JPH0229032B2 - - Google Patents
Info
- Publication number
- JPH0229032B2 JPH0229032B2 JP56132542A JP13254281A JPH0229032B2 JP H0229032 B2 JPH0229032 B2 JP H0229032B2 JP 56132542 A JP56132542 A JP 56132542A JP 13254281 A JP13254281 A JP 13254281A JP H0229032 B2 JPH0229032 B2 JP H0229032B2
- Authority
- JP
- Japan
- Prior art keywords
- prepolymer
- urea
- melamine
- microcapsules
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003094 microcapsule Substances 0.000 claims description 62
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 46
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 41
- 229920000877 Melamine resin Polymers 0.000 claims description 39
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 30
- 125000002091 cationic group Chemical group 0.000 claims description 29
- 239000004202 carbamide Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 102000010029 Homer Scaffolding Proteins Human genes 0.000 claims description 14
- 108010077223 Homer Scaffolding Proteins Proteins 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000003945 anionic surfactant Substances 0.000 claims description 12
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 7
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005354 coacervation Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 58
- 239000000243 solution Substances 0.000 description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 24
- 235000013877 carbamide Nutrition 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000002775 capsule Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 7
- 239000007903 gelatin capsule Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 methyl ethyl ketone Chemical compound 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001600 hydrophobic polymer Polymers 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- ZDTVBVUHESZSGN-UHFFFAOYSA-N 1,1-diaminoethanol Chemical compound CC(N)(N)O ZDTVBVUHESZSGN-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 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 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- AKTDWFLTNDPLCH-UHFFFAOYSA-N 1,1,3,3-tetrakis(hydroxymethyl)urea Chemical compound OCN(CO)C(=O)N(CO)CO AKTDWFLTNDPLCH-UHFFFAOYSA-N 0.000 description 1
- GNPWYHFXSMINJQ-UHFFFAOYSA-N 1,2-dimethyl-3-(1-phenylethyl)benzene Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CC=CC=C1 GNPWYHFXSMINJQ-UHFFFAOYSA-N 0.000 description 1
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 206010068516 Encapsulation reaction Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
Description
本発明は感圧記録紙用微小カプセルおよびその
製造方法に関する。更に詳しくは、微小カプセル
の殻が主としてメラミン尿素ホルムアルデヒド樹
脂からなり、従来の感圧記録紙に比べ耐溶剤性が
格段に優れた感圧記録紙の製造に適した微小カプ
セルを提供することにある。
一般の感圧記録紙は、たとえばロイコ型染料
（カラーホーマー）の溶液を芯物質として内包す
