CN102807853B - Reversible thermochromic microcapsule and preparation method thereof - Google Patents
Reversible thermochromic microcapsule and preparation method thereof Download PDFInfo
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- CN102807853B CN102807853B CN201210285247.3A CN201210285247A CN102807853B CN 102807853 B CN102807853 B CN 102807853B CN 201210285247 A CN201210285247 A CN 201210285247A CN 102807853 B CN102807853 B CN 102807853B
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- leuco dye
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- 230000002441 reversible effect Effects 0.000 title claims abstract description 113
- 239000003094 microcapsule Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000975 dye Substances 0.000 claims abstract description 102
- 239000000203 mixture Substances 0.000 claims abstract description 73
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 39
- -1 ester compound Chemical class 0.000 claims abstract description 38
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 37
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract description 37
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 21
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 claims description 38
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 claims description 36
- 239000000839 emulsion Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000004945 emulsification Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- CZRVYUSTYDMLND-UHFFFAOYSA-N O1C(CC2=C1C=CC=C2)=O.N2C=CC=CC=C2 Chemical compound O1C(CC2=C1C=CC=C2)=O.N2C=CC=CC=C2 CZRVYUSTYDMLND-UHFFFAOYSA-N 0.000 claims description 18
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical group C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 claims description 18
- 229920006026 co-polymeric resin Polymers 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 claims description 9
- NNDMTQHMGCAHRD-UHFFFAOYSA-N 3-(1-butyl-2-methylindol-3-yl)-6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C12=CC=CC=C2N(CCCC)C(C)=C1C1(C2=CC=C(C=C2C(=O)O1)N(C)C)C1=CC=C(N(C)C)C=C1 NNDMTQHMGCAHRD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011162 core material Substances 0.000 abstract 2
- XBCTUDRVBSOUQD-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3-phenyl-2-benzofuran-1-one Chemical compound C12=CC=CC=C2C(=O)OC1(C=1NC2=CC=CC=C2C=1)C1=CC=CC=C1 XBCTUDRVBSOUQD-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 14
- 238000004061 bleaching Methods 0.000 description 13
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000004040 coloring Methods 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000006735 deficit Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 241000220317 Rosa Species 0.000 description 2
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ACNUVXZPCIABEX-UHFFFAOYSA-N 3',6'-diaminospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N)C=C1OC1=CC(N)=CC=C21 ACNUVXZPCIABEX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004218 Orcein Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019248 orcein Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001047 purple dye Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- RLGKSXCGHMXELQ-ZRDIBKRKSA-N trans-2-styrylquinoline Chemical compound C=1C=C2C=CC=CC2=NC=1\C=C\C1=CC=CC=C1 RLGKSXCGHMXELQ-ZRDIBKRKSA-N 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
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- Heat Sensitive Colour Forming Recording (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Color Printing (AREA)
Abstract
The invention provides a reversible thermochromic microcapsule. The reversible thermochromic microcapsule comprises a core material and a wall material, wherein the core material comprises 3-6 parts by weight of first leuco dye, 0.3-0.4 part by weight of second leuco dye, 6-7 parts by weight of color developing agent and 30-40 parts by weight of ester compound by weight, wherein the first leuco dye is a fluorane dye, phenyl indolyl aza-2-benzofuraone, phenyl indolyl phthalide or phenyl aza-phthalide; the second leuco dye is a leuco dye with the melting point of 80-100 DEG C; the color developing agent is a mixture of bisphenol F and phthalimide; and the wall material is a wall system formed by a styrene-maleic anhydride copolymer and a urea formaldehyde resin prepolymer. The invention further provides a preparation method for the reversible thermochromic microcapsule. Due to the adoption of the compounded leuco dyes, the color development intensity of the microcapsule can be improved and the usage amount of the microcapsule in an ink can be reduced; and due to the adoption of the compounded color developing agent, the price is lower and the popularization is facilitated.
Description
Technical field
The present invention relates to fine chemical technology field, particularly a kind of reversible thermochromic microcapsule and preparation method thereof.
Background technology
Thermal discoloration material is a kind of specific functionality material, has the characteristic that color changes with temperature.Wherein, in the time that material is heated to certain temperature, color changes, and demonstrates a kind of new color, and when cooling again, again returns to again original color, and this material is called reversible thermochromic material.At present, the every field to daily life to the applied research of reversible thermochromic material wide spread.
