CN112639033A - 双酚芴二酯化合物和包含其的热致变色颜料组合物 - Google Patents
双酚芴二酯化合物和包含其的热致变色颜料组合物 Download PDFInfo
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- CN112639033A CN112639033A CN201980055654.5A CN201980055654A CN112639033A CN 112639033 A CN112639033 A CN 112639033A CN 201980055654 A CN201980055654 A CN 201980055654A CN 112639033 A CN112639033 A CN 112639033A
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 239000000049 pigment Substances 0.000 title claims abstract description 56
- -1 Bisphenol fluorene diester compound Chemical class 0.000 title claims description 40
- 229930185605 Bisphenol Natural products 0.000 title claims description 27
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 239000003094 microcapsule Substances 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 230000008859 change Effects 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 14
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 claims description 9
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- RCVMSMLWRJESQC-UHFFFAOYSA-N 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(1-ethyl-2-methylindol-3-yl)furo[3,4-b]pyridin-5-one Chemical compound CCOC1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=NC=CC=C2C(=O)O1 RCVMSMLWRJESQC-UHFFFAOYSA-N 0.000 claims description 9
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 239000012429 reaction media Substances 0.000 claims description 8
- DXYZIGZCEVJFIX-UHFFFAOYSA-N 2'-(dibenzylamino)-6'-(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC=C3N(CC=1C=CC=CC=1)CC1=CC=CC=C1 DXYZIGZCEVJFIX-UHFFFAOYSA-N 0.000 claims description 6
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- SVOBELCYOCEECO-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)cyclohexyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=CC=2)=C1 SVOBELCYOCEECO-UHFFFAOYSA-N 0.000 claims description 6
- GFGSEGIRJFDXFP-UHFFFAOYSA-N 6'-(diethylamino)-2'-(2,4-dimethylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=C(C)C=C1C GFGSEGIRJFDXFP-UHFFFAOYSA-N 0.000 claims description 6
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 claims description 5
- YDYKGVWORCQOTN-UHFFFAOYSA-N 7-[4-(diethylamino)-2-hexoxyphenyl]-7-(1-ethyl-2-methylindol-3-yl)furo[3,4-b]pyridin-5-one Chemical compound CCCCCCOC1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=NC=CC=C2C(=O)O1 YDYKGVWORCQOTN-UHFFFAOYSA-N 0.000 claims description 5
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 claims description 5
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 4
