチレンジオキシ）－ビス［２－（１－ジエチルアミノフェニル）キナゾリン］、４，４’－（エチレンジオキシ）－ビス［２－（１－ジ－ｎ－ブチルアミノフェニル）キナゾリン］等；
（ｍ）エチレノフタリド類…３，３－ビス［１，１－ビス－（ｐ－ジメチルアミノフェニル）エチレノ－３］フタリド等；
（ｎ）エチレノアザフタリド類…３，３－ビス［１，１－ビス－（ｐ－ジメチルアミノフェニル）エチレノ－２］－４－アザフタリド、３，３－ビス［１，１－ビス－（ｐ－ジメチルアミノフェニル）エチレノ－２］－４，７－ジアザフタリド等；
（ｏ）トリフェニルメタンフタリド類…クリスタルバイオレットラクトン、マラカイトグリーンラクトン等；
（ｐ）ポリアリールカルビノール類…ミヒラーヒドロール、クリスタルバイオレットカルビノール、マラカイトグリーンカルビノール等；
（ｑ）ロイコオーラミン類…Ｎ－（２，３－ジクロロフェニル）ロイコオーラミン、Ｎ－ベンゾイルオーラミン、Ｎ－アセチルオーラミン等；
（ｒ）ローダミンラクタム類…ローダミンβラクタム等；
（ｓ）インドリン類…２－（フェニルイミノエチリデン）－３，３－ジメチルインドリン等；
（ｔ）スピロピラン類…Ｎ－３，３－トリメチルインドリノベンゾスピロピラン、８－メトキシ－Ｎ－３，３－トリメチルインドリノベンゾスピロピラン等；
また、本発明では、これらのほか、ジアザローダミンラクトン類、キサンテン類等も使用することができる。 (A) Fluoranes 2 ′-[(2-chlorophenyl) amino] -6 ′-(dibutylamino) -spiro [isobenzofuran-1 (3H), 9 ′-(9H) xanthen] -3-one, 3 -Diethylamino-6-methyl-7-chlorofluorane, 3-dimethylaminobenzo (a) -fluorane, 3-amino-5-methylfluorane, 2-methyl-3-amino-6,7-dimethylfluorane, 2-Bromo-6-cyclohexylaminofluorane, 6 '-(ethyl (4-methylphenyl) amino-2'-(N-methylphenylamino) -spiro (isobenzofuran 1 (3H), 9 '-(9H) Xanthene) -3-one, 3,6-diphenylaminofluorane, etc .;
(B) Fluorenes: 3,6-bis (diethylamino) fluorene spiro (9,3 ′)-4′-azaphthalide, 3,6-bis (diethylamino) fluorene spiro (9,3 ′)-4 ′, 7 ′ -Diazaphthalide etc .;
(C) Diphenylmethanephthalides: 3,3-bis- (p-ethoxy-4-dimethylaminophenyl) phthalide and the like;
(D) Diphenylmethane azaphthalides ... 3,3-bis- (1-ethoxy-4-diethylaminophenyl) -4-azaphthalide and the like;
(F) Indolylphthalides: 3,3-bis (n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide etc;
(G) Phenylindolylphthalides: 3- (1-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide and the like;
(H) Phenylindolyl azaphthalides 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- [2- Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide and the like;
(I) styrylquinolines: 2- (3-methoxy-4-dodecoxystyryl) quinoline and the like;
(J) Pyridines: 2,6-diphenyl-4- (6-dimethylaminophenyl) pyridine, 2,6-diethoxy-4- (4-diethylaminophenyl) pyridine and the like;
(K) quinazolines: 2- (4-N-methylanilinophenyl) -1-phenoxyquinazoline, 2- (4-dimethylaminophenyl) -4- (1-methoxyphenyloxy) quinazoline and the like;
(L) Biskinazolines: 4,4 ′-(ethylenedioxy) -bis [2- (1-diethylaminophenyl) quinazoline], 4,4 ′-(ethylenedioxy) -bis [2- (1-di -N-butylaminophenyl) quinazoline] and the like;
(M) Ethylenophthalides: 3,3-bis [1,1-bis- (p-dimethylaminophenyl) ethyleno-3] phthalide and the like;
(N) Ethylene azaphthalides: 3,3-bis [1,1-bis- (p-dimethylaminophenyl) ethyleno-2] -4-azaphthalide, 3,3-bis [1,1-bis- (P-dimethylaminophenyl) ethyleno-2] -4,7-diazaphthalide and the like;
(O) Triphenylmethanephthalides: crystal violet lactone, malachite green lactone, etc .;
(P) Polyaryl carbinols: Michler hydrol, crystal violet carbinol, malachite green carbinol, etc .;
(Q) leucooramines: N- (2,3-dichlorophenyl) leucooramine, N-benzoyloramine, N-acetyloramine, etc .;
(R) Rhodamine lactams: Rhodamine β-lactam, etc .;
(S) Indolines: 2- (phenyliminoethylidene) -3,3-dimethylindoline and the like;
(T) Spiropyrans: N-3,3-trimethylindolinobenzospiropyran, 8-methoxy-N-3,3-trimethylindolinobenzospiropyran, etc .;
In addition to these, diazarhodamine lactones, xanthenes and the like can also be used in the present invention.
本発明では、これらロイコ染料のうちフルオラン類の少なくとも１種を好適に用いることができる。特に、２’－[（２－クロロフェニル）アミノ]－６’－（ジブチルアミノ）－スピロ[イソベンゾフラン－１（３Ｈ），９’－（９Ｈ）キサンテン]－３－オン及び３，６－ジフェニルアミノフルオランの少なくとも１種がより好ましい。
In the present invention, among these leuco dyes, at least one of fluorans can be suitably used. In particular, 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.
ロイコ染料の含有量は、その化合物の種類等に応じて適宜設定できるが、一般的には本発明の感温変色性組成物中０．１～５０重量％程度、特に０．８～１５重量％とすることが望ましい。前記含有量が０．１重量％未満の場合は発色濃度が低くなるおそれがある。また、上記含有量が５０重量％を超える場合は地発色が大きくなるおそれがある。
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.
顕色性物質
顕色性物質としては、限定的でなく、公知又は市販のものを適宜使用することができる。例えば、下記の化合物を好適に用いることができる。これらは１種又は２種以上で用いることができる。 Developer The developer is not limited, and a known or commercially available one can be used as appropriate. For example, the following compounds can be preferably used. These can be used alone or in combination of two or more.