Pilot Ink Co., Ltd. has released a kind of reversible thermochromic pen of evil spirit friction pen by name, and this writing writing out will fade while running into 60 DEG C of above thermals source, in the time that the writing having faded runs into the low-temperature receiver below-20 DEG C, can reappear again.The Chinese patent literature that is CN101965386A referring to application publication number, the core technology of described reversible thermochromic pen is exactly the reversible thermochromic microcapsule pigment that its ink adopts.Described reversible thermochromic microcapsule pigment comprises a kind of reversible thermochromic composition by leuco dye, developer and variable color temperature control solvent composition, makes above-mentioned reversible thermochromic pen have These characteristics.
Because Pilot Ink Co., Ltd. adopts supplied for electronic tint permanence organic compound as ditane 2-benzo (c) furanone, Phenylindole base 2-benzo (c) furanone, indyl 2-benzo (c) furanone, ditane azepine 2-benzo (c) furanone, Phenylindole base azepine 2-benzo (c) furanone, fluorane, styryl quinoline and diaza rhodamine lactone are as leuco dye, its quality is generally 1% ~ 5% of described reversible thermochromic composition total mass, make the coloring intensity of described reversible thermochromic microcapsule pigment lower, large usage quantity in the ink of described reversible thermochromic pen, cause the expensive of described reversible thermochromic pen, be unfavorable for marketing.Meanwhile, the developer in described reversible thermochromic microcapsule pigment is a kind of expensive bisphenol compound, has further increased the cost of ink, has brought certain difficulty to the marketing of ink.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of reversible thermochromic microcapsule and preparation method thereof, the coloring intensity of reversible thermochromic microcapsule provided by the invention is higher.
The invention provides a kind of reversible thermochromic microcapsule, comprise the wall material of core and the described core of parcel;
The raw material that described core comprises following weight part:
The first leuco dye of 3 ~ 6 weight parts, described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide;
The second leuco dye of 0.3 ~ 0.4 weight part, described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C;
The developer of 6 ~ 7 weight parts, described developer is Bisphenol F and phthalic imidine;
The ester compound of 30 ~ 40 weight parts;
Described wall material is the bag wall body system that styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer form.
Preferably, described the second leuco dye is 4-[2-(2-octyloxy-phenyl)-6-phenyl-4-pyridyl]-N, two (N-octyl group-2 methyl indole) the O-phthalic lactones of N-xylidene(s) or 3,3-.
Preferably, described the first leuco dye is 3-(2-octyloxy-4-diethylin phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl)-4-azepine-benzo (c) furanone, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinfluorane, 6-dibutylamino-1,2-benzo fluorane, 1,3-dimethyl-6-dibutylamino fluorane, 3, two (2-oxyethyl group-4-N, N-diethylamino the phenyl)-7-azepine phthalides of 3-, 3-(4-dimethylamino phenyl)-3-(1-butyl-2-methyl-indol-3-yl)-6-dimethylamino phthalide or the chloro-6-dibutylamino of 2-fluorane.
Preferably, the particle diameter of described core is below 8 μ m.
Preferably, the mass ratio of described urea-formaldehyde resin prepolymer and described core is 1:3 ~ 3:1; The mass ratio of described styrene maleic anhydride copolymer and described core is (0.02 ~ 3): 1.
Compared with prior art, the core of reversible thermochromic microcapsule provided by the invention is reversible thermochromic composition, the first leuco dye that comprises 3 ~ 6 weight parts, described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide; The second leuco dye of 0.3 ~ 0.4 weight part, described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C; The developer of 6 ~ 7 weight parts, described developer is Bisphenol F and phthalic imidine; The ester compound of 30 ~ 40 weight parts.The present invention adds the leuco dye of a small amount of fusing point between 80 DEG C ~ 100 DEG C to carry out composite at fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide, the coloring intensity of reversible thermochromic microcapsule is significantly increased, in the time of follow-up manufacture ink, can greatly reduce like this usage quantity of reversible thermochromic microcapsule, thereby the cost that greatly reduces ink, is beneficial to marketing.
Meanwhile, the present invention carries out Bisphenol F and phthalic imidine composite, and as the developer of reversible thermochromic composition, it is general chemical, and price is lower, has obvious cost advantage, for the final popularization of product has alleviated partial impairment.