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 3
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004101 4-Hexylresorcinol Substances 0.000 claims description 3
- 235000019360 4-hexylresorcinol Nutrition 0.000 claims description 3
- CEZCCHQBSQPRMU-UHFFFAOYSA-L chembl174821 Chemical compound [Na+].[Na+].COC1=CC(S([O-])(=O)=O)=C(C)C=C1N=NC1=C(O)C=CC2=CC(S([O-])(=O)=O)=CC=C12 CEZCCHQBSQPRMU-UHFFFAOYSA-L 0.000 claims description 3
- 229960003258 hexylresorcinol Drugs 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 3
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000003125 aqueous solvent Substances 0.000 description 3
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- 238000004042 decolorization Methods 0.000 description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
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- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 2
- IXHBSOXJLNEOPY-UHFFFAOYSA-N 2'-anilino-6'-(n-ethyl-4-methylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(CC)C1=CC=C(C)C=C1 IXHBSOXJLNEOPY-UHFFFAOYSA-N 0.000 description 2
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- XZXFZILEZWXEND-UHFFFAOYSA-N 3',6'-bis(diethylamino)-2-(4-nitrophenyl)spiro[isoindole-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C2C=1OC1=CC(N(CC)CC)=CC=C1C2(C1=CC=CC=C1C1=O)N1C1=CC=C([N+]([O-])=O)C=C1 XZXFZILEZWXEND-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本发明涉及双酚芴二酯化合物及其在热致变色颜料组合物中作为反应介质的用途。本发明还涉及包含此类热致变色颜料组合物的热致变色颜料微胶囊、包含此类热致变色颜料微胶囊的热致变色墨水组合物以及最终包含此类热致变色墨水组合物的书写工具。
热致变色颜料组合物表现出与温度变化有关的可逆变色特性。它们显示在着色和脱色状态之间可逆的颜色变化,具有由于温度变化所致的显著滞后特性,并且即使在终止施加颜色变化所需的热和冷之后,它们也以可互换和可逆的方式保持着色状态或脱色状态。当墨水标记需要重复擦除时,可以使用这些组合物。
墨水的热致变色效果通过以下三种化合物的组合起作用:
(A)给电子显色有机化合物(无色染料化合物),
(B)受电子化合物(显色剂化合物),和
(C)用作反应介质的化合物,其控制所述组分(A)和(B)之间的颜色反应,并能够导致可归因于化合物(A)和(B)的可逆的给/受电子反应。
温度变化可逆地导致墨水着色或脱色。对于本发明的热致变色墨水组合物,温度的升高将引起墨水的擦除,而冷却墨水将导致颜色重新出现。这些更改遵循图1的方案。在该方案中,墨水颜色的脱色起始温度为T3,完全脱色温度为T4,并且,TG为T3和T4之间的平均温度。相反,墨水颜色开始重新出现的温度为T2,完全重新着色的温度为T1,并且,TH为T1和T2之间的平均温度。变色滞后宽度(ΔH)是(TH)和(TG)之间的差。
令人惊讶地,发明人发现了新型双酚芴二酯化合物,其允许制备具有最佳熔融和结晶温度范围的热致变色颜料微胶囊,所述最佳熔融和结晶温度范围分别对应于脱色和重新着色温度。因此,本发明的化合物显示出许多优点,可用作热致变色颜料组合物中的温度变化调节剂:它们显示出优异的滞后特性,并且在着色状态和脱色状态之间具有极高的颜色对比度。包含本发明的双酚芴二酯化合物的热致变色墨水组合物还具有在接近70℃的温度下完全消失的优点,因此具有在炎热地区使用的优点。另外,本发明的热致变色颜料组合物具有抗紫外线特性,这些特性是本发明化合物所固有的,而无需在组合物中添加抗紫外线剂。
JP2008150483公开了一种热致变色变色组合物,其包含双酚芴化合物作为受电子化合物(B)。然而,当在热致变色颜料组合物中用作反应介质(C)时,JP2008150483的双酚芴化合物不提供热致变色效果。
因此,本发明涉及下式(I)表示的双酚芴二酯化合物作为热致变色墨水组合物中的温度变化调节剂的用途:
其中R1和R2相同或不同,表示C2-C30烷基、C2-C30烯基、C2-C30炔基或C2-C30烷氧基,所述烷基、烯基、炔基或烷氧基任选被至少一个羟基、卤素、氨基、C1-C8烷基或C1-C8烷氧基取代。