顕色性物質としては、限定的でなく、公知又は市販のものを適宜使用することができる。例えば、下記の化合物を好適に用いることができる。これらは１種又は２種以上で用いることができる。 Developer The developer is not limited, and a known or commercially available one can be used as appropriate. For example, the following compounds can be preferably used. These can be used alone or in combination of two or more.
（ａ）フェノール類…ビスフェノールＡ又はその誘導体、ビスフェノールＳ又はその誘導体、ｐ－フェニルフェノール、ドデシルフェノール、ｏ－ブロモフェノール、ｐ－オキシ安息香酸エチル、没食子酸メチル、フェノール樹脂等；
（ｂ）フェノール類の金属塩…フェノール類のＮａ、Ｋ、Ｌｉ、Ｃａ、Ｚｎ、Ａｌ、Ｍｇ、Ｎｉ、Ｃｏ、Ｓｎ、Ｃｕ、Ｆｅ、Ｔｉ、Ｐｂ、Ｍｏ等の金属塩等；
（ｃ）芳香族カルボン酸及び炭素数２～５の脂肪族カルボン酸類…フタル酸、安息香酸、酢酸、プロピオン酸等；
（ｄ）カルボン酸類の金属塩…オレイン酸ナトリウム、サリチル酸亜鉛、安息香酸ニッケル等；
（ｅ）酸性リン酸エステル類…ブチルアシッドフォスフェート、２－エチルヘキシル－アシッドフォスフェート、ドデシルアシッドフォスファイト等；
（ｆ）酸性リン酸エステル類の金属塩…酸性リン酸エステル類のＮａ、Ｋ、Ｌｉ、Ｃａ、Ｚｎ、Ａｌ、Ｍｇ、Ｎｉ、Ｃｏ、Ｓｎ、Ｆｅ、Ｔｉ、Ｐｂ、Ｍｏ等の金属塩等；
（ｇ）トリアゾール化合物…１，２，３－トリアゾール、１，２，３－ベンゾトリアゾール等；
（ｈ）チオ尿素及びその誘導体…ジフェニルチオ尿素、ジ－ｏ－トルイル尿素等；
（ｉ）ハロヒドリン類…２，２，２－トリクロロエタノール、１，１，１－トリブロモ－２－メチル－２－プロパノール、Ｎ－３－ピリジル－Ｎ’－（１－ヒドロキシ－２，２，２－トリクロロエチル）尿素等；
（ｊ）ベンゾチアゾール類…２－メルカプトベンゼンチアゾール、２－（４’－モルホリノジチオ）ベンゾチアゾール、Ｎ－tert－ブチル－２－ベンゾチアゾリルスルフェンアミド、２－メルカプトベンゾチアゾールのＺｎ塩等；
本発明では、これら電子受容性化合物のうちフェノール類及びその金属塩の少なくとも１種を好適に用いることができる。特に、１）ビスフェノールＡ及びその誘導体ならびに２）ビスフェノールＳ及びその誘導体から選ばれる少なくとも１種がより好ましく、最も好ましくは２，２－ビス(４－ヒドロキシフェニル)ヘキサフルオロプロパン、２，２－ビス（４－ヒドロキシフェニル）プロパン及び１，１－ビス（４’－ヒドロキシフェニル）－１－フェニルエタンの少なくとも１種が挙げられる。 (A) Phenols: bisphenol A or derivatives thereof, bisphenol S or derivatives thereof, p-phenylphenol, dodecylphenol, o-bromophenol, ethyl p-oxybenzoate, methyl gallate, phenol resin, etc .;
(B) 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 .;
(D) Metal salts of carboxylic acids: sodium oleate, zinc salicylate, nickel benzoate, etc .;
(E) Acid phosphate esters: butyl acid phosphate, 2-ethylhexyl acid phosphate, dodecyl acid phosphate, etc .;
(F) Metal salts of acidic phosphate esters: Metal salts of acidic phosphate esters such as Na, K, Li, Ca, Zn, Al, Mg, Ni, Co, Sn, Fe, Ti, Pb, and Mo ;
(G) Triazole compound: 1,2,3-triazole, 1,2,3-benzotriazole, etc .;
(H) Thiourea and derivatives thereof: diphenylthiourea, di-o-toluylurea, etc .;
(I) Halohydrins: 2,2,2-trichloroethanol, 1,1,1-tribromo-2-methyl-2-propanol, N-3-pyridyl-N ′-(1-hydroxy-2,2,2 -Trichloroethyl) urea and the like;
(J) benzothiazoles: 2-mercaptobenzenethiazole, 2- (4′-morpholinodithio) benzothiazole, N-tert-butyl-2-benzothiazolylsulfenamide, Zn salt of 2-mercaptobenzothiazole, and the like;
In the present invention, among these electron-accepting compounds, at least one of phenols and metal salts thereof can be suitably used. In particular, 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.