る微小カプセルを紙の裏面に塗布した上葉紙
（CB紙）と酸性白土或いは酸性を呈する樹脂など
の呈色剤を塗布した下葉紙（CF紙）とを重ね合
せ、筆圧又はタイプライターの印字圧等により、
その部分の微小カプセルを破壊し、カラーホーマ
ーと呈色剤を接触させることにより発色記録させ
るものである。
感圧記録紙は、近年事務の効率化、特にコンピ
ユーターの発展普及に伴い益々多方面に使用され
るようになり、それに応じ使用条件の厳しいとこ
ろでの使用が求められ、そのために、感圧記録紙
用の微小カプセルとして耐湿性、耐熱性、耐光性
に優れたものが要望されている。また、感圧記録
紙の製造においては耐溶剤性に優れた微小カプセ
ルが要求されている。
即ち、従来感圧記録紙は、通常水を分散媒と
し、水溶性のバインダーおよび添加物からなるス
ラリー状微小カプセルを紙に塗布することにより
製造されている。しかし乍ら、水を分散媒とする
場合には、乾燥に時間がかかり、またヒジワを生
ずるので寸法安定性に欠ける。これらの欠点を解
消し、且つ、感圧記録紙の生産性を向上させるた
めには微小カプセルを塗布する際に用いる分散媒
として、より速乾性の分散媒を用いることが考え
られる。このような分散媒としては通常印刷等で
インキ溶剤として用いられる有機溶剤例えばイソ
プロピルアルコール、エチルアルコールの如きア
ルコール類、酢酸エチルの如きエステル類、メチ
ルエチルケトンの如きケトン類、ケロシン、トル
エン、キシレンの如き炭化水素溶剤等、又は亜麻
仁油、ヒマシ油の如き植物油などが適している。
しかし乍ら従来、実用化されあるいは提案されて
いる感圧記録紙用微小カプセルはいずれも上述し
た如き有機溶剤中で安定して存在し得ない。これ
ら溶剤中で安定して存在し得る微小カプセルがあ
れば、感圧記録紙の製造に当り、カラーホーマー
を内包した微小カプセルを塗布した紙の乾燥に要
する時間を短かくすることができ生産性を大巾に
向上させることができるのみならず、ヒジワ発生
のおそれもない。更にはスポツト印刷等による部
分感圧記録紙の製造も容易となる。上述の如く
種々の利点があることが、耐溶剤性に優れた感圧
記録紙用微小カプセルの要望される所以である。
現在実用されている殆んどの感圧記録紙に使用
されている微小カプセルの膜壁はゼラチンを主材
としたもの（以下ゼラチンカプセルと云う）であ
り、ゼラチンカプセルは耐湿性が悪く、耐光性が
悪く、微生物に弱いなどの欠点があり、更に耐溶
剤性に欠けている。一方ゼラチンカプセルに代る
ものとして疎水性高分子を膜壁材とする微小カプ
セルが種々提案されている。これら微小カプセル
の膜壁の材料としては尿素ホルムアルデヒド樹
脂、メラミン樹脂ポリアミド、ポリウレタン等が
用いられており、これらの膜壁材料をin situ重
合法又は界面重合法によりカプセル化している。
しかし乍ら、これら従来の微小カプセルは耐湿
性、耐光性等においてゼラチンカプセルに比べ若
干改良されているとはいえ、感圧記録紙用微小カ
プセルとして未だ満足なものではなく、特に耐溶
剤性に欠けている。
本発明は、メラミン、尿素及びホルムアルデヒ
ドよりなる樹脂ポリマーを膜材とするが従来の方
法でメラミン、尿素及びホルムアルデヒドよりな
る樹脂を膜材として形成された微小カプセルはゼ
ラチンカプセルに比して勝る面があるとは言え耐
溶剤性に欠ける。例えばメラミン、尿素及びホル
ムアルデヒドよりなるプレポリマーのみで微小カ
プセルを形成させる方法（特開昭54−150212）が
提示されているが感圧記録紙用に適した微小カプ
セルを得る事が出来ないし耐溶剤性も著しく劣
る。又、反応性界面活性剤と称する尿素ホルムア
ルデヒド化合物又はメラミンホルムアルデヒド化
合物から誘導された疎水性基と親水性基とを有す
る物質をプレポリマーと併用する方法（特開昭46
−7313）、或いはスチレン無水マレイン酸共重合
体を酢酸ビニル無水マレイン酸共重合体とをプレ
ポリマーと併用する方法（特開昭54−10876）等
が提案されている。
しかし乍ら、これらの方法はゼラチンカプセル
製造時に於ける欠点例えば低濃度溶液からのみカ
プセル化が可能であるという欠点を解決したが、
これらの方法により得られる微小カプセルは耐湿
性、耐光性等においてゼラチンカプセルに比べ若
干改良されているとはいえ、感圧記録紙用微小カ
プセルとして未だ満足なものではなく、殊に、後
述する如く有機溶剤中における安定性に欠けてい
る。
本発明者等は、上述した如き現状に鑑み、メラ
ミン尿素ホルムアルデヒド系樹脂を膜壁とする微
小カプセルが疎水性であり、その原料が安価に入
手できるという特性を生かした上、耐溶剤性に優
れる感圧記録紙用微小カプセルの製造について鋭
意研究した結果本発明をなすに至つた。
本発明の感圧記録紙用微小カプセルは、カラー
ホーマー溶液を内包する膜壁が、メラミンホルム
アルデヒドプレポリマー、尿素ホルムアルデヒド
プレポリマー及びメラミン尿素ホルムアルデヒド
プレポリマーから選択される少なくとも２種のプ
レポリマー又はメラミン尿素ホルムアルデヒドプ
レポリマーであるプレポリマーと水溶性カチオニ
ツク尿素樹脂とをアニオニツク界面活性剤の存在
のもとに重縮合させてなる樹脂であることを特徴
とする。
更に、本発明の感圧記録紙用微小カプセルの製
造方法は、上述の水系分散液に酸触媒を加えて水
溶性カチオニツク尿素樹脂とアニオニツク界面活
性剤によるコンプレツクス・コアセルベーシヨン
を生起させつつ、プレポリマーおよび水溶性カチ
オニツク尿素樹脂を重縮合させて、分散している
カラーホーマー溶液の微小液滴を完全に被覆する
疎水性高分子膜壁を形成させて微小カプセル化す
る。
上記本発明の実施において特に重要なことは水
溶性カチオニツク尿素樹脂とアニオニツク界面活
性剤を、即ち、電荷が異付号である２種の物質を
プレポリマーと併用することにある。プレポリマ
ーの縮重合に際し、少量のカチオニツク尿素樹脂
とアニオニツク界面活性剤を共存させることによ
り安定な分散液を得ることができると同時に、均
質なカプセルを得ることができる。
次に本発明の微小カプセルの製造法を具体的に
説明する。
先ず、少なくとも水溶性カチオニツク尿素樹脂
とアニオニツク界面活性剤の存在する水系混合液
とカラーホーマー溶液とを適当な手段、例えば、
ホモジナイザー、攪拌機、超音波等を用いてカラ