此类温度变化调节剂能够引起给电子显色有机化合物(A)与受电子化合物(B)之间的可逆的给/受电子反应。
根据优选实施例,R1和R2相同并且表示直链或支链C2-C30烷基,优选直链或支链C4-C20烷基,并且更优选直链或支链C6-C18烷基。
根据优选实施例,R1和R2相同并且表示直链或支链C6-C30烷基,优选直链或支链C6-C18烷基,并且更优选直链C13烷基。
本发明的另一个主题是由下式(II)表示的双酚芴二酯化合物:
其中,R1a和R2b相同或不同,表示直链或支链C6-C30烷基,优选直链或支链C6-C18烷基,并且更优选直链C13烷基。
根据本发明的由式(I)表示的化合物可以根据第一方法制备,该方法包含使双酚芴与式R1C(O)Cl和R2C(O)Cl的酰氯反应的步骤,其中R1和R2相同或不同,并且表示C2-C30烷基、C2-C30烯基、C2-C30炔基或C2-C30烷氧基,所述烷基、烯基、炔基或烷氧基任选被至少一个羟基、卤素、氨基、C1-C8烷基或C1-C8烷氧基取代,根据以下反应方案:
在该第一种方法中,双酚芴/酰氯R1C(O)Cl/酰氯R2C(O)Cl的摩尔比优选为1/1/1。
在该第一方法中,反应优选在-30至20℃,优选-10至10℃范围内的温度下进行。
根据本发明的由式(I)表示的化合物也可以根据第二方法制备,该方法包含使双酚芴与式R1COOH的羧酸反应的步骤,其中R1表示C2-C30烷基、C2-C30烯基、C2-C30炔基或C2-C30烷氧基,所述烷基、烯基、炔基或烷氧基任选被至少一个羟基、卤素、氨基、C1-C8烷基或C1-C8烷氧基取代,根据以下反应方案:
在该第二种方法中,双酚芴/羧酸R1COOH的摩尔比有利地在1/2至1/6范围内,并且优选为1/4。
在该第二方法中,反应优选在120至200℃,优选140至160℃范围内的温度下进行。
本发明的另一主题是一种热致变色颜料组合物,其包含:
(A)给电子显色有机化合物(无色染料化合物),
(B)受电子化合物(显色剂化合物),和
(C)根据本发明的式(I)化合物,作为控制所述组分(A)和(B)之间的颜色反应的反应介质。
令人惊奇的是,发明人发现了根据本发明的双酚芴二酯化合物具有特定的熔融和结晶温度,这使得它们可以用作热致变色颜料组合物中的化合物(C)或温度变化调节剂。
因此,本发明还描述了式(I)的双酚芴二酯化合物作为热致变色墨水组合物中的温度变化调节剂的用途。此类温度变化调节剂能够引起给电子显色有机化合物(A)与受电子化合物(B)之间的可逆的给/受电子反应。
化合物(A)、(B)和(C)的重量比受这些化合物中的每一个的结构和反应性影响。
相对于热致变色颜料组合物的总重量,给电子显色有机化合物(A)以重量计的量可以在1至10重量%,优选1至6重量%,并且甚至更优选2至4重量%内变化。
相对于热致变色颜料组合物的总重量,受电子化合物(B)以重量计的量可以在1至20重量%,优选1至14重量%,并且再更优选4至10重量%内变化。
相对于热致变色颜料组合物的总重量,用作反应介质的式(I)化合物(C)以重量计的量可以在70至98重量%,优选80至98重量%,并且甚至更优选86至94重量%内变化。
因此,本发明的热致变色颜料组合物可包含:
(A)1至10重量%,优选1至6重量%,并且甚至更优选2至4重量%的至少一种给电子显色有机化合物,
(B)1至20重量%,优选1至14重量%,并且甚至更优选4至10重量%的至少一种受电子化合物,以及
(C)70至98重量%,优选80至98重量%,并且甚至更优选86至94重量%的至少一种式(I)化合物。
有利地,本发明的热致变色颜料组合物在封装后具有20至80℃,优选30-80℃,并且甚至更优选40至70℃范围内的变色滞后宽度(ΔH)。
作为有机染料-电子给体化合物(A),可以无限制地涉及常规已知的化合物,例如二苯基甲烷酞化物、苯基吲哚基酞化物、吲哚基酞化物、二苯基甲烷氮杂酞化物、苯基吲哚基氮杂酞化物、荧烷、苯乙烯基喹啉和内酯二氮杂罗丹明,这些化合物的实例在下文中给出。
因此,有机染料-电子给体化合物(A)可以选自3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞(蓝色63,CAS号:69898-40-4)、3,3-双(对-二甲基氨基苯基)-6-二甲基氨基邻苯二甲酸酯(CAS号:1552-42-7)、2'-氯-6'-(二乙基氨基)-3'-甲基荧烷(CAS号:21121-62-0)、6'-(二乙氨基)-1',3'-二甲基荧烷(CAS号:21934-68-9)、6'-(二乙氨基)-1',3'-二甲基荧烷(CAS号:21934-68-9)、2-氯-6-(二乙基氨基)-荧烷(CAS号:26567-23-7)、3-二乙基氨基苯并荧烷(CAS号:26628-47-7)、3',6'-双(二乙基氨基)-2-(4-硝基苯基)螺[异吲哚-1,9'-呫吨]-3-酮(CAS号:29199-09-5)、2-苯氨基-3-甲基-6-二乙氨基荧烷(CAS号:29512-49-0)、2'-(二苄胺基)-6'-(二乙氨基)荧烷(CAS号:34372-72-0)、2-(2,4-二甲基苯氨基)-3-甲基-6-二乙氨基荧烷(黑色15,CAS号:36431-22-8)、3-(1,2-二甲基-3-吲哚基)-3-[4-(二乙基氨基)-2-甲基苯基]苯酞(CAS号:36499-49-7)、3',6'-二甲氧基荧烷(CAS号:36886-76-7)、3,3-双-(1-丁基-2-甲基-吲哚-3-基)-3H-异苯并呋喃-1-酮(红色40,CAS号:50292-91-6)、3,3-双-(2-甲基-1-辛基-1H-吲哚-3-基)-3H-异苯并呋喃-1-酮(CAS号:50292-95-0)、2'-苯胺基-6'-[乙基(对甲苯基)氨基]-3'-甲基螺[异苯并呋喃-1(3H)、9'-[9H]呫吨]-3-酮(CAS号:59129-79-2)、3