（ｂ）フェノール類の金属塩…フェノール類のＮａ、Ｋ、Ｌｉ、Ｃａ、Ｚｎ、Ａｌ、Ｍｇ、Ｎｉ、Ｃｏ、Ｓｎ、Ｃｕ、Ｆｅ、Ｔｉ、Ｐｂ、Ｍｏ等の金属塩等；
（ｃ）芳香族カルボン酸及び炭素数２～５の脂肪族カルボン酸類…フタル酸、安息香酸、酢酸、プロピオン酸等；
（ｄ）カルボン酸類の金属塩…オレイン酸ナトリウム、サリチル酸亜鉛、安息香酸ニッケル等；
（ｅ）酸性リン酸エステル類…ブチルアシッドフォスフェート、２－エチルヘキシル－アシッドフォスフェート、ドデシルアシッドフォスファイト等；
（ｆ）酸性リン酸エステル類の金属塩…酸性リン酸エステル類のＮａ、Ｋ、Ｌｉ、Ｃａ、Ｚｎ、Ａｌ、Ｍｇ、Ｎｉ、Ｃｏ、Ｓｎ、Ｆｅ、Ｔｉ、Ｐｂ、Ｍｏ等の金属塩等；
（ｇ）トリアゾール化合物…１，２，３－トリアゾール、１，２，３－ベンゾトリアゾール等；
（ｈ）チオ尿素及びその誘導体…ジフェニルチオ尿素、ジ－ｏ－トルイル尿素等；
（ｉ）ハロヒドリン類…２，２，２－トリクロロエタノール、１，１，１－トリブロモ－２－メチル－２－プロパノール、Ｎ－３－ピリジル－Ｎ’－（１－ヒドロキシ－２，２，２－トリクロロエチル）尿素等；
（ｊ）ベンゾチアゾール類…２－メルカプトベンゼンチアゾール、２－（４’－モルホリノジチオ）ベンゾチアゾール、Ｎ－tert－ブチル－２－ベンゾチアゾリルスルフェンアミド、２－メルカプトベンゾチアゾールのＺｎ塩等；
本発明では、これら電子受容性化合物のうちフェノール類及びその金属塩の少なくとも１種を好適に用いることができる。特に、１）ビスフェノールＡ及びその誘導体ならびに２）ビスフェノールＳ及びその誘導体から選ばれる少なくとも１種がより好ましく、最も好ましくは２，２－ビス(４－ヒドロキシフェニル)ヘキサフルオロプロパン、２，２－ビス（４－ヒドロキシフェニル）プロパン及び１，１－ビス（４’－ヒドロキシフェニル）－１－フェニルエタンの少なくとも１種が挙げられる。 (A) Phenols: bisphenol A or derivatives thereof, bisphenol S or derivatives thereof, p-phenylphenol, dodecylphenol, o-bromophenol, ethyl p-oxybenzoate, methyl gallate, phenol resin, etc .;
(B) 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 .;
(D) Metal salts of carboxylic acids: sodium oleate, zinc salicylate, nickel benzoate, etc .;
(E) Acid phosphate esters: butyl acid phosphate, 2-ethylhexyl acid phosphate, dodecyl acid phosphate, etc .;
(F) Metal salts of acidic phosphate esters: Metal salts of acidic phosphate esters such as Na, K, Li, Ca, Zn, Al, Mg, Ni, Co, Sn, Fe, Ti, Pb, and Mo ;
(G) Triazole compound: 1,2,3-triazole, 1,2,3-benzotriazole, etc .;
(H) Thiourea and derivatives thereof: diphenylthiourea, di-o-toluylurea, etc .;
(I) Halohydrins: 2,2,2-trichloroethanol, 1,1,1-tribromo-2-methyl-2-propanol, N-3-pyridyl-N ′-(1-hydroxy-2,2,2 -Trichloroethyl) urea and the like;
(J) benzothiazoles: 2-mercaptobenzenethiazole, 2- (4′-morpholinodithio) benzothiazole, N-tert-butyl-2-benzothiazolylsulfenamide, Zn salt of 2-mercaptobenzothiazole, and the like;
In the present invention, among these electron-accepting compounds, at least one of phenols and metal salts thereof can be suitably used. In particular, 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.
顕色性物質の含有量は、その化合物の種類等に応じて適宜設定できるが、一般的には本発明の感温変色性組成物中０．０５～９８重量％程度、特に０．５～７７重量％とすることが望ましい。前記含有量が０．０５重量％未満の場合は発色濃度が低くなるおそれがある。また、上記含有量が９８重量％を超える場合は地発色が大きくなるおそれがある。
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. When the content is less than 0.05% by weight, the color density may be lowered. Moreover, when the said content exceeds 98 weight%, there exists a possibility that background coloring may become large.
また、本発明では、ロイコ染料との関係では、ロイコ染料１重量部に対して顕色性物質０．１～１００重量部、特に０．５～２０重量部とすることが好ましい。
In the present invention, 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.
変色温度調整剤（減感剤）
本発明にて使用できる変色温度調整剤としては、下記の化合物ａ～ｅの１種以上である。
化合物ａ
化合物ｂ
化合物ｃ
化合物ｄ
化合物ｅ
式中ＲはそれぞれＣ４～２２の脂肪族炭化水素基を表す。
式中Ｒは共にＣ４～２２の脂肪族炭化水素基を表し、直鎖の脂肪族炭化水素基でもよく分岐した脂肪族炭化水素基でも良い。さらに環状の脂肪族炭化水素基を有しても良いし、芳香環を有しても良い。中でも変色温度の調整が容易であることを考慮すると、Ｃ７～Ｃ１３の直鎖又は分岐した脂肪族炭化水素基であることが望ましい。
このような変色温度調整剤の含有量（合計量）は、その化合物の種類等に応じて適宜設定できるが、一般的には本発明の感温変色性組成物中１～９９重量％程度、特に１９～９９重量％、さらには６０～９５重量％とすることが望ましい。前記含有量が１重量％未満の場合は地発色が大きくなるおそれがある。また、上記含有量が９９重量％を超える場合は発色濃度が低くなるおそれがある。 Discoloration temperature regulator (desensitizer)
The discoloration temperature adjusting agent that can be used in the present invention is one or more of the following compounds a to e.
Compound a
Compound b
Compound c
Compound d
Compound e
In the formula, each R represents a C4-22 aliphatic hydrocarbon group.
In the formula, 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.
本発明にて使用できる変色温度調整剤としては、下記の化合物ａ～ｅの１種以上である。
化合物ａ
式中Ｒは共にＣ４～２２の脂肪族炭化水素基を表し、直鎖の脂肪族炭化水素基でもよく分岐した脂肪族炭化水素基でも良い。さらに環状の脂肪族炭化水素基を有しても良いし、芳香環を有しても良い。中でも変色温度の調整が容易であることを考慮すると、Ｃ７～Ｃ１３の直鎖又は分岐した脂肪族炭化水素基であることが望ましい。
このような変色温度調整剤の含有量（合計量）は、その化合物の種類等に応じて適宜設定できるが、一般的には本発明の感温変色性組成物中１～９９重量％程度、特に１９～９９重量％、さらには６０～９５重量％とすることが望ましい。前記含有量が１重量％未満の場合は地発色が大きくなるおそれがある。また、上記含有量が９９重量％を超える場合は発色濃度が低くなるおそれがある。 Discoloration temperature regulator (desensitizer)
The discoloration temperature adjusting agent that can be used in the present invention is one or more of the following compounds a to e.
Compound a
In the formula, 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.
その他の成分
本発明の感温変色性組成物では、必要に応じて、紫外線吸収剤、赤外線吸収剤、酸化防止剤、非感温変色性顔料、非感温変色性染料、蛍光増白剤、界面活性剤、消泡剤、レベリング剤、溶剤、増粘剤等の公知の添加剤を組成物中に配合しても良い。 Other components In the temperature-sensitive color-changing composition of the present invention, 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 | blend well-known additives, such as surfactant, an antifoamer, a leveling agent, a solvent, and a thickener, in a composition.