ーホーマー溶液が１〜8μの微小液滴となるよう
に乳化分散させる。プレポリマーはこの乳化前の
混合液中に予め存在させておいてもよいが、乳化
の途中又は乳化後に一度に又は数回に分けて添加
してもよい。このプレポリマーを含む分散液をゆ
るやかに攪拌しながら酸触媒を加えて、PH2.5〜
6.0、反応温度15〜60℃で２〜15時間反応させる
ことにより微小カプセル化は終了する。なお、こ
の反応過程中適当量の水を加えることもできる。
本発明に使用するプレポリマーはメラミン、尿
素及びホルムアルデヒドより製造されるものであ
り、メラミンホルムアルデヒドプレポリマー
（MFプレポリマー）と尿素ホルムアルデヒドプ
レポリマー（UFプレポリマー）との併用又はメ
ラミン、尿素およびホルムアルデヒドを反応させ
て得られるメラミン尿素ホルムアルデヒドプレポ
リマー（MUFプレポリマー）単独又は前記MF
プレポリマー、UFプレポリマーと併用しても用
いられる。ここでメラミンホルムアルデヒドプレ
ポリマーとは、モノメチロールメラミンからヘキ
サメチロールメラミンに至るメチロールメラミン
又はこれらメチロール化度の異なるメチロールメ
ラミンの混合物又は上記メチロールメラミンとメ
ラミンとホルムアルデヒドとの混合物を意味し、
更にはメラミンとホルムアルデヒドの反応を更に
すすめたオリゴマー、すなわち重合度２〜10のメ
チロールメラミンの塩酸処理等によつて得られた
透明なコロイド溶液であつてもよい。このメラミ
ンホルムアルデヒドプレポリマーはメラミンとホ
ルマリンとの混合物をアルカリ性で加熱すること
により容易に生成することができ、この水系反応
液はそのままカプセル化に供することができる。
尿素ホルムアルデヒドプレポリマーはモノメチ
ロール尿素からテトラメチロール尿素に至るメチ
ロール化尿素又はこれらメチロール化度の異なる
メチロール尿素の混合物又は前記メチロール尿素
と尿素とホルムアルデヒドとの混合物を意味し、
さらには尿素とホルムアルデヒドの反応をさらに
すすめたオリゴマー、すなわち重合度２〜５の親
水基を持つた透明なコロイド溶液であつてもよ
い。
原料のメラミン；尿素およびホルムアルデヒド
の比は膜形成に重要な影響を与える。ホルムアル
デヒドはプレポリマーを構成するメラミン１モル
に対し1.0〜9.0モル好ましくは1.6〜7.0モル及び
尿素１モルに対し0.6〜4.0モル好ましくは1.0〜
3.0モルの割合になる量とする。又メラミンと尿
素の比は尿素１モルに対してメラミン0.05〜9.0
モルの範囲である。このような比は微小カプセル
の膜壁形成を均質に行なわしめ生成膜に充分な膜
強度、不透過性、特に耐溶剤性を保持せしめるた
めである。
用いるプレポリマー中におけるメラミンと尿素
の比が変ることにより得られる微小カプセルの性
状が異なつてくる。例えばプレポリマーとして
MFプレポリマー単独に近い組成のものを用いて
得られる微小カプセルは比重が重くカプセルが沈
降しやすく高濃度のカプセルスラリーを得ること
ができるが一方沈降しない分散液を得たい時は
UFプレポリマーに近い組成のものが好ましい。
又耐溶剤性という観点からするとメラミン／尿素
のモル比が0.15〜5.0付近のものが優れている。
カプセル化に際し、用いるプレポリマーの量はカ
ラーホーマー溶液１ｇ当り0.1〜１ｇの範囲で使
用することが好ましい。
本発明で使用する水溶性カチオニツク尿素樹脂
は、尿素ホルムアルデヒド樹脂にカチオニツクな
変性剤を導入したものであり、例えば尿素ホルム
アルデヒドプレポリマーに変性剤としてテトラエ
チレンペンタミン、ジアミノエタノール、ジシア
ンジアミド、ジエチルアミノエタノール、グアニ
ール尿素又はこれらに類するものを加え公知の方
法で縮重合して容易に得られる。プレポリマーに
対する水溶性カチオニツク尿素樹脂の割合は重量
比で１対0.01乃至0.5の範囲であることが好まし
い。
また、アニオニツク界面活性剤としては脂肪酸
塩類、高級アルコール硫酸エステル類、アルキル
アリルスルホン酸塩類等を例示し得るが、ドデシ
ルベンゼンスルホン酸ソーダが好ましい。
このアニオニツク界面活性剤の使用量は水溶性
カチオニツク尿素樹脂１重量部に対し0.01〜0.1
重量部にすることにより広いPH領域即ちPH2.5〜
6.0の範囲で安定な分散液を得ることができる。
更に酸触媒としては、ギ酸、酢酸又はくえん酸
のような低分子カルボン酸、塩酸、硝酸又はリン
酸のような無機酸、或は硫酸アルミニウム、オキ
シ塩化チタン、塩化マグネシウム、塩化アンモニ
ウム、硝酸アンモニウム、硫酸アンモニウム、酢
酸アンモニウムのような酸性塩又は加水分解し易
い塩などを例示し得、これらは単独又は混合して
使用できる。
上述の如くして行なわれる本発明による微小カ
プセルの製造に於ては、従来のプレポリマーの水
溶液のみを使用する場合、又はプレポリマーとカ
チオニツク尿素樹脂だけとの併用の場合、或いは
プレポリマーと尿素樹脂より誘導された反応性界
面活性剤（例えば特開昭46−7313号）との併用の
場合等に比べ、カラーホーマー溶液の乳化力が大
であり、低粘度で安定な分散液とすることがで
き、更に形成されるカプセル膜壁は、前述の公知
の方法によるカプセルに比べ膜の透過性が著しく
少ない特長を有する。
このような利点を有するゆえんは、水溶性カチ
オニツク尿素樹脂とアニオニツク界面活性剤とが
或る組成とPHに設定されるとコンプレツクスコア
セルベートを生成することにある。液組成が同じ
であれば、PH１〜６付近の領域でコアセルベート
の生成が最も少なく、PH７付近およびをPH３以下
になるとコアセルベートの生成は著しい。従つて
カラーホーマ溶液の乳化分散は、粒子の凝進防止
を考慮して、コアセルベートの生成の少ないPH領
域で行ない、次いで酸触媒でPHを低下させること
によりカプセル化反応を起させる。このときプレ
ポリマーの高分子化とコンプレツクスコアセルベ
ートの生成とが連続的に行なわれる結果カプセル
膜壁が形成され、又水溶性カチオニツク尿素樹脂
も縮合反応して、疎水性高分子となり、緻密で均
一な膜壁が形成され微小カプセルとなる。上述し
た如く、本発明による微小カプセル化はコンプレ
ツクコアセルベーシヨン法とin situ重合法を組
合せ同時的に進行させるようにして行うものであ
り、従来技術にみられない新規な方法である。