In addition, the bag wall body that the present invention forms with styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer is the wall material of reversible thermochromic microcapsule, make reversible thermochromic microcapsule after freezing colour developing, can be directly used in the production of ink, dry without separating, be easy to scale operation.
The preparation method who the invention provides a kind of reversible thermochromic microcapsule, comprises the following steps:
The ester compound of the developer of the second leuco dye of the first leuco dye of 3 ~ 6 weight parts, 0.3 ~ 0.4 weight part, 6 ~ 7 weight parts and 30 ~ 40 weight parts is mixed, after heating, obtain molten mixture; Described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide; Described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C; Described developer is Bisphenol F and phthalic imidine;
To after described molten mixture and styrene maleic anhydride copolymer aqueous solution, carry out emulsification, the emulsion of the particle diameter that obtains described molten mixture below 8 μ m;
After described emulsion is mixed with urea-formaldehyde resin prepolymer, be cured, obtain reversible thermochromic microcapsule.
Preferably, the temperature of described emulsification is 50 DEG C ~ 90 DEG C.
Preferably, the mass concentration of the described styrene maleic anhydride copolymer aqueous solution is 2% ~ 30%, and the mass ratio of the described styrene maleic anhydride copolymer aqueous solution and described molten mixture is 1:1 ~ 10:1.
Preferably, the mass ratio of described urea-formaldehyde resin prepolymer and described molten mixture is 1:3 ~ 3:1.
Preferably, described curing temperature is 60 DEG C ~ 90 DEG C, and the described curing time is 0.1 hour ~ 10 hours.
Compared with prior art, the preparation method of reversible thermochromic microcapsule provided by the invention is taking fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide as the first leuco dye, leuco dye taking fusing point between 80 DEG C ~ 100 DEG C is the second leuco dye, according to certain weight part, with Bisphenol F and phthalic imidine as developer, mix as the ester compound of solvent, heating obtains the molten mixture as core; Then taking described molten mixture as oil phase, taking the styrene maleic anhydride copolymer aqueous solution as external phase, after emulsification, obtain the emulsion of particle diameter below 8 μ m, add urea-formaldehyde resin prepolymer, the bag wall body that obtains after solidifying forming with styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer is the reversible thermochromic microcapsule of wall material again.The present invention adds the leuco dye of a small amount of fusing point between 80 DEG C ~ 100 DEG C to carry out composite at fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide, the coloring intensity of reversible thermochromic microcapsule is significantly increased, in the time of follow-up manufacture ink, can greatly reduce like this usage quantity of reversible thermochromic microcapsule, thereby the cost that greatly reduces ink, is beneficial to marketing.
Meanwhile, the present invention carries out Bisphenol F and phthalic imidine composite, and as the developer of reversible thermochromic composition, it is general chemical, and price is lower, has obvious cost advantage, for the final popularization of product has alleviated partial impairment.
The bag wall body that the present invention forms with styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer is the wall material of microcapsule in reversible thermochromic microcapsule slurry, make reversible thermochromic microcapsule after freezing colour developing, can be directly used in the production of ink, dry without separating, simple to operate, process stabilizing, has greatly reduced the production cost of warm change ink and has applied obstacle.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of reversible thermochromic microcapsule, comprise the wall material of core and the described core of parcel;
The raw material that described core comprises following weight part:
The first leuco dye of 3 ~ 6 weight parts, described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide;
The second leuco dye of 0.3 ~ 0.4 weight part, described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C;
The developer of 6 ~ 7 weight parts, described developer is Bisphenol F and phthalic imidine;
The ester compound of 30 ~ 40 weight parts;
Described wall material is the bag wall body system that styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer form.
Leuco dye is some materials that can develop the color in conjunction with proton, in variable color system as supplied for electronic part.Developer is a kind of acid compound of releasing that discharges proton, is electrophilic compound.The variable color system of leuco dye and developer will just can reach color changeable effect in special solvent, and the molten mass of this solvent has good dissolving power to leuco dye and developer, and energy enhancing system is to hot susceptibility, therefore can be described as sensitizing agent; It also directly determines the discoloring temperature of variable color system, as fusible high fatty alcohol, aromatic hydrocarbons and ester compound etc.Microcapsule refer to the miniature vessel below the micron order with polymeric shell wall, can hold or wrap up core.