本発明の感温変色性組成物では、必要に応じて、紫外線吸収剤、赤外線吸収剤、酸化防止剤、非感温変色性顔料、非感温変色性染料、蛍光増白剤、界面活性剤、消泡剤、レベリング剤、溶剤、増粘剤等の公知の添加剤を組成物中に配合しても良い。 Other components In the temperature-sensitive color-changing composition of the present invention, 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 | blend well-known additives, such as surfactant, an antifoamer, a leveling agent, a solvent, and a thickener, in a composition.
上記のうち、紫外線吸収剤としては、太陽光等に含まれる紫外線を効果的に吸収して、発色剤の光反応による励起状態によって生ずる光劣化を防止する化合物であればよい。紫外線吸収剤としては、例えば、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系、トリアジン系、サリチル酸系、シュウ酸アリニド系、マロン酸エステル系、安息香酸系、ケイ皮酸系、ジベンゾイルメタン系等の化合物が挙げられる。この中でも、ベンゾトリアゾール系紫外線吸収剤が好ましい。紫外線吸収剤の含有量（合計量）は、その化合物の種類等に応じて適宜設定できるが、一般的には本発明の感温変色性組成物中０～９６重量％程度、特に０～６１重量％とすることが望ましい。
の う ち Among the above, 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. Examples of the ultraviolet absorber include benzophenone, benzotriazole, cyanoacrylate, triazine, salicylic acid, alinide oxalate, malonic ester, benzoic acid, cinnamic acid, and dibenzoylmethane. Compounds. Among these, 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%.
（１）感温変色性組成物の製造方法
本発明の感温変色性組成物は、これらの成分を攪拌機、ミキサー、ホモジナイザー等の公知の混合機に投入し、均一に混合することによって調製することができる。この場合、加熱しながら混合することが好ましい。加熱温度は限定的ではないが、通常は１２０～１８０℃程度とすれば良い。 (1) Manufacturing method of temperature-sensitive color-changing composition 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.
本発明の感温変色性組成物は、これらの成分を攪拌機、ミキサー、ホモジナイザー等の公知の混合機に投入し、均一に混合することによって調製することができる。この場合、加熱しながら混合することが好ましい。加熱温度は限定的ではないが、通常は１２０～１８０℃程度とすれば良い。 (1) Manufacturing method of temperature-sensitive color-changing composition 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.
（２）感温変色性マイクロカプセル
本発明は、前記の感温変色性組成物をマイクロカプセルに内包してなる感温変色性マイクロカプセルを包含する。内容物として本発明の感温変色性組成物を用いるほかは、公知のマイクロカプセルと同様の構造を採用することができる。例えば、感温変色性組成物を含む内容物を壁膜により内包してなるマイクロカプセルが挙げられる。 (2) Thermochromic microcapsules The present invention includes 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. For example, the microcapsule which encloses the content containing a temperature-sensitive color-change composition with a wall film is mentioned.
本発明は、前記の感温変色性組成物をマイクロカプセルに内包してなる感温変色性マイクロカプセルを包含する。内容物として本発明の感温変色性組成物を用いるほかは、公知のマイクロカプセルと同様の構造を採用することができる。例えば、感温変色性組成物を含む内容物を壁膜により内包してなるマイクロカプセルが挙げられる。 (2) Thermochromic microcapsules The present invention includes 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. For example, the microcapsule which encloses the content containing a temperature-sensitive color-change composition with a wall film is mentioned.
内容物としては、感温変色性組成物のほか、必要に応じて溶剤（溶解助剤）、乳化剤等が含まれていて良い。
The soot contents may contain a solvent (dissolution aid), an emulsifier, and the like, if necessary, in addition to the thermochromic composition.
感温変色性組成物の含有量は限定的ではないが、一般的にはマイクロカプセルを１００重量％とすると６～９８重量％程度、特に５０～９５重量％とすることが望ましい。
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.
溶剤としては、感温変色性組成物と壁膜原料とを均一に溶解させることができ、感温変色性能を阻害しないものである限り、公知の溶剤から適宜選択することができる。特に、後工程で取り除けるものが望ましい。例えば、エステル系溶剤（但し、前記化合物ａ及びｄを除く。）、ケトン系溶剤、エーテル系溶剤、グリコールエーテル系溶剤、炭化水素系溶剤、芳香族系溶剤、含窒素系溶剤、シリコン系溶剤、含ハロゲン系溶剤等が使用できる。これらは１種又は２種以上で用いることができる。
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. For example, ester solvents (excluding the compounds a and d), ketone solvents, ether solvents, glycol ether solvents, hydrocarbon solvents, aromatic solvents, nitrogen-containing solvents, silicon solvents, Halogen-containing solvents can be used. These can be used alone or in combination of two or more.
乳化剤は、内容物を水中で乳化する際に油滴表面に吸着して安定化させる両親媒性物質を好適に用いることができる。これらは公知の乳化剤から採用することができる。例えば、水溶性天然高分子、水溶性合成高分子、界面活性剤、無機微粒子等を挙げることができる。これらは１種又は２種以上で用いることができる。乳化剤は、壁膜を構成する樹脂成分の種類等に応じて適宜決定することができる。例えば、樹脂成分がエポキシ樹脂である場合には、乳化剤としてアラビアゴム等の多糖類のほか、ゼラチン、カゼイン等のタンパク質も好適に使用することができる。また例えば、樹脂成分としてメラミンホルマリン樹脂を用いる場合には、乳化剤としてエチレン無水マレイン酸共重合体等を好適に用いることができる。さらに、樹脂成分としてウレタン（イソシアネート）を用いる場合には、ゼラチン、ポリビニルアルコール等を用いることができる。
As the 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. For example, 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. For example, when 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. For example, when a melamine formalin resin is used as a resin component, an ethylene maleic anhydride copolymer or the like can be suitably used as an emulsifier. Furthermore, when urethane (isocyanate) is used as the resin component, gelatin, polyvinyl alcohol, or the like can be used.
壁膜としては、通常は樹脂系壁膜を好適に採用することができる。樹脂としては、例えば各種の熱可塑性樹脂及び熱硬化性樹脂を使用するこができる。より具体的には、エポキシ樹脂、ポリアミド樹脂、アクリロニトリル樹脂、ポリウレタン樹脂、ポリウレア樹脂、尿素－ホルムアルデヒド系樹脂、メラミン－ホルムアルデヒド系樹脂、ベンゾグアナミン樹脂、ブチル化メラミン樹脂、ブチル化尿素樹脂、尿素－メラミン系樹脂等が挙げられる。これら樹脂成分は１種又は２種以上で使用することができる。マイクロカプセルを製造する際は、これらの原料を用い、これらを高分子化することにより好適にマイクロカプセル化することができる。
In general, a resin-based wall film can be suitably used as the wall film. As 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.