かくして得られる本発明の微小カプセルは、カ
ラーホーマ溶液を芯物質とし、メラミン尿素ホル
ムアルデヒド系高分子よりなる均一で緻密な膜壁
で芯物質を被覆してなる。本発明の微小カプセル
は以下で述べる耐溶剤性試験からも明らかなよう
に、従来方法により製造される微小カプセルには
みられない優れた耐溶剤性を有する。従つて本発
明微小カプセルは分散媒として有機液体（所謂有
機溶剤）に分散したスラリーにして感圧記録紙の
製造に供することができるため感圧記録紙の生産
性を著しく向上させることができ得る。
尚本発明による微小カプセルの芯材となるカラ
ーホーマー溶液は、既知の感圧記録紙に使用でき
るものであればよく、特に制限はない。例えば溶
剤としては、アルキルナフタレン、フエニルキシ
リルエタン、アルキルビフエニル、水添ターフエ
ニル、塩素化パラフイン油又は鉱油等及びそれ等
の混合物などが挙げられる。
実施例 １
（プレポリマーの作成）
メラミン63ｇと２％NaOH水溶液でPH9.0に調
整したホルマリン（37％ホルムアルデヒド水溶液
以下同じ）162ｇを混合し70℃で反応させメラミ
ンが溶解したら直ちに水225ｇを加えてそのまま
３分間攪拌してメラミンホルムアルデヒドプレポ
リマー水溶液（M4Fプレポリマーと云う。M4F
はメラミン１モルに対しホルムアルデヒド４モル
であることを示す。以下同じ）を作成した。
別に、トリエタノールアミンでPH8.5に調整し
たホルマリン146ｇと尿素60ｇを混合し、70℃で
１時間反応させて尿素ホルムアルデヒドプレポリ
マー水溶液（U1.8Fプレポリマーと云う）を得
た。
（カチオニツク尿素樹脂の作成）
37％ホルムアルデヒド水溶液162ｇと尿素60ｇ
を混合攪拌し、この混合物にトリエタノールアミ
ンを加えてPHを8.8に調整した後、温度70℃で30
分間反応させた。この反応混合物40ｇを取り、こ
れに水24ｇとテトラエチレンペンタミン６ｇを加
え、温度70℃で攪拌しながら15％塩酸でPHを３に
調整し、１時間反応させた。この反応に伴いPHが
低下するので反応生成物に10％カセイソーダ水溶
液を加えてそのPHを３に調整しなおし、温度を55
℃に下げて反応を続け粘度が200cpsとなつた時点
で10％カセイソーダ水溶液で中和し、水400ｇを
加え水溶性カチオニツク尿素樹脂の水溶液を得
た。
（微小カプセル化）
M4Fプレポリマー100ｇ、U1.8Fプレポリマー
50ｇ、上述のカチオニツク尿素樹脂158ｇ、水62
ｇ及びトリエタノールアミン１ｇの混合液を10％
クエン酸水溶液でPH5.2に調整した後、10％ネオ
ペレツクス水溶液（アルキルベンゼンスルホン酸
ソーダ水溶液、花王アトラス社製）３ｇを加えＡ
液とした。
別にクリスタルバイオレツトラクトン30ｇを
970ｇのジイソプロピルナフタレン（DIPN）に
溶かした油をＢ液（カラーホーマー溶液）とし
た。Ａ液中にＢ液150c.c.をホモジナイザーで液滴
の径が２〜3μになるように乳化させその後ゆつ
くり攪拌しながら温度を30℃に保持し、10％クエ
ン酸水溶液を加えてPH3.6にした。１時間後200ｇ
の水を加えた。さらに１時間後クエン酸を加えて
PHを3.0にして２時間攪拌させると下葉紙上に塗
布しても青色に発色しなくなり、カプセル化が完
了したことがわかつた。このカプセルスラリーを
メンブランフイルターを通し微小カプセルを分離
し、水洗後、35℃熱風乾燥器中で乾燥し205ｇの
粉末カプセルを得た。
実施例 ２〜５
実施例１により作成したM4Fプレポリマーと
U1.8Fプレポリマーの混合比を第１表に示すよう
にかえ、実施例１と略同様にして微小カプセルを
製造した。
実施例 ６
実施例１におけるMFプレポリマーの作成にお
いてメラミンとホルムアルデヒドのモル比を１：
２にし、使用したメラミンとホルマリンの合計と
同量の水を加えてM2Fプレポリマーを作成しま
たUFプレポリマーとしては尿素とホルムアルデ
ヒドのモル比を１：１としてUFプレポリマーを
作成した。これを用いた以外は実施例１と同様に
して微小カプセルを製造した。
実施例 ７
実施例１におけるプレポリマーの作成において
MFプレポリマーの作成はメラミンとホルムアル
デヒドのモル比を１：８とし使用したメラミンと
ホルマリンの合計と同量の水を加えてM8Fプレ
ポリマーを作成し、またUFプレポリマーとして
は尿素とホルムアルデヒドのモル比を１：３とし
てU3Fプレポリマーを作成し、実施例１と同様に
して微小カプセルを製造した。
The present invention relates to microcapsules for pressure-sensitive recording paper and a method for producing the same. More specifically, it is an object of the present invention to provide microcapsules whose shells are mainly made of melamine urea formaldehyde resin and which are suitable for producing pressure-sensitive recording paper, which has much better solvent resistance than conventional pressure-sensitive recording paper. . General pressure-sensitive recording paper is made of, for example, top paper (CB paper) coated with microcapsules containing a solution of leuco dye (color homer) as a core substance on the back side of the paper, and acid clay or acidic resin. Layer the bottom paper (CF paper) coated with a coloring agent, and use writing pressure or typewriter printing pressure, etc.