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞(CAS号:69898-40-0)、3-(N-乙基-N-异戊氨基)-6-甲基-7-苯胺基-芴(CAS号:70516-41-5)、3-[4-(二乙基氨基)苯基]-3-(1-乙基-2-甲基-1H-吲哚-3-基)苯酞(CAS号:75805-17-3)、2'-(2-氯苯胺)-6'-(二丁基氨基)荧烷(CAS号:82137-81-3)、2-苯基氨基-3-甲基-6-二丁基氨基荧烷(CAS号:89331-94-2)、3-(1-丁基-2-甲基-1H-吲哚-3-基)-6-(二甲氨基)-3-[4-(二甲氨基)苯基]-3-(1(3H)-异苯并呋喃酮(CAS号:92453-31-1)、7-(4-二乙基氨基-2-己基氧基苯基)-7-(1-乙基-2-甲基-1H-吲哚-3-基)-7H-呋喃并[3,4-b]吡啶-5-酮(蓝色203,CAS号:98660-18-5)、7,7-双[4-(二乙基氨基)-2-乙氧基苯基]呋喃并[3,4-b]吡啶-5-酮(CAS号:132467-74-4)、N,N-二甲基-4-[2-[2-(辛氧基)苯基]-6-苯基-4-吡啶基]苯胺(黄色CK37,CAS号:144190-25-0)、3-(2,2-双(1-乙基-2-甲基吲哚-3-基)乙烯基)-3-(4-二乙基氨基苯基)-苯酞(CAS号:148716-90-9)及其混合物。
根据优选实施例,有机染料-电子给体化合物(A)选自3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞(蓝色63,CAS号:69898-40-4)、2'-(二苄氨基)-6'-(二乙氨基)荧烷(CAS号:34372-72-0)、N,N-二甲基-4-\[2-[2-(辛氧基)苯基]-6-苯基-4-吡啶基]苯胺(黄色CK37,CAS号:144190-25-0)、7-(4-二乙基氨基-2-己基氧基苯基)-7-(1-乙基-2-甲基-1H-吲哚-3-基)-7H-呋喃并[3,4-b]吡啶-5-酮(蓝色203,CAS号:98660-18-5)、2-(2,4-二甲基苯基氨基)-3-甲基-6-二乙基氨基荧烷(黑色15,CAS号:36431-22-8)、3,3-双-(1-丁基-2-甲基-吲哚-3-基)-3H-异苯并呋喃-1-酮(红色40,CAS号:50292-91-6)及其混合物。
作为受电子化合物(B),可以涉及但不限于具有活性质子的化合物,例如具有酚羟基的化合物(单酚或多酚),例如双酚或三酚,及其衍生物,其具有取代基,例如烷基、芳基、酰基、烷氧羰基、羧基及其酯,以及酰胺基、卤素原子和酚醛缩合树脂。
在本发明的受电子化合物(B)中,下列术语是指:
烷基:饱和、直链或支链的C1-C20,优选C1-C12,更优选C1-C6,并且甚至更优选C1-C4烃基脂族基团。术语“支链”意味着直链烷基链带有至少一个低级烷基,例如甲基或乙基。作为烷基,可涉及例如甲基、乙基、正丙基、异丙基、正丁基、叔丁基和正戊基。
芳基:衍生自至少一个芳环的任何官能团或取代基;芳环对应于包含离域π-***的任何平面单环或多环基团,其中环的每个原子包含p轨道,所述p轨道彼此重叠;在此类芳基中,可以涉及的是苯基、联苯基、萘和蒽基。本发明的芳基优选包含4至12个碳原子,并且甚至更优选5至6个碳原子。甚至更优选地,本发明的芳基是苯基。
因此,受电子化合物(B)可以选自2,2-双(4-羟基-3-甲基苯基)丙烷(双酚C,CAS号:79-97-0)、4-己基-1,3-二羟基苯(4-己基间苯二酚,CAS号:136-77-6)、4,4'-亚环己基双酚(BPZ,CAS号:843-55-0)、4,4'-(六氟异亚丙基)二酚(双酚AF,CAS号:1478-61-1)、4,4'-(1-苯基亚乙基)双酚(CAS号:1571-75-1)、2,2'-二羟基联苯(CAS号:1806-29-7)、4,4'-亚乙基双苯酚(CAS号:2081-08-5)、4,4'-(1,4-亚苯基二异亚丙基)双酚(CAS号:2167-51-3)、1,1-双(4-羟基-3-甲基苯基)环己烷(CAS号:2362-14-3)、9,9-双(4-羟基苯基)芴(CAS号:3236-71-3)、4,4'-(1,3-亚苯基二异亚丙基)双酚(CAS号:13595-25-0)、1,1,1-三(4-羟基苯基)乙烷(CAS号:27955-94-8)、4,4'-(2-乙基亚己基)二酚(CAS号:74462-02-5)、α,α,α'-三(4-羟基苯基)-1-乙基-4-异丙苯(CAS号:110726-28-8)、4-(1,1,3,3-四甲基丁基)苯酚(CAS号:140-66-9)、4-羟基二苯醚(CAS号:831-82-3)、双(2-羟基-1-萘基)甲烷(CAS号:1096-84-0)、4-(甲基磺酰基)苯酚(CAS号:14763-60-1)、4-羟基苯基-4'-异丙氧基苯基砜(CAS号:95235-30-6)、4,4'-二羟基联苯(CAS号:92-88-6)、4-羟基联苯(CAS号:92-69-3)、对羟基枯烯(CAS号:99-89-8)、2,4-二羟基二苯甲酮(CAS号:131-56-6)、氢醌单甲醚(HQMME,CAS号:150-76-5)、3-正十五烷基苯酚(CAS号:501-24-6)、4-(2-苯基异丙基)苯酚(CAS号:599-64-4)、5-氯-2-(2,4-二氯苯氧基)苯酚(CAS号:3380-34-5)、N-(对甲苯磺酰基)-N'-(3-(对甲苯磺酰基)苯基)脲(CAS号:232938-43-1)、2,2-双(3,5-二溴-4-羟基苯基)丙烷(CAS号:79-94-7)、4,4'-亚异丙基二苯酚(CAS号:80-05-7)和4,4'-磺酰二苯酚(CAS号:80-09-1)。