（３）感温変色性マイクロカプセルの製造方法
本発明の感温変色性マイクロカプセルの製造方法としては、内容物として本発明の感温変色性組成物を用いるほかは、公知のマイクロカプセル化に従って実施することができる。マイクロカプセル化の方法として、例えば界面重合法（重縮合、付加重合）、インサイチュー重合法、コアセルベーション法、液中乾燥法、噴霧乾燥法等を挙げることができる。 (3) Method for producing thermochromic microcapsules The method for producing 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. Examples of 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.
本発明の感温変色性マイクロカプセルの製造方法としては、内容物として本発明の感温変色性組成物を用いるほかは、公知のマイクロカプセル化に従って実施することができる。マイクロカプセル化の方法として、例えば界面重合法（重縮合、付加重合）、インサイチュー重合法、コアセルベーション法、液中乾燥法、噴霧乾燥法等を挙げることができる。 (3) Method for producing thermochromic microcapsules The method for producing 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. Examples of 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.
具体的に、本発明のマイクロカプセルの製造方法の一例としては、例えば、１）溶剤の存在下又は不存在下において、壁膜を構成し得る主原料（架橋剤を除く。）を感温変色性組成物と混合又は溶解することにより溶液を調製する第１工程、２）得られた溶液を乳化剤水溶液中に添加し、Ｏ／Ｗエマルションを調製する第２工程、３）架橋剤又はその溶液をＯ／Ｗエマルションに添加する第３工程を含む方法により、好適にマイクロカプセルを製造することができる。以下、各工程について説明する。
Specifically, as an example of the method for producing the microcapsules of the present invention, for example, 1) Temperature-sensitive discoloration of main raw materials (excluding the crosslinking agent) that can constitute the wall film in the presence or absence of a solvent. 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. Hereinafter, each step will be described.
第１工程
第１工程では、溶剤の存在下又は不存在下において、壁膜を構成し得る主原料（架橋剤を除く。）を感温変色性組成物と混合又は溶解することにより溶液を調製する。 First Step In the first step, 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.
第１工程では、溶剤の存在下又は不存在下において、壁膜を構成し得る主原料（架橋剤を除く。）を感温変色性組成物と混合又は溶解することにより溶液を調製する。 First Step In the first step, 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.
感温変色性組成物は、前記で説明したものを用いる。感温変色性組成物の使用量は、通常は乳化剤水溶液１００重量部に対して５～５０重量部、特に１０～４０重量部となるようにすることが好ましい。前記使用量が５重量部未満の場合は、生産性が低下することがある。また、前記使用量が５０重量部を超える場合は、乳化が困難になるおそれがある。
As the wrinkle-sensitive temperature-changing composition, those described above are used. 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. When the amount used is less than 5 parts by weight, productivity may be reduced. Moreover, when the said usage-amount exceeds 50 weight part, there exists a possibility that emulsification may become difficult.
前記主原料及び架橋剤としては、前記（２）で説明した壁膜を構成する成分となるものを使用すれば良い。この場合、特にマイクロカプセル化の方法に応じて適宜設定することがより望ましい。例えば、インサイチュー重合法でマイクロカプセル化する場合において、壁膜をメラミン樹脂、ポリウレア樹脂等とする場合は、主原料としてメラミン、尿素等を用い、架橋剤としてホルマリンを使用すれば良い。インサイチュー重合法でマイクロカプセル化する場合において、壁膜がウレタン樹脂等である場合は、主原料としてイソシアネート化合物を用い、架橋剤としてポリアルコールを使用すれば良い。例えば、界面重合法（重縮合）でマイクロカプセル化する場合において、壁膜がエポキシ樹脂等である場合は、主原料としてエポキシ化合物を用い、架橋剤としてポリアミン化合物を使用すれば良い。界面重合法（重縮合）でマイクロカプセル化する場合において、壁膜がウレタン樹脂、ウレアウレタン樹脂等である場合は、主原料としてイソシアネート化合物を用い、架橋剤としてポリアミン化合物、ポリアルコール、水等を使用すれば良い。界面重合法（重縮合）でマイクロカプセル化する場合において、壁膜がポリアミド樹脂等である場合は、主原料として酸クロライド化合物を用い、架橋剤としてポリアミン化合物を使用すれば良い。界面重合法（付加重合）でマイクロカプセル化する場合において、壁膜がアクリル樹脂等である場合は、主原料としてアクリル化合物を用い、架橋剤としてペルオキシ化合物を使用すれば良い。
As 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. In this case, it is more desirable to set appropriately according to the microencapsulation method. For example, in the case of microencapsulation by an in situ polymerization method, when 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. In the case of microencapsulation by an in situ polymerization method, 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. For example, in the case of microencapsulation by the interfacial polymerization method (polycondensation), when the wall film is an epoxy resin or the like, an epoxy compound may be used as a main raw material and a polyamine compound may be used as a crosslinking agent. In the case of microencapsulation by the interfacial polymerization method (polycondensation), when the wall film is a urethane resin, urea urethane resin, etc., 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. In the case of microencapsulation by the interfacial polymerization method (polycondensation), when the wall film is a polyamide resin or the like, an acid chloride compound may be used as a main raw material and a polyamine compound may be used as a crosslinking agent. In the case of microencapsulation by the interfacial polymerization method (addition polymerization), 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.
主原料及び架橋剤の使用量は特に制限されない。主原料は、乳化剤水溶液１００重量部に対して通常１～５０重量部の範囲内、好ましくは２～１０重量部の範囲内で適宜設定することができる。架橋剤は、乳化剤水溶液１００重量部に対して通常０．５～２５重量部の範囲内、好ましくは１～５重量部の範囲内で適宜設定することができる。主原料又は架橋剤の使用量が少なすぎる場合又は多すぎる場合は、反応が不十分となり、カプセル（壁膜）の強度、耐熱性等が低くなるおそれがある。
使用 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.
第１工程では、必要に応じて溶剤を使用することができる。溶剤としては前記で掲げたものを用いることができる。
溶 剤 In the first step, a solvent can be used as necessary. As the solvent, those listed above can be used.
溶剤の使用量は限定的ではないが、通常は乳化剤水溶液１００重量部に対して０～１００重量部の範囲内、好ましくは０～４０重量部の範囲内で適宜設定することができる。
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.
第２工程
第２工程では、得られた溶液を乳化剤水溶液中に添加し、Ｏ／Ｗエマルションを調製する。 Second Step In the second step, the obtained solution is added to an aqueous emulsifier solution to prepare an O / W emulsion.