The microcapsules in that area are destroyed and a color former is brought into contact with a coloring agent to record color. In recent years, pressure-sensitive recording paper has come to be used in more and more fields as the efficiency of office work has improved, especially with the development and spread of computers. There is a demand for microcapsules with excellent moisture resistance, heat resistance, and light resistance. Furthermore, in the production of pressure-sensitive recording paper, microcapsules with excellent solvent resistance are required. That is, conventional pressure-sensitive recording paper is usually manufactured by using water as a dispersion medium and coating paper with slurry-like microcapsules made of a water-soluble binder and additives. However, when water is used as a dispersion medium, it takes a long time to dry and wrinkles occur, resulting in a lack of dimensional stability. In order to eliminate these drawbacks and improve the productivity of pressure-sensitive recording paper, it is conceivable to use a faster-drying dispersion medium as the dispersion medium used when coating the microcapsules. Examples of such dispersion media include organic solvents commonly used as ink solvents in printing, etc. Alcohols such as isopropyl alcohol and ethyl alcohol, esters such as ethyl acetate, ketones such as methyl ethyl ketone, and carbonized solvents such as kerosene, toluene, and xylene. Hydrogen solvents or vegetable oils such as linseed oil or castor oil are suitable.
However, none of the microcapsules for pressure-sensitive recording paper that have been put to practical use or proposed so far can exist stably in the above-mentioned organic solvents. If there were microcapsules that could exist stably in these solvents, it would be possible to reduce the time required to dry paper coated with microcapsules containing color homers in the production of pressure-sensitive recording paper, thereby increasing productivity. Not only can this greatly improve the appearance, but there is no fear of wrinkles occurring. Furthermore, it becomes easy to manufacture partial pressure-sensitive recording paper by spot printing or the like. The various advantages mentioned above are the reason why microcapsules for pressure-sensitive recording paper with excellent solvent resistance are desired. The membrane walls of the microcapsules used in most pressure-sensitive recording papers currently in use are mainly gelatin-based (hereinafter referred to as gelatin capsules), and gelatin capsules have poor moisture resistance and poor light resistance. It has disadvantages such as poor corrosion resistance and susceptibility to microorganisms, and also lacks solvent resistance. On the other hand, various microcapsules using hydrophobic polymers as membrane wall materials have been proposed as alternatives to gelatin capsules. Urea formaldehyde resin, melamine resin polyamide, polyurethane, etc. are used as materials for the membrane walls of these microcapsules, and these membrane wall materials are encapsulated by in situ polymerization or interfacial polymerization.
However, although these conventional microcapsules are slightly improved compared to gelatin capsules in terms of moisture resistance, light resistance, etc., they are still not satisfactory as microcapsules for pressure-sensitive recording paper, especially in terms of solvent resistance. Missing. In the present invention, a resin polymer made of melamine, urea, and formaldehyde is used as a membrane material, but microcapsules formed by a conventional method using a resin made of melamine, urea, and formaldehyde as a membrane material have advantages over gelatin capsules. However, it lacks solvent resistance. For example, a method for forming microcapsules using only a prepolymer consisting of melamine, urea, and formaldehyde has been proposed (Japanese Patent Application Laid-Open No. 150212/1982), but it is not possible to obtain microcapsules suitable for pressure-sensitive recording paper, and it is difficult to obtain solvent-resistant The quality is also significantly inferior. Furthermore, a method in which a substance having a hydrophobic group and a hydrophilic group derived from a urea formaldehyde compound or a melamine formaldehyde compound, called a reactive surfactant, is used in combination with a prepolymer (Japanese Patent Application Laid-Open No. 1983-1996)
-7313), or a method in which a styrene maleic anhydride copolymer and a vinyl acetate maleic anhydride copolymer are used in combination with a prepolymer (Japanese Patent Application Laid-Open No. 10876/1983). However, although these methods have overcome the disadvantages in producing gelatin capsules, such as the fact that encapsulation is possible only from low concentration solutions,
Although the microcapsules obtained by these methods are slightly improved compared to gelatin capsules in moisture resistance, light resistance, etc., they are still unsatisfactory as microcapsules for pressure-sensitive recording paper, especially as described below. Lacks stability in organic solvents. In view of the above-mentioned current situation, the present inventors have made use of the characteristics that microcapsules whose membrane walls are made of melamine urea formaldehyde resin are hydrophobic and can be obtained at low cost, and have excellent solvent resistance. As a result of intensive research into the production of microcapsules for pressure-sensitive recording paper, the present invention has been completed. In the microcapsule for pressure-sensitive recording paper of the present invention, the membrane wall encapsulating the color homer solution is at least two kinds of prepolymers selected from melamine formaldehyde prepolymer, urea formaldehyde prepolymer, and melamine urea formaldehyde prepolymer, or melamine urea It is characterized by being a resin formed by polycondensing a prepolymer, which is a formaldehyde prepolymer, and a water-soluble cationic urea resin in the presence of an anionic surfactant. Furthermore, the method for producing microcapsules for pressure-sensitive recording paper of the present invention involves adding an acid catalyst to the above-mentioned aqueous dispersion to generate complex coacervation by a water-soluble cationic urea resin and anionic surfactant. , the prepolymer and the water-soluble cationic urea resin are polycondensed to form a hydrophobic polymer membrane wall that completely covers the dispersed microdroplets of the color homer solution to form microcapsules. What is particularly important in carrying out the present invention is the use of a water-soluble cationic urea resin and an anionic surfactant, ie, two substances with different charges, in combination with the prepolymer. By coexisting a small amount of a cationic urea resin and an anionic surfactant during the condensation polymerization of the prepolymer, a stable dispersion can be obtained, and at the same time, homogeneous capsules can be obtained. Next, the method for manufacturing microcapsules of the present invention will be specifically explained. First, an aqueous mixture containing at least a water-soluble cationic urea resin and an anionic surfactant and a color homer solution are mixed by appropriate means, for example,