The present invention is using as fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or the phenyl azepine phthalide of the first leuco dye and as the fusing point of the second leuco dye, the leuco dye between 80 DEG C ~ 100 DEG C carries out composite, Bisphenol F and phthalic imidine are carried out composite, use as developer, mix with ester compound again, obtain reversible thermochromic composition, after heating, obtain core, described core is the reversible thermochromic composition after heating; The bag wall body forming with styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer is wall material, form reversible thermochromic microcapsule, its coloring intensity is higher, in the time of follow-up manufacture ink, can greatly reduce the usage quantity of reversible thermochromic microcapsule, thereby the cost that greatly reduces ink, is beneficial to marketing.
In the present invention, the first leuco dye that described reversible thermochromic composition comprises 3 ~ 6 weight parts, preferably comprises the first leuco dye of 4 ~ 5 weight parts.Described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide, and coloring intensity is higher; Described the first leuco dye is preferably 3-(2-octyloxy-4-diethylin phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl)-4-azepine-benzo (c) furanone, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinfluorane, 6-dibutylamino-1,2-benzo fluorane, 1,3-dimethyl-6-dibutylamino fluorane, 3, two (2-oxyethyl group-4-N, N-diethylamino the phenyl)-7-azepine phthalides of 3-, 3-(4-dimethylamino phenyl)-3-(1-butyl-2-methyl-indol-3-yl)-6-dimethylamino phthalide or the chloro-6-dibutylamino of 2-fluorane.
Wherein, 3-(2-octyloxy-4-diethylin phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl)-4-azepine-benzo (c) furanone is a kind of blue dyes, can be described as BLUE-O, its structure as shown in the formula (I):
3-N-isopentyl-N-ethylamino-6-methyl-7-anilinfluorane is a kind of black dyes, can be described as S-205, is for No. CAS 70516-41-5, its structure as shown in the formula (II):
6-dibutylamino-1,2-benzo fluorane is a kind of that pink dyestuff, its structure as shown in the formula (III):
1,3-dimethyl-6-dibutylamino fluorane is a kind of orange red dyestuff, and its structure is suc as formula shown in (IV):
Two (2-oxyethyl group-4-N, N-diethylamino the phenyl)-7-azepine phthalides of 3,3-are a kind of green colouring material, can be described as GN-1, are for No. CAS 132467-74-4, and its structure is as shown in formula V:
3-(4-dimethylamino phenyl)-3-(1-butyl-2-methyl-indol-3-yl)-6-dimethylamino phthalide is a kind of purple dye, can be described as LBC-51, is for No. CAS 92453-31-1, its structure is suc as formula shown in (VI):
The chloro-6-dibutylamino of 2-fluorane is a kind of orchil, and its structure is suc as formula shown in (VII):
In the present invention, the second leuco dye that described reversible thermochromic composition comprises 0.3 ~ 0.4 weight part, preferably comprises the second leuco dye of 0.3 weight part.
Described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C, is preferably 4-[2-(2-octyloxy-phenyl)-6-phenyl-4-pyridyl]-N, two (N-octyl group-2 methyl indole) the O-phthalic lactones of N-xylidene(s) or 3,3-, fusing point is lower.
Wherein, 4-[2-(2-octyloxy-phenyl)-6-phenyl-4-pyridyl]-N, N-xylidene(s) is a kind of yellow dyes, can be described as CK-37, is for No. CAS 144190-25-0, its structure is suc as formula shown in (VIII):
Two (N-octyl group-2 methyl indole) the O-phthalic lactones of 3,3-are a kind of rose dye, can be described as CK-16, are for No. CAS 50292-95-0, and its structure is suc as formula shown in (IX):
The present invention is undertaken composite by leuco dye and fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide a small amount of, low melting point, the usage quantity of this composite leuco dye is more, can make the coloring intensity of reversible thermochromic microcapsule significantly increase, in the time of follow-up manufacture ink, can greatly reduce like this usage quantity of reversible thermochromic microcapsule, thereby the cost that greatly reduces ink, is beneficial to marketing.
In the present invention, the developer that described reversible thermochromic composition comprises 6 ~ 7 weight parts, preferably comprises the developer of 6 weight parts.Described developer is Bisphenol F and phthalic imidine, and it is general chemical, and price is lower, has obvious cost advantage, for the final popularization of product has alleviated partial impairment.The weight part ratio of described Bisphenol F and described phthalic imidine is preferably 2:4 ~ 5.