根据优选实施例,受电子化合物(B)选自2,2-双(4-羟基-3-甲基苯基)丙烷(双酚C,CAS号:79-97-0)、4-己基-1,3-二羟基苯(4-己基间苯二酚,CAS号:136-77-6)、4,4'-亚环己基双酚(BPZ,CAS号:843-55-0)、4,4'-(六氟异亚丙基)二酚(双酚AF,CAS号:1478-61-1)、4,4'-(1-苯基亚乙基)双酚(CAS号:1571-75-1),2,2'-二羟基联苯(CAS号:1806-29-7)、4,4'-(1,4-亚苯基二异亚丙基)双酚(CAS号:2167-51-3)、1,1-双(4-羟基-3-甲基苯基)环己烷(CAS号:2362-14-3)、9,9-双(4-羟基苯基)芴(CAS号:3236-71-3)、4,4'-(1,3-亚苯基二异亚丙基)双酚(CAS号:13595-25-0)、1,1,1-三(4-羟基苯基)乙烷(CAS号:27955-94-8)、4,4'-(2-乙基亚己基)二酚(CAS号:74462-02-5)、α,α,α'-三(4-羟基苯基)-1-乙基-4-异丙基苯(CAS号:110726-28-8)、及其混合物。
本发明的热致变色颜料组合物通过如下制备:将化合物(A)和(B)溶解在根据本发明定义的式(I)的双酚芴二酯化合物中,然后使用搅拌器,如均质混合器或分散器搅拌直至获得均匀混合物。
因此,与本发明的式(I)的双酚芴二酯化合物相关的化合物(A)和(B)可以配制成微胶囊的形式。因此,本发明的热致变色颜料组合物被封装在微胶囊中以形成微胶囊化的热致变色颜料。这种热致变色颜料微胶囊构成了本发明的另一主题。它们具有抗机械应力、不溶并因此可分散在水中以及缓慢聚集的优点。在本发明的微胶囊内的热致变色颜料组合物的熔融温度(或脱色温度T4)可以在20至80℃,优选30至80℃,并且甚至更优选40至70℃内变化。
在本发明的微胶囊内的热致变色颜料组合物的结晶温度(或重新着色温度T1)可以在-40到20℃,优选-30到10℃,并且甚至更优选-20到0℃内变化。
包含本发明的热致变色颜料组合物的微胶囊的平均直径在0.5至30μm,优选1至10μm,并且甚至更优选3至5μm范围内。该平均直径对应于体积d90,并且意味着90体积%的微胶囊小于d90的指示值。该平均直径可以使用来自马尔文公司(Malvern)的Zetasizer NanoZS***通过激光粒度测定法确定。
使用的微胶囊化方法包括但不限于常规方法,例如:
-依赖于微胶囊壳的原位形成的化学工艺。化学方法的代表性实例包括复合凝聚、界面聚合(IFP)、聚合物-聚合物不相容性、原位聚合、离心力工艺和浸入式喷嘴工艺,其中界面聚合(IFP)是首选方法,
-物理化学过程,例如通过相分离或凝聚、通过溶剂的蒸发萃取、通过乳液热凝胶化(热熔)或
-机械过程,例如通过雾化/干燥(喷雾干燥)、通过胶凝或冷冻滴、通过在流化床中涂覆(喷涂)。
包含本发明的热致变色颜料组合物的微胶囊有利地基于氨基塑料树脂,并且优选地基于三聚氰胺树脂、脲树脂或苯并苯并胍胺树脂。
包含本发明的热致变色颜料组合物的微胶囊优选通过三聚氰胺树脂的原位聚合制备。
本发明的另一个主题是一种热致变色墨水组合物,其包含根据本发明的热致变色颜料微胶囊和载体。
为了本发明的目的,术语“热致变色墨水组合物”意味着旨在用于书写工具如圆珠笔、毛笔、彩色铅笔、记号笔、荧光笔、粉笔和毡笔的墨水。它不应与印刷机中使用的印刷墨水混淆,并且其不对应于相同的技术限制,因此不对应于相同的规格。实际上,打算在本发明的框架内用在书写工具中的“热致变色墨水组合物”必须不含有其尺寸大于书写工具的通道的固体颗粒,以避免阻塞它们,从而不可避免地导致写作不可逆地停止。另外,它不能太流动,以免在写入过程中泄漏。但是,它必须足够流动以促进书写动作的顺畅。此外,它必须允许适合所用书写工具的墨水流量,特别是10到700mg/200m的书写速度,最好在250到650mg/200m的书写速度之间。它还必须足够快地干燥,以免弄脏书写介质。它还必须避免随着时间流逝的墨水迁移(渗色)问题。因此,本发明的热致变色墨水组合物将适用于其打算用于的书写工具。
相对于热致变色墨水组合物的总重量,存在于墨水组合物中的本发明的热致变色颜料微胶囊占5至40重量%,优选15至30重量%,并且更优选15至25重量%。
本发明的热致变色墨水组合物也主要由水组成。有利地,水占热致变色墨水组合物总重量的40至80重量%。
它可以进一步包含一种或多种与水混溶的溶剂。因此,本发明的热致变色墨水组合物可以含有有机或水性溶剂,优选水性溶剂。
在可以添加到热致变色墨水组合物中的溶剂中,可以涉及可与水混溶的极性溶剂,例如:
-醇:C1-C15直链或支链醇,如异丙醇、丁醇、异丁醇、戊醇、苯甲醇、甘油、二甘醇、聚甘油,
-酯,例如乙酸乙酯或乙酸丙酯,
-碳酸酯,例如碳酸丙烯酯或碳酸乙烯酯,
-酮,例如甲基异丁基酮(MIBK)、丙酮或环己酮,
-二醇如乙二醇、二甘醇、三甘醇、丙二醇、聚乙二醇、乙二醇单甲醚(EGME)、3-丁二醇和硫代乙二醇,
-酰胺,例如二甲基乙酰胺或二甲基甲酰胺,以及
-他们的混合物。
一种或多种溶剂可以占热致变色墨水组合物总重量的5至20重量%。
本发明的热致变色颜料微胶囊也可以与一种或多种特定的助剂混合,所述助剂根据预期的最终用途可以发挥不同的作用。这些应用可以包括用于书写工具的墨水,如圆珠笔、毛笔、彩色铅笔、记号笔、荧光笔、粉笔和毡笔。本发明的热致变色颜料微胶囊也可以添加到热塑性或热固性树脂组合物中以形成模制品。
在上述助剂中,可以涉及:
-能够产生胶凝作用的流变改性剂(流变剂),例如黄原胶或***胶,
-pH调节剂,例如氢氧化钠、三乙醇胺,
-表面活性剂,例如聚醚多元醇(DOW的TERGITOLTM),
-防腐剂,例如苯并***,
-润滑剂,
-分散剂,
-聚结剂,
-交联剂,
-润湿剂,
-增塑剂,
-抗氧化剂,
-紫外线稳定剂。
本发明的另一主题涉及书写工具,其包含:
-容纳根据本发明的热致变色墨水组合物的轴筒,和
-笔体,其传递储存在所述轴筒中的所述热致变色墨水组合物。
这些工具通常由包含本发明的墨水组合物的主体以及可能的摩擦构件组成。