第２工程では、得られた溶液を乳化剤水溶液中に添加し、Ｏ／Ｗエマルションを調製する。 Second Step In the second step, the obtained solution is added to an aqueous emulsifier solution to prepare an O / W emulsion.
乳化剤水溶液は、前記の乳化剤を水に溶解して得られる水溶液を使用できる。乳化剤水溶液の濃度は、乳化剤の種類等に応じて適宜設定することができるが、一般に０．１～１５重量％、特に０．５～８重量％とすることが好ましい。前記濃度が０．２重量％を下回る場合は、乳化が困難となるおそれがある。前記濃度が１５重量％を超える場合は、起泡することがある。
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.
本発明では、Ｏ／Ｗエマルションの調製は、攪拌法、膜透過法等の公知の方法に従って実施することができる。この場合のＯ／Ｗエマルションの液滴径は０．１～２０μｍ程度の範囲内で適宜設定すれば良い。
In the present invention, the O / W emulsion can be prepared according to a known method such as a stirring method or a membrane permeation method. In this case, the droplet diameter of the O / W emulsion may be set as appropriate within a range of about 0.1 to 20 μm.
第３工程
第３工程では、架橋剤又はその溶液をＯ／Ｗエマルションに添加する。架橋剤としては、前記で列挙した各架橋剤を用いることができる。架橋剤の溶液は、例えば架橋剤を水に溶解して得られる架橋剤水溶液を好適に用いることができる。この場合の水溶液の濃度は限定されないが、通常は１～１００重量％程度の範囲内で適宜すれば良い。架橋剤の添加方法は特に制限されないが、滴下することにより添加することが好ましい。 Third Step In the third step, a crosslinking agent or a solution thereof is added to the O / W emulsion. As a crosslinking agent, each crosslinking agent enumerated above can be used. As 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.
第３工程では、架橋剤又はその溶液をＯ／Ｗエマルションに添加する。架橋剤としては、前記で列挙した各架橋剤を用いることができる。架橋剤の溶液は、例えば架橋剤を水に溶解して得られる架橋剤水溶液を好適に用いることができる。この場合の水溶液の濃度は限定されないが、通常は１～１００重量％程度の範囲内で適宜すれば良い。架橋剤の添加方法は特に制限されないが、滴下することにより添加することが好ましい。 Third Step In the third step, a crosslinking agent or a solution thereof is added to the O / W emulsion. As a crosslinking agent, each crosslinking agent enumerated above can be used. As 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.
また、特殊な例として、壁膜原料にイソシアネート化合物を用いる場合は、架橋剤を新たに添加しなくても乳化剤水溶液中の水とイソシアネートの反応によって生じるアミン化合物を架橋剤として利用することができる。
As a special example, when an isocyanate compound is 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. .
架橋剤又はその溶液を添加した後、架橋が進行し、架橋が完了すれば、所望のマイクロカプセルをスラリーの形態で得ることができる。その後、必要に応じて、例えばろ過、遠心分離等の公知の固液分離方法に従って、マイクロカプセルを固形分として回収することもできる。また、必要に応じて、マイクロカプセルを洗浄することもできる。
After adding the cross-linking agent or solution thereof, if the cross-linking proceeds and the cross-linking is completed, 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.
実施例
表１に示す各成分を１２０～１８０℃で加熱しながら攪拌機にて均一に混合することによって、各感温変色性組成物を調製した。得られた感温変色性組成物を下記の方法によりマイクロカプセル化した。 Examples Each temperature-sensitive color-changing 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.
表１に示す各成分を１２０～１８０℃で加熱しながら攪拌機にて均一に混合することによって、各感温変色性組成物を調製した。得られた感温変色性組成物を下記の方法によりマイクロカプセル化した。 Examples Each temperature-sensitive color-changing 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.
まず、酢酸エチル１０部とアセトン５部からなる溶解助剤（溶剤）を用いてカプセル壁膜となるトルイレンジイソシアネートのトリメチロールプロパン付加物（樹脂主剤（主原料））３．６部と、表１及び２により得た感温変色性組成物１０部とを均一に混合し、溶解し、溶液を得た。
次いで、３０～６０℃に加温した４％ゼラチン水溶液（乳化剤水溶液）７１．４部中に、中せん断攪拌しながら前記溶液を添加した。次に、高せん断攪拌を行うことにより前記溶液からＯ／Ｗエマルション（液滴の粒径：５μｍ程度）を得た。その後、低せん断攪拌に切り換え、架橋剤水溶液を前記Ｏ／Ｗエマルションに滴下した。６０～９０℃の温度下で３～１２時間反応を行った後、室温まで冷却することにより、マイクロカプセルが分散したスラリーを得た。 First, 3.6 parts of a trimethylolpropane adduct of toluylene diisocyanate (resin main agent (main raw material)) to be a capsule wall film using a dissolution aid (solvent) consisting of 10 parts of ethyl acetate and 5 parts of acetone, 10 parts of the thermochromic composition obtained in 1 and 2 were uniformly mixed and dissolved to obtain a solution.
Next, 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. Next, O / W emulsion (droplet particle size: about 5 μm) was obtained from the solution by performing high shear stirring. Thereafter, the stirring was switched to low shear stirring, and the aqueous crosslinking agent solution was dropped into the O / W emulsion. After reacting at a temperature of 60 to 90 ° C. for 3 to 12 hours, the slurry was cooled to room temperature to obtain a slurry in which microcapsules were dispersed.
次いで、３０～６０℃に加温した４％ゼラチン水溶液（乳化剤水溶液）７１．４部中に、中せん断攪拌しながら前記溶液を添加した。次に、高せん断攪拌を行うことにより前記溶液からＯ／Ｗエマルション（液滴の粒径：５μｍ程度）を得た。その後、低せん断攪拌に切り換え、架橋剤水溶液を前記Ｏ／Ｗエマルションに滴下した。６０～９０℃の温度下で３～１２時間反応を行った後、室温まで冷却することにより、マイクロカプセルが分散したスラリーを得た。 First, 3.6 parts of a trimethylolpropane adduct of toluylene diisocyanate (resin main agent (main raw material)) to be a capsule wall film using a dissolution aid (solvent) consisting of 10 parts of ethyl acetate and 5 parts of acetone, 10 parts of the thermochromic composition obtained in 1 and 2 were uniformly mixed and dissolved to obtain a solution.