In the present invention, the ester compound that described reversible thermochromic composition comprises 30 ~ 40 weight parts, preferably comprises the ester compound of 30 ~ 35 weight parts.The solvent of the present invention taking ester compound as temperature-control discoloring, described ester compound is preferably 4-benzyloxy styroyl decylate.
The present invention is taking the molten mixture that obtains after the heating of described reversible thermochromic composition as core, and wherein, the particle diameter of described core is preferably below 8 μ m, and more preferably 1 μ m ~ 8 μ m, most preferably is 2 μ m ~ 3 μ m; The temperature of described heating is can be by the temperature of described reversible thermochromic composition melting, is preferably 110 DEG C ~ 120 DEG C, more preferably 110 DEG C.
The bag wall body that the present invention forms with styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer is wall material, makes reversible thermochromic microcapsule after freezing colour developing, can be directly used in the production of ink, is dried without separating, and is easy to scale operation.
Wherein, the present invention is not particularly limited styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer, adopts conventional styrene maleic anhydride copolymer and the urea-formaldehyde resin prepolymer in this area; The mass ratio of described urea-formaldehyde resin prepolymer and described core is preferably 1:3 ~ 3:1; The mass ratio of described styrene maleic anhydride copolymer and described core is preferably (0.02 ~ 3): 1, and more preferably (0.03 ~ 2): 1.
The present invention also provides a kind of preparation method of reversible thermochromic microcapsule, comprises the following steps:
The ester compound of the developer of the second leuco dye of the first leuco dye of 3 ~ 6 weight parts, 0.3 ~ 0.4 weight part, 6 ~ 7 weight parts and 30 ~ 40 weight parts is mixed, after heating, obtain molten mixture; Described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide; Described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C; Described developer is Bisphenol F and phthalic imidine;
To after described molten mixture and styrene maleic anhydride copolymer aqueous solution, carry out emulsification, the emulsion of the particle diameter that obtains described molten mixture below 8 μ m;
After described emulsion is mixed with urea-formaldehyde resin prepolymer, be cured, obtain reversible thermochromic microcapsule.
According to above-mentioned weight part, the present invention mixes the first leuco dye, the second leuco dye, developer, ester compound, obtains reversible thermochromic composition.Wherein, described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide; Described the second leuco dye is the leuco dye of fusing point between 80 DEG C ~ 100 DEG C; Described developer is Bisphenol F and phthalic imidine.
The present invention heats described reversible thermochromic composition, obtains molten mixture.Wherein, the temperature of described heating is can be by the temperature of described reversible thermochromic composition melting, is preferably 110 DEG C ~ 120 DEG C, more preferably 110 DEG C.
The present invention is taking fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide as the first leuco dye, leuco dye taking fusing point between 80 DEG C ~ 100 DEG C is the second leuco dye, according to certain weight part, with Bisphenol F and phthalic imidine as developer, mix as the ester compound of solvent, heating obtains the molten mixture as core.The present invention adds the leuco dye of a small amount of fusing point between 80 DEG C ~ 100 DEG C to carry out composite at fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide, the coloring intensity of reversible thermochromic microcapsule is significantly increased, in the time of follow-up manufacture ink, can greatly reduce like this usage quantity of reversible thermochromic microcapsule, thereby the cost that greatly reduces ink, is beneficial to marketing.
Meanwhile, the present invention carries out Bisphenol F and phthalic imidine composite, and as the developer of reversible thermochromic composition, it is general chemical, and price is lower, has obvious cost advantage, for the final popularization of product has alleviated partial impairment.The weight part ratio of described Bisphenol F and described phthalic imidine is preferably 2:4 ~ 5.
Obtain after molten mixture, the present invention is taking it as oil phase, taking styrene maleic anhydride copolymer (SMA) aqueous solution as external phase, and the emulsion of the particle diameter that obtains described molten mixture after emulsification below 8 μ m.
In the present invention, the mass concentration of the described styrene maleic anhydride copolymer aqueous solution is preferably 2% ~ 30%, and more preferably 3% ~ 20%, most preferably be 3% ~ 8%; The mass ratio of the described styrene maleic anhydride copolymer aqueous solution and described molten mixture is preferably 1:1 ~ 10:1, more preferably 1:3 ~ 1:6.