Using a homogenizer, stirrer, ultrasonic wave, etc., the color homer solution is emulsified and dispersed into minute droplets of 1 to 8 microns. The prepolymer may be pre-existing in the mixed solution before emulsification, or may be added at once or in several portions during or after emulsification. While gently stirring the dispersion containing this prepolymer, add an acid catalyst and
6.0, microencapsulation is completed by reacting for 2 to 15 hours at a reaction temperature of 15 to 60°C. Incidentally, an appropriate amount of water can also be added during this reaction process. The prepolymer used in the present invention is produced from melamine, urea, and formaldehyde, and may be a combination of melamine formaldehyde prepolymer (MF prepolymer) and urea formaldehyde prepolymer (UF prepolymer), or melamine, urea, and formaldehyde. Melamine urea formaldehyde prepolymer (MUF prepolymer) obtained by the reaction alone or the above MF
It can also be used in combination with prepolymers and UF prepolymers. The melamine formaldehyde prepolymer herein refers to methylolmelamine ranging from monomethylolmelamine to hexamethylolmelamine, a mixture of these methylolmelamines with different degrees of methylolation, or a mixture of the above-mentioned methylolmelamine, melamine, and formaldehyde,
Furthermore, it may be a transparent colloidal solution obtained by further reacting melamine and formaldehyde, that is, by treating methylolmelamine with a degree of polymerization of 2 to 10 with hydrochloric acid. This melamine formaldehyde prepolymer can be easily produced by heating a mixture of melamine and formalin in alkaline conditions, and this aqueous reaction solution can be directly used for encapsulation. Urea formaldehyde prepolymer means methylol urea ranging from monomethylol urea to tetramethylol urea, a mixture of these methylol ureas with different degrees of methylol, or a mixture of the methylol urea, urea, and formaldehyde,
Furthermore, it may be an oligomer obtained by further reacting urea and formaldehyde, that is, a transparent colloidal solution having a hydrophilic group with a degree of polymerization of 2 to 5. The raw material melamine: urea and formaldehyde ratio has an important influence on film formation. Formaldehyde is 1.0 to 9.0 mol per mol of melamine constituting the prepolymer, preferably 1.6 to 7.0 mol, and 0.6 to 4.0 mol per mol of urea, preferably 1.0 to 1.0 mol.
The amount should be 3.0 moles. Also, the ratio of melamine to urea is 0.05 to 9.0 melamine to 1 mole of urea.
It is in the molar range. Such a ratio is intended to uniformly form the membrane wall of the microcapsules and to ensure that the resulting membrane maintains sufficient membrane strength, impermeability, and especially solvent resistance. The properties of the resulting microcapsules vary depending on the ratio of melamine to urea in the prepolymer used. For example, as a prepolymer
Microcapsules obtained using a composition similar to that of MF prepolymer alone have a heavy specific gravity and tend to sediment, making it possible to obtain a highly concentrated capsule slurry.On the other hand, when you want to obtain a dispersion that does not sediment,
Preferably, the composition is close to that of the UF prepolymer.
Also, from the viewpoint of solvent resistance, those with a melamine/urea molar ratio of around 0.15 to 5.0 are excellent.
During encapsulation, the amount of prepolymer used is preferably in the range of 0.1 to 1 g per 1 g of color homer solution. The water-soluble cationic urea resin used in the present invention is a urea-formaldehyde resin in which a cationic modifier is introduced. For example, tetraethylenepentamine, diaminoethanol, dicyandiamide, diethylaminoethanol, guanyl is added to the urea-formaldehyde prepolymer as a modifier. It can be easily obtained by adding urea or something similar thereto and performing condensation polymerization using a known method. The ratio of the water-soluble cationic urea resin to the prepolymer is preferably in the range of 1:0.01 to 0.5 by weight. Further, examples of the anionic surfactant include fatty acid salts, higher alcohol sulfates, alkylaryl sulfonates, etc., but sodium dodecylbenzenesulfonate is preferred. The amount of this anionic surfactant used is 0.01 to 0.1 part by weight of water-soluble cationic urea resin.
Wide PH range, i.e. PH2.5~ by weight part
A stable dispersion can be obtained within the range of 6.0. Furthermore, acid catalysts include low molecular weight carboxylic acids such as formic acid, acetic acid or citric acid, inorganic acids such as hydrochloric acid, nitric acid or phosphoric acid, or aluminum sulfate, titanium oxychloride, magnesium chloride, ammonium chloride, ammonium nitrate, ammonium sulfate. , acid salts such as ammonium acetate, or salts that are easily hydrolyzed, and these can be used alone or in combination. In the production of microcapsules according to the present invention as described above, only a conventional aqueous solution of a prepolymer is used, a prepolymer and a cationic urea resin alone are used together, or a prepolymer and a urea resin are used in combination. The emulsifying power of the color homer solution is greater than when used in combination with a reactive surfactant derived from a resin (e.g., JP-A No. 46-7313), resulting in a stable dispersion with low viscosity. The membrane wall of the