Next, 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. Next, O / W emulsion (droplet particle size: about 5 μm) was obtained from the solution by performing high shear stirring. Thereafter, the stirring was switched to low shear stirring, and the aqueous crosslinking agent solution was dropped into the O / W emulsion. After reacting at a temperature of 60 to 90 ° C. for 3 to 12 hours, the slurry was cooled to room temperature to obtain a slurry in which microcapsules were dispersed.
ロイコ染料：２’－[(２－クロロフェニル)アミノ]－６’－(ジブチルアミノ)スピロ[イソベンゾフルオラン－１(３Ｈ),９’－(９Ｈ)キサンテン)]－３－オン
顕色剤（顕色性物質）：２，２－ビス(４－ヒドロキシフェニル)ヘキサフルオロプロパン
変色温度調整剤ａ：４－ヒドロキシメチルビフェニルデカン酸エステル
変色温度調整剤ｂ：安息香酸フェニル－ｎ－デシルエーテル
変色温度調整剤c：４－ヒドロキシベンゾフェノンラウリルエーテル
変色温度調整剤d：４－クロロ－４’－ヒドロキシベンゾフェノンラウリン酸エステル
変色温度調整剤e：４－ヒドロキシメチルビフェニルのデシルエーテル
変色温度調整剤f：ベンジルフェニルケトン
変色温度調整剤g：パルミチン酸ステアリル 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
顕色剤（顕色性物質）：２，２－ビス(４－ヒドロキシフェニル)ヘキサフルオロプロパン
変色温度調整剤ａ：４－ヒドロキシメチルビフェニルデカン酸エステル
変色温度調整剤ｂ：安息香酸フェニル－ｎ－デシルエーテル
変色温度調整剤c：４－ヒドロキシベンゾフェノンラウリルエーテル
変色温度調整剤d：４－クロロ－４’－ヒドロキシベンゾフェノンラウリン酸エステル
変色温度調整剤e：４－ヒドロキシメチルビフェニルのデシルエーテル
変色温度調整剤f：ベンジルフェニルケトン
変色温度調整剤g：パルミチン酸ステアリル 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
ヒステリシスΔＨの測定方法
表１及び表２に示す各成分より調整した各感温変色性組成物を液状組成物とケント紙上に塗布し、室温で乾燥させ、試験サンプルを作成した。
変色温度曲線の測定
１．温度調節プレート上に試験サンプルを乗せ、下記の順序で１０℃／分の昇温速度でプレート温度を変化させた。
２０℃ → ９０℃ → －３０℃ → ２０℃
２．約２℃毎にミノルタ株式会社製色彩色度計ＣＲ－３００で測色し、各温度のケント紙からの色差ΔＥ＊を算出した。
３．図１に示すような、得られた変色温度曲線から、ヒステリシス幅ΔＨ、完全呈色温度Ｔ１、発消色分岐温度Ｔ２を評価した。 Method for Measuring Hysteresis ΔH Each temperature-sensitive color-changing composition prepared from each component shown in Tables 1 and 2 was applied onto a liquid composition and Kent paper, and dried at room temperature to prepare a test sample.
Measurement of discoloration temperature curve The test sample was placed on the temperature control plate, and the plate temperature was changed at a temperature increase rate of 10 ° C./min in the following order.
20 ° C → 90 ° C → -30 ° C → 20 ° C
2. The color difference ΔE * from Kent paper at each temperature was calculated with a color chromaticity meter CR-300 manufactured by Minolta Co., Ltd. every approximately 2 ° C.
3. From the obtained discoloration temperature curve as shown in FIG. 1, the hysteresis width ΔH, the complete coloration temperature T1, and the color development / erasing branch temperature T2 were evaluated.
表１及び表２に示す各成分より調整した各感温変色性組成物を液状組成物とケント紙上に塗布し、室温で乾燥させ、試験サンプルを作成した。
変色温度曲線の測定
１．温度調節プレート上に試験サンプルを乗せ、下記の順序で１０℃／分の昇温速度でプレート温度を変化させた。
２０℃ → ９０℃ → －３０℃ → ２０℃
２．約２℃毎にミノルタ株式会社製色彩色度計ＣＲ－３００で測色し、各温度のケント紙からの色差ΔＥ＊を算出した。
３．図１に示すような、得られた変色温度曲線から、ヒステリシス幅ΔＨ、完全呈色温度Ｔ１、発消色分岐温度Ｔ２を評価した。 Method for Measuring Hysteresis ΔH Each temperature-sensitive color-changing composition prepared from each component shown in Tables 1 and 2 was applied onto a liquid composition and Kent paper, and dried at room temperature to prepare a test sample.
Measurement of discoloration temperature curve The test sample was placed on the temperature control plate, and the plate temperature was changed at a temperature increase rate of 10 ° C./min in the following order.
20 ° C → 90 ° C → -30 ° C → 20 ° C
2. The color difference ΔE * from Kent paper at each temperature was calculated with a color chromaticity meter CR-300 manufactured by Minolta Co., Ltd. every approximately 2 ° C.
3. From the obtained discoloration temperature curve as shown in FIG. 1, the hysteresis width ΔH, the complete coloration temperature T1, and the color development / erasing branch temperature T2 were evaluated.
評価結果
本発明中の化合物ａ～ｅを使用してなる実施例１～５の感温変色性組成物によると、完全呈色温度Ｔ１が－５℃以下、発消色分岐温度Ｔ２が４０℃以上であって、日常的な温度環境がこれらのＴ１及びＴ２の範囲内である結果が得られた。これは日常的な温度範囲では変色せず、その温度範囲を超えた加熱された温度において消色、もしくは冷却された温度においては呈色することを示している。この結果によれば、日常的に使用する温度範囲を包含するように広いヒステリシスの幅の温度範囲が存在するから、場合により消色された状態と呈色された状態の感温変色性組成物を使い分けることが可能である。
特に実施例１～３及び５によれば、完全呈色温度Ｔ１が特に低く、一旦消色した組成物が寒冷地の屋外においても再発色しにくいという効果を奏する。 Evaluation Results According to the 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. As described above, 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. According to this result, since there is a temperature range with a wide hysteresis width so as to encompass the temperature range used on a daily basis, the thermochromic composition in a decolored state and a colored state in some cases Can be used properly.
In particular, according to Examples 1 to 3 and 5, 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.