In the present invention, described emulsification is preferably high speed shear emulsification; The temperature of described emulsification is preferably 50 DEG C ~ 90 DEG C, more preferably 60 DEG C ~ 70 DEG C; The time of described emulsification is preferably 30 minutes ~ and 40 minutes, more preferably 30 minutes; In described emulsion, the particle diameter of described molten mixture, below 8 μ m, is preferably 1 μ m ~ 8 μ m, and more preferably 2 μ m ~ 3 μ m, disperse comparatively stable.
Obtain after emulsion, the present invention mixes it with urea-formaldehyde resin prepolymer, be then cured, and obtains reversible thermochromic microcapsule.
The present invention adopts styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer to form bag wall body system, as the wall material of reversible thermochromic microcapsule, make reversible thermochromic microcapsule after freezing colour developing, can be directly used in the production of ink, dry without separating, simple to operate, process stabilizing, has greatly reduced the production cost of warm change ink and has applied obstacle.
In the present invention, described urea-formaldehyde resin prepolymer adopts the conventional urea-formaldehyde resin prepolymer in this area; The mass ratio of described urea-formaldehyde resin prepolymer and described molten mixture is preferably 1:3 ~ 3:1.
In the present invention, described curing temperature is preferably 60 DEG C ~ 90 DEG C, more preferably 80 DEG C ~ 85 DEG C; The described curing time is preferably 0.1 hour ~ and 10 hours, more preferably 0.5 hour ~ 5 hours, most preferably be 1 hour ~ 2 hours.
Obtain after reversible thermochromic microcapsule, the present invention carries out reversible thermochromic performance testing to it.Test result shows, the present invention is in fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide, add the leuco dye of a small amount of fusing point between 80 DEG C ~ 100 DEG C to carry out composite, the coloring intensity of reversible thermochromic microcapsule is significantly increased, reversible thermochromic behavior is normal, in the time of follow-up manufacture ink, can greatly reduce like this usage quantity of reversible thermochromic microcapsule, thereby greatly reduce the cost of ink, be beneficial to marketing.Meanwhile, the present invention adopts composite developer, and price is lower, has further reduced cost.The features such as the present invention has that cost is low, temperature of reaction is moderate, simple to operate, process stabilizing, are easy to scale operation.
In order further to understand the present invention, below in conjunction with embodiment, reversible thermochromic microcapsule provided by the invention and preparation method thereof are explained.
Embodiment 1
By 1 of 6 weight parts, the CK-16 of 3-dimethyl-6-dibutylamino fluorane, 0.3 weight part, the Bisphenol F of 4 weight parts, the phthalic imidine of 2 weight parts and the 4-benzyloxy styroyl decylate of 30 weight parts mix, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from orange, and its complete bleaching temperature is 58 DEG C, are starting colour temperature and are being-2 DEG C, and colour temp is-20 DEG C completely.
Embodiment 2
By 1 of 6 weight parts, the CK-37 of 3-dimethyl-6-dibutylamino fluorane, 0.3 weight part, the Bisphenol F of 4 weight parts, the phthalic imidine of 2 weight parts and the 4-benzyloxy styroyl decylate of 30 weight parts mix, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 70 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 85 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.0 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from orange, and its complete bleaching temperature is 62 DEG C, and starting colour temperature is 0 DEG C, and colour temp is-18 DEG C completely.
Embodiment 3
By 1 of 3 weight parts, the CK-16 of 3-dimethyl-6-dibutylamino fluorane, 0.4 weight part, the Bisphenol F of 4 weight parts, the phthalic imidine of 2 weight parts and the 4-benzyloxy styroyl decylate of 40 weight parts mix, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 65 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.0 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from orange, and its complete bleaching temperature is 62 DEG C, are starting colour temperature and are being-2 DEG C, and colour temp is-25 DEG C completely.
Embodiment 4
By 1 of 3 weight parts, the CK-37 of 3-dimethyl-6-dibutylamino fluorane, 0.4 weight part, the Bisphenol F of 4 weight parts, the phthalic imidine of 2 weight parts and the 4-benzyloxy styroyl decylate of 30 weight parts mix, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from orange, and its complete bleaching temperature is 58 DEG C, and starting colour temperature is 0 DEG C, and colour temp is-18 DEG C completely.