本发明的书写工具有利地选自圆珠笔、毛笔、彩色铅笔、荧光笔、粉笔和记号笔,并且甚至更有利地是可通过摩擦擦除的圆珠笔。在优选的实施例中,书写工具是可通过摩擦擦除的圆珠笔,书写速度优选地在10至700mg/200m之间,并且更优选地在250至650mg/200m之间。
书写工具的摩擦构件优选是橡胶。
本发明的墨水组合物可以应用的载体是纸、纤维、皮革、塑料、玻璃、金属、木材、混凝土。
除上述内容外,本发明还包含其它的规定,这些规定将从下面的附加说明中得出,这些规定涉及根据本发明的式(I)的双酚芴二酯化合物作为热致变色颜料组合物中的温度变化调节剂的用途,以及它们的表征。
实例:
根据本发明的实例:
式(I)的双酚芴二酯化合物(1)的制备:
根据两种不同的方法合成化合物(1):
方法1:通过酰氯进行酯化
在该方法中,将14.2g的双酚FL(CAS号:3236-71-3)溶解在300mL的四氢呋喃(THF,CAS号:109-99-9)中。然后加入4.0g用作催化剂的三乙胺(CAS号:121-44-8)。然后将反应混合物冷却并保持在0℃的温度。反应混合物的温度通过包含干冰的乙醇冷浴来保持。通过将氮气引入反应容器中使反应混合物呈惰性。在30分钟时段内,向反应容器中逐滴缓慢加入20.0g肉豆蔻酰氯(CAS号:112-64-1)。使用的双酚/酰氯摩尔比为1/2。完全加入酰氯后,将反应容器加热至25℃,并在机械搅拌下搅拌2小时。
用200mL乙酸乙酯萃取粗反应混合物。将回收的有机相用200mL蒸馏水洗涤三次。然后将有机相用硫酸镁干燥,过滤,并通过旋转蒸发除去溶剂。然后将回收的残余物从乙醇中重结晶两次,得到纯度大于98%的化合物(1),通过气相色谱法(GC)确认。
方法2:通过羧酸酯化
在该方法中,将19.2g双酚FL(CAS号:3236-71-3)与50.0g肉豆蔻酸(CAS号:544-63-8)缩合,所述羧酸化合物用作溶剂。过量使用羧酸化合物,摩尔比为4/1。加入1.9g对甲苯磺酸(pTs-OH,CAS号:104-15-4)和一种有机可溶性酸性催化剂,催化剂/双酚摩尔比为0.05/1。然后在1天的时间内,在400毫巴的减压下将反应混合物加热至160℃的温度。如薄层色谱法所证实,当双酚被完全消耗时,终止反应。从反应混合物中回收得到的化合物(1),并通过从乙醇中反复重结晶来纯化,通过气相色谱法(GC)证实,得到的化合物(1)的纯度>97%。
热致变色颜料组合物的制备:
通过混合2.2重量份的3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞(化合物(A),蓝色63,CAS号:69898-40-4)、2.5重量份4,4'-(六氟异亚丙基)二酚(化合物(B1),双酚AF,CAS号:1478-61-1)、2.5重量份的2,2-双(4-羟基-3-甲基苯基)丙烷(化合物(B2),CAS号:79-97-0)和92.8重量份的前述方法1制备的化合物(1)(化合物(C))来制备热致变色颜料组合物。
在搅拌下将所得混合物在110℃的温度下加热1小时,直到化合物(A)、(B1)和(B2)在化合物(C)中完全溶解。
热致变色颜料微胶囊的制备:
将7.8重量份的(马来酸酐)-共-(马来酸甲基乙烯基醚)共聚物的水溶液(31重量%的共聚物的溶液)用14.8重量份的氢氧化钠水溶液(1.0M溶液)中和至pH=4.5。用31.4重量份的水稀释所得溶液,并在1小时内用均质混合器以15m.s-1的速度均化混合物。加入27.4重量份的先前制备的热致变色颜料组合物,并将形成的乳液在85℃的温度下保持30分钟时段。在10分钟内将18.6重量份的三聚氰胺-甲醛预聚物溶液(50重量%的预聚物的水溶液)缓慢加入到混合物中。预聚物溶液完全加入后,将混合物在90℃的温度下以15m.s-1的速度加热4小时。
将热致变色颜料微胶囊以水基分散液(也称为浆液)的形式回收。
浆液由分散在水性溶剂中的热致变色颜料微胶囊组成,该微胶囊的d90直径为5.2μm,所述直径使用马尔文仪器公司(Malvern Instruments)的Zaltaizer Nano ZS***在632nm的光照下测定。
所获得的热致变色颜料微胶囊具有在高于68℃的温度下将颜色从蓝色改变为无色的性质,并具有变色的滞后效应。
热致变色墨水组合物的制备:
在机械搅拌器的搅拌下将15重量份的甘油加热至30℃。然后将0.25重量份的苯并***、0.25重量份的杀菌剂水溶液(其含有2.5重量%的1,2-苯并异噻唑啉-3-酮和2.5重量%的2-甲基-4-异噻唑啉-3-酮)、0.5重量份的聚硅氧烷聚合物的水分散体(其含有50重量%的聚合物)和0.5重量份的聚醚多元醇加入到混合物中。将混合物在30℃下搅拌约15分钟,直到苯并***完全溶解。一旦均匀,加入0.5重量份的黄原胶,并在机械搅拌下混合15分钟。黄原胶分散后,在15分钟内缓慢加入33重量份的软化水。在机械搅拌下将水合混合物搅拌3小时。向该混合物中加入49.5重量份先前制备的热致变色微胶囊浆料组合物。通过添加0.5重量份的三乙醇胺将pH控制为pH=8。然后使用高速分散器以至少15ms-1的切向速度将获得的蓝色墨水组合物分散30分钟。然后在注入墨盒之前,将制备的墨水组合物在减压下(100至400mbar之间)脱气。
确定包含化合物(1)的热致变色颜料微胶囊的脱色和重新着色温度:
使用TA Instruments Q20设备,通过差示扫描量热法(DSC),在-50至100℃的温度范围内,以20℃/分钟的冷却/加热速度,测量所获得的热致变色颜料微胶囊的转变温度。测得的温度示于下表1中。
表1:根据实例的热致变色颜料微胶囊的转变温度
转变温度如下所示:
T1:完全重新着色温度,
T2:部分重新着色温度,
T3:部分脱色温度,
T4:完全脱色温度,
ΔH=滞后窗口=TG-TH。
比较实例:
根据与本发明实例相同的程序进行对比实例,但是通过用下式的双酚FL(CAS号:3236-71-3)代替由方法1制备的本发明双酚芴二酯化合物(1):