capsule thus formed has a feature of significantly lower membrane permeability than the capsule formed by the above-mentioned known method. The reason for this advantage is that the water-soluble cationic urea resin and the anionic surfactant form a complex coacervate when set at a certain composition and pH. If the liquid composition is the same, the least amount of coacervate is produced in the pH range of 1 to 6, and the production of coacervate is significant when the pH is around 7 and below 3. Therefore, the emulsification and dispersion of the color former solution is carried out in a pH range where coacervate formation is low, taking into consideration the prevention of particle coagulation, and then the encapsulation reaction is caused by lowering the pH with an acid catalyst. At this time, the polymerization of the prepolymer and the production of complex coacervate occur continuously, resulting in the formation of a capsule membrane wall, and the water-soluble cationic urea resin also undergoes a condensation reaction to form a hydrophobic polymer, which is dense and uniform. A membrane wall is formed and becomes a microcapsule. As mentioned above, the microencapsulation according to the present invention is carried out by combining complex coacervation method and in situ polymerization method and proceeding simultaneously, and is a novel method not seen in the prior art. The microcapsules of the present invention thus obtained are made by using a color former solution as a core material and covering the core material with a uniform and dense membrane wall made of a melamine urea formaldehyde polymer. As is clear from the solvent resistance test described below, the microcapsules of the present invention have excellent solvent resistance not found in microcapsules produced by conventional methods. Therefore, the microcapsules of the present invention can be made into a slurry dispersed in an organic liquid (so-called organic solvent) as a dispersion medium and used in the production of pressure-sensitive recording paper, which can significantly improve the productivity of pressure-sensitive recording paper. . The color homer solution serving as the core material of the microcapsule according to the present invention is not particularly limited as long as it can be used for known pressure-sensitive recording paper. For example, examples of the solvent include alkylnaphthalene, phenylxylylethane, alkylbiphenyl, hydrogenated terphenyl, chlorinated paraffin oil or mineral oil, and mixtures thereof. Example 1 (Creation of prepolymer) 63 g of melamine and 162 g of formalin adjusted to pH 9.0 with 2% NaOH aqueous solution (the same applies below 37% formaldehyde aqueous solution) were mixed and reacted at 70°C. Once the melamine was dissolved, 225 g of water was immediately added. melamine formaldehyde prepolymer aqueous solution (referred to as M4F prepolymer. M4F
indicates that there are 4 moles of formaldehyde per 1 mole of melamine. (same below) was created. Separately, 146 g of formalin adjusted to pH 8.5 with triethanolamine and 60 g of urea were mixed and reacted at 70° C. for 1 hour to obtain an aqueous urea-formaldehyde prepolymer solution (referred to as U1.8F prepolymer). (Creation of cationic urea resin) 162g of 37% formaldehyde aqueous solution and 60g of urea
Mix and stir, add triethanolamine to this mixture to adjust the pH to 8.8, and then stir at a temperature of 70℃ for 30 minutes.
Allowed to react for minutes. 40 g of this reaction mixture was taken, 24 g of water and 6 g of tetraethylenepentamine were added thereto, the pH was adjusted to 3 with 15% hydrochloric acid while stirring at a temperature of 70° C., and the mixture was allowed to react for 1 hour. As the PH decreases with this reaction, 10% caustic soda aqueous solution is added to the reaction product to readjust the PH to 3, and the temperature is set to 55.
℃ and continued the reaction, and when the viscosity reached 200 cps, it was neutralized with a 10% caustic soda aqueous solution, and 400 g of water was added to obtain an aqueous solution of water-soluble cationic urea resin. (Microcapsulation) M4F prepolymer 100g, U1.8F prepolymer
50g, 158g of the above cationic urea resin, 62g of water
10% mixture of g and 1 g of triethanolamine
After adjusting the pH to 5.2 with a citric acid aqueous solution, add 3 g of a 10% Neoperex aqueous solution (sodium alkylbenzenesulfonate aqueous solution, manufactured by Kao Atlas Co., Ltd.).
It was made into a liquid. Separately, take 30g of crystal violet lactone.
An oil dissolved in 970 g of diisopropylnaphthalene (DIPN) was used as a B solution (color homer solution). Emulsify 150 c.c. of liquid B in liquid A using a homogenizer so that the droplet diameter is 2 to 3 μm. Then, while stirring slowly, maintain the temperature at 30°C, add 10% citric acid aqueous solution, and adjust the pH to 3. I set it to .6. 200g after 1 hour
of water was added. After another hour, add citric acid.
When the pH was adjusted to 3.0 and the mixture was stirred for 2 hours, no blue color developed when applied to the bottom paper, indicating that encapsulation was complete. This capsule slurry was passed through a membrane filter to separate microcapsules, washed with water, and dried in a hot air dryer at 35° C. to obtain 205 g of powder capsules. Examples 2 to 5 M4F prepolymer prepared according to Example 1 and
Microcapsules were produced in substantially the same manner as in Example 1, except that the mixing ratio of the U1.8F prepolymer was changed as shown in Table 1. Example 6 In creating the MF prepolymer in Example 1, the molar ratio of melamine and formaldehyde was set to 1:
2 and added the same amount of water as the total of melamine and formalin used to create an M2F prepolymer, and as a UF prepolymer, a UF prepolymer was created by setting the molar ratio of urea and formaldehyde to 1:1. Microcapsules were produced in the same manner as in Example 1 except that this was used. Example 7 In the preparation of the prepolymer in Example 1
The MF prepolymer was created by setting the molar ratio of melamine and formaldehyde to 1:8 and adding the same amount of water as the sum of the melamine and formalin used to create the M8F prepolymer. A U3F prepolymer was prepared at a ratio of 1:3, and microcapsules were produced in the same manner as in Example 1.