Embodiment 5
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-16 of chloro-2-of 6 weight parts 6-dibutylamino fluorane, 0.3 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.0 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from redness, and its complete bleaching temperature is 60 DEG C, and starting colour temperature is 0 DEG C, and colour temp is-20 DEG C completely.
Embodiment 6
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-16 of chloro-2-of 3 weight parts 6-dibutylamino fluorane, 0.4 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.0 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from rose, and its complete bleaching temperature is 45 DEG C, are starting colour temperature and are being-12 DEG C, and colour temp is-30 DEG C completely.
Embodiment 7
By 6-dibutylamino-1 of 6 weight parts, the 4-benzyloxy styroyl decylate of the phthalic imidine of the CK-16 of 2-benzo fluorane, 0.3 weight part, the Bisphenol F of 4 weight parts, 2 weight parts and 30 weight parts mixes, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.0 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from pink, and its complete bleaching temperature is 60 DEG C, are starting colour temperature and are being-2 DEG C, and colour temp is-20 DEG C completely.
Embodiment 8
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-37 of the S-205 of 6 weight parts, 0.3 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from black, and its complete bleaching temperature is 60 DEG C, are starting colour temperature and are being-5 DEG C, and colour temp is-20 DEG C completely.
Embodiment 9
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-16 of the S-205 of 5 weight parts, 0.3 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from black, and its complete bleaching temperature is 56 DEG C, and starting colour temperature is 5 DEG C, and colour temp is-10 DEG C completely.
Embodiment 10
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-37 of the BLUE-O of 3 weight parts, 0.3 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from blueness, and its complete bleaching temperature is 60 DEG C, are starting colour temperature and are being-4 DEG C, and colour temp is-20 DEG C completely.
Embodiment 11
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-16 of the LBC-51 of 6 weight parts, 0.3 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from purple, and its complete bleaching temperature is 60 DEG C, are starting colour temperature and are being-4 DEG C, and colour temp is-20 DEG C completely.
Embodiment 12
The 4-benzyloxy styroyl decylate of the phthalic imidine of the Bisphenol F of the CK-37 of the GN-1 of 6 weight parts, 0.3 weight part, 4 weight parts, 2 weight parts and 30 weight parts is mixed, be heated to after 110 DEG C, obtain molten mixture;
Taking described molten mixture as oil phase, the SMA aqueous solution taking the concentration of 180 weight parts as 5%, as external phase, carries out high speed shear emulsification at the temperature of 60 DEG C, and after 30 minutes, obtaining oil phase particle diameter is the emulsion of 2 μ m ~ 3 μ m;
To the urea-formaldehyde resin prepolymer that adds 30 weight parts in described emulsion, at the temperature of 80 DEG C, solidify, after 2 hours, obtain reversible thermochromic microcapsule.
The median size of described reversible thermochromic microcapsule is 2.5 μ m; Described reversible thermochromic microcapsule, by the variation of temperature, become colorless from green, and its complete bleaching temperature is 47 DEG C, are starting colour temperature and are being-14 DEG C, and colour temp is-21 DEG C completely.
As seen from the above embodiment, the complete bleaching temperature of described reversible thermochromic microcapsule provided by the invention is 60 DEG C of left and right, and starting colour temperature is 0 DEG C of left and right, and colour temp is-20 DEG C of left and right completely.