本発明中の化合物ａ～ｅを使用してなる実施例１～５の感温変色性組成物によると、完全呈色温度Ｔ１が－５℃以下、発消色分岐温度Ｔ２が４０℃以上であって、日常的な温度環境がこれらのＴ１及びＴ２の範囲内である結果が得られた。これは日常的な温度範囲では変色せず、その温度範囲を超えた加熱された温度において消色、もしくは冷却された温度においては呈色することを示している。この結果によれば、日常的に使用する温度範囲を包含するように広いヒステリシスの幅の温度範囲が存在するから、場合により消色された状態と呈色された状態の感温変色性組成物を使い分けることが可能である。
特に実施例１～３及び５によれば、完全呈色温度Ｔ１が特に低く、一旦消色した組成物が寒冷地の屋外においても再発色しにくいという効果を奏する。 Evaluation Results According to the 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. As described above, 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. According to this result, since there is a temperature range with a wide hysteresis width so as to encompass the temperature range used on a daily basis, the thermochromic composition in a decolored state and a colored state in some cases Can be used properly.
In particular, according to Examples 1 to 3 and 5, 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.
一方、本発明中の化合物ａ～ｅのいずれも使用せず、変色温度調整剤としてベンジルフェニルケトンを使用した比較例１の熱変色組成物によれば、完全呈色温度Ｔ１が２４℃とちょうど室温であり、ヒステリシスの幅が狭く、そのヒステリシスの幅は常温を包含するものではなく、日常的な使用状況の下において意図せずに熱変色を起こすことを示しているから、通常使用する温度条件下において変色を必要としない用途には不向きである。
また変色温度調整剤gとしてパルミチン酸ステアリルを使用する比較例２によれば、ヒステリシスの幅がせまく、かつ完全呈色温度Ｔ１が４０℃と高温で、日常的に使用する温度範囲では呈色をしており、加熱により発消色分岐温度Ｔ２である６１℃以上として消色する性質を示すので、日常的な温度において場合により呈色及び消色の二通りを求めることはできない。 On the other hand, according to the 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.
Further, according to Comparative Example 2 in which stearyl palmitate is used as the color change temperature adjusting agent g, the hysteresis width is wide, and the complete color temperature T1 is as high as 40 ° C. In addition, 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.
また変色温度調整剤gとしてパルミチン酸ステアリルを使用する比較例２によれば、ヒステリシスの幅がせまく、かつ完全呈色温度Ｔ１が４０℃と高温で、日常的に使用する温度範囲では呈色をしており、加熱により発消色分岐温度Ｔ２である６１℃以上として消色する性質を示すので、日常的な温度において場合により呈色及び消色の二通りを求めることはできない。 On the other hand, according to the 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.
Further, according to Comparative Example 2 in which stearyl palmitate is used as the color change temperature adjusting agent g, the hysteresis width is wide, and the complete color temperature T1 is as high as 40 ° C. In addition, 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.
Claims (2)
- ロイコ染料、顕色性物質、変色温度調整剤を含有する感温変色性組成物において、変色温度調整剤が下記化合物ａ～ｅの少なくとも１種以上の化合物である組成物。
化合物ａ
化合物ｂ
化合物ｃ
化合物ｄ
化合物ｅ
式中ＲはそれぞれＣ４～２２の脂肪族炭化水素基を表す。 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 at least one of the following compounds a to e.
Compound a
Compound b
Compound c
Compound d
Compound e
In the formula, each R represents a C4-22 aliphatic hydrocarbon group. - 請求項１記載の組成物を内包するマイクロカプセル。 A microcapsule containing the composition according to claim 1.
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| EP3192845B1 (en) * | 2014-08-18 | 2019-05-01 | The Pilot Ink Co., Ltd. | Thermochromic color-memory composition and thermochromic color-memory microcapsule pigment including same |
| KR102562352B1 (en) * | 2015-06-26 | 2023-08-01 | 동아연필 주식회사 | Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same |
| CN104893421A (en) * | 2015-06-29 | 2015-09-09 | 蔡武军 | Reversible temperature-sensitive color-changeable solid ink composition |
| US20180142141A1 (en) * | 2016-11-24 | 2018-05-24 | The Gillette Company Llc | Handle for shaving device comprising a thermochromic material |
| JP7068267B2 (en) * | 2017-02-27 | 2022-05-16 | パイロットインキ株式会社 | Thermochromic color memorizing composition and its contained thermochromic color memorizing microcapsule pigment |
| KR101988916B1 (en) * | 2017-05-25 | 2019-06-13 | 주식회사 엑티브온 | Irreversible thermochromic molded object for preventing overheating and process for the preparation thereof |
| CN109575664B (en) * | 2018-12-21 | 2021-03-26 | 上海晨光文具股份有限公司 | Long-term stable color-changing oil painting stick and preparation method thereof |
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- 2012-02-22 CN CN201280010292.6A patent/CN103391984B/en not_active Expired - Fee Related
- 2012-02-22 WO PCT/JP2012/054180 patent/WO2012115121A1/en active Application Filing
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| JP2003253149A (en) * | 2001-12-27 | 2003-09-10 | Pilot Ink Co Ltd | Thermally color-developing, reversibly thermochromic pigment |
| JP2007332232A (en) * | 2006-06-14 | 2007-12-27 | Matsui Shikiso Chem Co Ltd | Thermochromic hysteresis composition |
| WO2010131684A1 (en) * | 2009-05-12 | 2010-11-18 | パイロットインキ株式会社 | Thermochromic color-memory composition, and thermochromic color-memory microcapsule pigment having the composition encapsulated therein |
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| EP3109293A1 (en) * | 2015-06-26 | 2016-12-28 | Dong-A Pencil Co., Ltd. | Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same |
| US9909025B2 (en) | 2015-06-26 | 2018-03-06 | Dong-A Pencil Co., Ltd. | Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same |
| WO2017037284A1 (en) * | 2015-09-03 | 2017-03-09 | Thermographic Measurements Ltd | Compound for use in colour change compositions |
| US11225577B2 (en) | 2015-09-03 | 2022-01-18 | Thermographic Measurements Ltd | Temperature-sensitive indicator |
| US11339296B2 (en) | 2015-09-03 | 2022-05-24 | Societe Bic | Compound for use in colour change compositions |
| US11608440B2 (en) | 2015-09-03 | 2023-03-21 | Thermographic Measurements Ltd | Compound for use in colour change compositions |
| WO2018094630A1 (en) * | 2016-11-24 | 2018-05-31 | The Gillette Company Llc | Handle for shaving device comprising a thermochromic material |
| US11192395B2 (en) | 2017-09-08 | 2021-12-07 | Crayola Llc | Color development writing compositions and writing instruments |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5833457B2 (en) | 2015-12-16 |
| CN103391984A (en) | 2013-11-13 |
| JP2012188648A (en) | 2012-10-04 |
| CN103391984B (en) | 2016-02-24 |
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