下表2列出了所测试的热致变色颜料组合物的组成。与上述热致变色颜料组合物的唯一区别在于没有2,2-双(4-羟基-3-甲基苯基)丙烷(化合物(B2)),并且化合物(A)、(B)和化合物(1)的变化如下:
表2:所测试的热致变色颜料组合物的组成
包含本发明的化合物(1)作为反应介质的组合物表现出可逆的热致变色行为,在70℃以上有颜色损失并且在低于30℃的温度下(封装之前)发生重新着色。
相反,双酚-FL的熔点为225℃,远远超过了热致变色颜料组合物的目标熔点范围50-75℃。两种比较组合物在250℃(高于双酚-FL的熔点)的加热导致显色有机化合物(无色染料)永久分解和脱色。因此,没有观察到热致变色效应。因此,双酚FL显然不适合用作热致变色颜料组合物中的反应介质。
Claims (13)
2.根据权利要求1所述的化合物的用途,其中R1和R2相同并且表示直链或支链C2-C30烷基,优选直链或支链C4-C20烷基,并且更优选直链或支链C6-C18烷基。
3.根据权利要求1或权利要求2所述的化合物的用途,其中R1和R2相同并且表示直链或支链C6-C30烷基,优选直链或支链C6-C18烷基,并且更优选直链C13烷基。
4.一种热致变色颜料组合物,其包含:
(A)给电子显色有机化合物,
(B)受电子化合物,和
(C)根据权利要求1至3中任一项的由式(I)表示的化合物,作为控制所述组分(A)和(B)之间的颜色反应的反应介质。
5.根据权利要求4所述的热致变色颜料组合物,其中,所述化合物(A)选自3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞(蓝色63,CAS号:69898-40-4)、2'-(二苄氨基)-6'-(二乙氨基)荧烷(CAS号:34372-72-0)、N,N-二甲基-4-[2-[2-(辛氧基)苯基]-6-苯基-4-吡啶基]苯胺(黄色CK37,CAS号:144190-25-0)、7-(4-二乙基氨基-2-己基氧基苯基)-7-(1-乙基-2-甲基-1H-吲哚-3-基)-7H-呋喃并[3,4-b]吡啶-5-酮(蓝色203,CAS号:98660-18-5)、2-(2,4-二甲基苯基氨基)-3-甲基-6-二乙基氨基荧烷(黑色15,CAS号:36431-22-8)、3,3-双-(1-丁基-2-甲基-吲哚-3-基)-3H-异苯并呋喃-1-酮(红色40,CAS号:50292-91-6)及其混合物。
6.根据权利要求4或权利要求5所述的热致变色颜料组合物,其中,所述化合物(B)选自2,2-双(4-羟基-3-甲基苯基)丙烷(双酚C,CAS号:79-97-0)、4-己基-1,3-二羟基苯(4-己基间苯二酚,CAS号:136-77-6)、4,4'-亚环己基双酚(BPZ,CAS号:843-55-0)、4,4'-(六氟异亚丙基)二酚(双酚AF,CAS号:1478-61-1)、4,4'-(1-苯基亚乙基)双酚(CAS号:1571-75-1)、2,2’-二羟基联苯(CAS号:1806-29-7)、4,4'-(1,4-亚苯基二异亚丙基)双酚(CAS号:2167-51-3)、1,1-双(4-羟基-3-甲基苯基)环己烷(CAS号:2362-14-3)、9,9-双(4-羟基苯基)芴(CAS号:3236-71-3)、4,4'-(1,3-亚苯基二异亚丙基)双酚(CAS号:13595-25-0)、1,1,1-三(4-羟基苯基)乙烷(CAS号:27955-94-8)、4,4'-(2-乙基亚己基)二酚(CAS号:74462-02-5)、α,α,α'-三(4-羟基苯基)-1-乙基-4-异丙基苯(CAS号:110726-28-8)、及其混合物。
7.一种封装了根据权利要求4至6中任一项所述的热致变色颜料组合物的热致变色颜料微胶囊。
8.一种热致变色墨水组合物,其包含根据权利要求7所述的热致变色颜料微胶囊和载体。
9.根据权利要求8所述的热致变色墨水组合物,其中所述热致变色颜料微胶囊以相对于所述热致变色墨水组合物总重量的5至40重量%的量存在。
10.一种书写工具,其包含:
-轴筒,其容纳根据权利要求8或权利要求9所述的热致变色墨水组合物,和
-笔体,其传递储存在所述轴筒中的所述热致变色墨水组合物。
11.根据权利要求10所述的书写工具,其还包含摩擦构件。
12.根据权利要求10或权利要求11所述的书写工具,其选自圆珠笔、毛笔、彩色铅笔、荧光笔、粉笔和毡笔,并且优选地是可通过摩擦擦除的圆珠笔。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010064447A1 (ja) * | 2008-12-05 | 2010-06-10 | 株式会社松井色素化学工業所 | 可逆感温変色性ヒステリシス組成物 |
JP2017200748A (ja) * | 2016-05-07 | 2017-11-09 | 三菱鉛筆株式会社 | 熱変色性筆記具 |
CN108136804A (zh) * | 2015-09-03 | 2018-06-08 | 热成像测量有限公司 | 用于变色组合物中的化合物 |
WO2018150146A1 (fr) * | 2017-02-17 | 2018-08-23 | Societe Bic | Nouvelle composition de pigment thermochrome comprenant un composé de formule (i) en tant que milieu réactionnel. |
WO2018168488A1 (ja) * | 2017-03-14 | 2018-09-20 | 三菱鉛筆株式会社 | 色素、マイクロカプセル顔料及び筆記具用インク組成物 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4967306A (en) | 1989-05-05 | 1990-10-30 | Minnesota Mining And Manufacturing Company | High purity aromatic polyesters |