Test result shows, the present invention is in fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide, add the leuco dye of a small amount of fusing point between 80 DEG C ~ 100 DEG C to carry out composite, the coloring intensity of reversible thermochromic microcapsule is significantly increased, reversible thermochromic behavior is normal, in the time of follow-up manufacture ink, can greatly reduce like this usage quantity of reversible thermochromic microcapsule, thereby greatly reduce the cost of ink, be beneficial to marketing.Meanwhile, the present invention adopts composite developer, and price is lower, has further reduced cost.The features such as the present invention has that cost is low, temperature of reaction is moderate, simple to operate, process stabilizing, are easy to scale operation.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (7)
1. reversible thermochromic microcapsule, comprise core and the wall material that wraps up described core;
The raw material that described core comprises following weight part:
The first leuco dye of 3～6 weight parts, described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide;
The second leuco dye of 0.3～0.4 weight part, described the second leuco dye is the leuco dye of fusing point between 80 DEG C～100 DEG C; Described the second leuco dye is 4-[2-(2-octyloxy-phenyl)-6-phenyl-4-pyridyl]-N, two (N-octyl group-2 methyl indole) the O-phthalic lactones of N-xylidene(s) or 3,3-;
The developer of 6～7 weight parts, described developer is Bisphenol F and phthalic imidine;
The ester compound of 30～40 weight parts;
Described wall material is the bag wall body system that styrene maleic anhydride copolymer and urea-formaldehyde resin prepolymer form; The mass ratio of described urea-formaldehyde resin prepolymer and described core is 1:3～3:1; The mass ratio of described styrene maleic anhydride copolymer and described core is (0.02～3): 1;
Described the first leuco dye is 3-(2-octyloxy-4-diethylin phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl)-4-azepine-benzo (c) furanone, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinfluorane, 6-dibutylamino-1,2-benzo fluorane, 1,3-dimethyl-6-dibutylamino fluorane, 3, two (2-oxyethyl group-4-N, N-diethylamino the phenyl)-7-azepine phthalides of 3-, 3-(4-dimethylamino phenyl)-3-(1-butyl-2-methyl-indol-3-yl)-6-dimethylamino phthalide or the chloro-6-dibutylamino of 2-fluorane.
2. reversible thermochromic microcapsule according to claim 1, is characterized in that, the particle diameter of described core is below 8 μ m.
3. a preparation method for reversible thermochromic microcapsule as claimed in claim 1 or 2, comprises the following steps:
The ester compound of the developer of the second leuco dye of the first leuco dye of 3～6 weight parts, 0.3～0.4 weight part, 6～7 weight parts and 30～40 weight parts is mixed, after heating, obtain molten mixture; Described the first leuco dye is fluoran dyes, Phenylindole base azepine 2-benzofuranone, Phenylindole base phthalide or phenyl azepine phthalide; Described the second leuco dye is the leuco dye of fusing point between 80 DEG C～100 DEG C; Described developer is Bisphenol F and phthalic imidine;
To after described molten mixture and styrene maleic anhydride copolymer aqueous solution, carry out emulsification, the emulsion of the particle diameter that obtains described molten mixture below 8 μ m;
After described emulsion is mixed with urea-formaldehyde resin prepolymer, be cured, obtain reversible thermochromic microcapsule.
4. preparation method according to claim 3, is characterized in that, the temperature of described emulsification is 50 DEG C～90 DEG C.
5. preparation method according to claim 3, it is characterized in that, the mass concentration of the described styrene maleic anhydride copolymer aqueous solution is 2%～30%, and the mass ratio of the described styrene maleic anhydride copolymer aqueous solution and described molten mixture is 1:1～10:1.
6. preparation method according to claim 3, is characterized in that, the mass ratio of described urea-formaldehyde resin prepolymer and described molten mixture is 1:3～3:1.
7. preparation method according to claim 3, is characterized in that, described curing temperature is 60 DEG C～90 DEG C, and the described curing time is 0.1 hour～10 hours.
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| US4666949A (en) * | 1986-01-31 | 1987-05-19 | Matsui Shikiso Chemical Co., Ltd. | Thermochromic polyurethane foam |
| EP0480162A1 (en) * | 1990-10-09 | 1992-04-15 | Matsui Shikiso Chemical Co., Ltd | Dyeing method and dyed product |
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| CN1538912A (en) * | 2002-05-14 | 2004-10-20 | 王子制纸株式会社 | Thermal recording material |
| CN101965386A (en) * | 2008-02-29 | 2011-02-02 | 百乐墨水株式会社 | Reversible thermal discoloration aqueous ink composition and writing implement using the same and writing implement set |
| WO2011058652A1 (en) * | 2009-11-13 | 2011-05-19 | パイロットインキ株式会社 | Thermochromic color-memorization type toner, cartridge including same housed therein, image formation apparatus, cartridge set, and image formation apparatus set |
| CN102191032A (en) * | 2010-03-19 | 2011-09-21 | 陈铨荣 | Reversible thermochromic organic material microcapsule |
| CN102504592A (en) * | 2011-09-29 | 2012-06-20 | 上海俊彩文具用品有限公司 | Thermochromic solution encapsulated surface hydrophilic compound particles and thermochromic neutral ink made of same |
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