DE4107242A1 (de) * | 1991-03-07 | 1992-09-10 | Ruetgerswerke Ag | Verfahren zur herstellung von 9,9-bis-(4-hydroxyphenyl-)fluoren |
US5124307A (en) | 1991-08-15 | 1992-06-23 | Appleton Papers Inc. | Thermally-responsive record material |
JPH08175028A (ja) | 1994-12-21 | 1996-07-09 | Tomoegawa Paper Co Ltd | 感熱記録媒体 |
JP2008150483A (ja) | 2006-12-18 | 2008-07-03 | Sakura Color Prod Corp | 熱変色性組成物及び熱変色性マイクロカプセル |
US8865621B2 (en) * | 2012-08-06 | 2014-10-21 | Sanford, L.P. | Irreversible color changing ink compositions |
CN105308150A (zh) * | 2013-06-14 | 2016-02-03 | 百乐墨水株式会社 | 感温变色性色彩记忆性组合物及内包有该组合物的感温变色性色彩记忆性微胶囊颜料 |
EP3333240B1 (en) * | 2015-08-03 | 2020-08-19 | The Pilot Ink Co., Ltd. | Thermochromic color-memory composition and thermochromic color-memory microcapsule pigment encapsulating same |
EP3904468B1 (en) * | 2020-04-30 | 2022-10-19 | Société BIC | Method for preparing thermochromic water-based gel ink compositions, and thermochromic water-based gel ink compositions thereof |
-
2019
- 2019-09-20 BR BR112021003698-9A patent/BR112021003698A2/pt not_active Application Discontinuation
- 2019-09-20 CN CN201980055654.5A patent/CN112639033A/zh active Pending
- 2019-09-20 EP EP19769518.2A patent/EP3856855B1/en active Active
- 2019-09-20 MX MX2021002431A patent/MX2021002431A/es unknown
- 2019-09-20 WO PCT/EP2019/075305 patent/WO2020064537A1/en unknown
- 2019-09-20 JP JP2021510773A patent/JP2022500515A/ja active Pending
- 2019-09-20 US US17/278,457 patent/US11814528B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010064447A1 (ja) * | 2008-12-05 | 2010-06-10 | 株式会社松井色素化学工業所 | 可逆感温変色性ヒステリシス組成物 |
CN108136804A (zh) * | 2015-09-03 | 2018-06-08 | 热成像测量有限公司 | 用于变色组合物中的化合物 |
JP2017200748A (ja) * | 2016-05-07 | 2017-11-09 | 三菱鉛筆株式会社 | 熱変色性筆記具 |
WO2018150146A1 (fr) * | 2017-02-17 | 2018-08-23 | Societe Bic | Nouvelle composition de pigment thermochrome comprenant un composé de formule (i) en tant que milieu réactionnel. |
WO2018168488A1 (ja) * | 2017-03-14 | 2018-09-20 | 三菱鉛筆株式会社 | 色素、マイクロカプセル顔料及び筆記具用インク組成物 |
Non-Patent Citations (1)
Title |
---|
肖瑞华编著: "《煤焦油化工学》", 28 February 2009, 冶金工业出版社 * |
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US20210363371A1 (en) | 2021-11-25 |
WO2020064537A1 (en) | 2020-04-02 |
US11814528B2 (en) | 2023-11-14 |
JP2022500515A (ja) | 2022-01-04 |
MX2021002431A (es) | 2021-08-05 |
EP3856855A1 (en) | 2021-08-04 |
BR112021003698A2 (pt) | 2021-05-18 |
EP3856855B1 (en) | 2022-07-20 |
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