【表】
実施例 ８
あらかじめ２％NaOH水溶液でPH9.0に調整し
たホルマリン56.9ｇにメラミン20.5ｇと尿素22.6
ｇを混合し50℃で攪拌し、メラミンが溶解したら
水100mlを加えて60分後冷やし、メラミンと尿素
とホルムアルデヒドよりなるプレポリマー水溶液
を作成した。
実施例１で用いたカチオニツク尿素樹脂16ｇを
水６ｇに加え、20％クエン酸でPH5.2に調整した
後、10％ネオペレツクス0.3ｇを加えた液を調整
した。この液に実施例１で用いたのと同じカラー
ホーマー溶液15ｇを加えホモミキサーでカラーホ
ーマー溶液が平均3μの粒子になるまで分散させ
た。この分散液を35℃でゆつくり攪拌しながら上
記プレポリマー水溶液20ｇを加え、20％クエン酸
でPH3.6に調整し、２時間反応させた後水30mlを
添加しさらに20％クエン酸でPH2.5に調整した後
８時間攪拌して微小カプセルスラリーを得た。
実施例 ９
あらかじめ５％NaOH水溶液でPH8.6に調整し
たホルマリン87.6ｇにメラミン5.9ｇと尿素66.5ｇ
を加えて混合し70℃で攪拌しながら溶解させ、水
100mlを加えて２分後冷やしてメラミン尿素ホル
ムアルデヒドよりなるプレポリマー水溶液を得
た。
このプレポリマーを用いて実施例８と同様にし
て微小カプセルを製造した。
実施例 10〜12
メラミン（Ｍ）、尿素（Ｕ）とホルマリン（Ｆ）
の重量比を第２表に示すようにかえた以外は実施
例８と同様にしてプレポリマー水溶液を作成し
た。
又、微小カプセル化に当つては実施例11は10％
ネオペレツクス0.4ｇを使用し実施例12ではカチ
オニツク尿素樹脂24ｇと10％ネオペレツクス0.2
ｇを使用した以外は実施例８と同様にして微小カ
プセルを製造した。[Table] Example 8 56.9 g of formalin, adjusted to pH 9.0 with 2% NaOH aqueous solution in advance, 20.5 g of melamine and 22.6 g of urea
When the melamine was dissolved, 100 ml of water was added and cooled after 60 minutes to prepare an aqueous prepolymer solution consisting of melamine, urea, and formaldehyde. 16 g of the cationic urea resin used in Example 1 was added to 6 g of water, the pH was adjusted to 5.2 with 20% citric acid, and 0.3 g of 10% neopellex was added to prepare a solution. To this solution, 15 g of the same color homer solution used in Example 1 was added and dispersed using a homomixer until the color homer solution became particles with an average size of 3 μm. This dispersion was slowly heated at 35°C, and while stirring, 20g of the above prepolymer aqueous solution was added, and the pH was adjusted to 3.6 with 20% citric acid. After reacting for 2 hours, 30ml of water was added, and the pH was raised to 20% with 20% citric acid. .5 and stirred for 8 hours to obtain a microcapsule slurry. Example 9 5.9 g of melamine and 66.5 g of urea were added to 87.6 g of formalin, which had been adjusted to pH 8.6 with 5% NaOH aqueous solution in advance.
Add and mix and dissolve while stirring at 70℃, then add water
After 100 ml was added and cooled for 2 minutes, an aqueous prepolymer solution of melamine urea formaldehyde was obtained. Microcapsules were produced in the same manner as in Example 8 using this prepolymer. Examples 10-12 Melamine (M), urea (U) and formalin (F)
An aqueous prepolymer solution was prepared in the same manner as in Example 8 except that the weight ratio of . In addition, for microencapsulation, Example 11 was 10%
In Example 12, 24 g of cationic urea resin and 0.2 g of 10% Neopellex were used.
Microcapsules were produced in the same manner as in Example 8 except that g was used.
【表】
実施例 13〜15
実施例１で述べた水溶性カチオニツク尿素樹脂
の作成方法でテトラエチレンペンタミン６ｇに代
えジアミノエタノール15ｇ、ジシアンジアミド10
ｇ又はジエチルアミノエタノール８ｇを用いて
夫々カチオニツク尿素樹脂を作成した。
この夫々のカチオニツク尿素樹脂を実施例１で
用いたカチオニツク尿素樹脂に代えて実施例１と
同じ方法で微小カプセルを作成したところ実施例
１の微小カプセルと同様の性質を有する微小カプ
セルを得た。
比較例 １〜３
実施例１と同様の方法によつて作成したプレポ
リマー水溶液20ｇを用い、水溶性カチオニツク尿
素樹脂とネオペレツクスの代りに、第３表に示し
た第三成分を用いることによりカラーホーマー液
15mlを、実施例１と同一条件で分散させた。この
際、分散液がPH5.0以下になるようなものは乳化
前に水酸化ナトリウムでPH5.0に調整した。
分散液は30℃でゆつくり攪拌しながら10％のク
エン酸水溶液でPH3.8に調整し、１時間後水30ml
を加え更に２時間攪拌をつづけてカプセル化を終
了した。これらカプセルスラリーをメンブランフ
イルターで過水洗し、乾燥させようと試みた
が、比較例２および３の場合は過不能であり、
自由流動性の粉末は得られず、ブロツク状の乾燥
物となつた。従つて上記カプセルスラリーをその
ままスプレイドライング法で粉末化したが感圧紙
用として好ましい１〜20μの粒子径をもつ乾燥カ
プセルは得られなかつた。しかし乍ら、これらに
ついても後述の実施例16において本発明微小カプ
セルと同様の耐溶剤性テストを行なつたところ、
第４表に示すように非常に劣悪な結果で、これら
は有機溶剤を分散媒とする使用は不可能であるこ
とが判明した。[Table] Examples 13 to 15 Using the method for producing water-soluble cationic urea resin described in Example 1, 15 g of diaminoethanol and 10 g of dicyandiamide were used instead of 6 g of tetraethylenepentamine.
A cationic urea resin was prepared using 8 g of 100 g or diethylaminoethanol, respectively. Microcapsules were prepared in the same manner as in Example 1 except that each of these cationic urea resins was used in place of the cationic urea resin used in Example 1. Microcapsules having the same properties as the microcapsules in Example 1 were obtained. Comparative Examples 1 to 3 A color homer was produced by using 20 g of a prepolymer aqueous solution prepared in the same manner as in Example 1, and using the third component shown in Table 3 instead of the water-soluble cationic urea resin and neopellex. liquid
15 ml was dispersed under the same conditions as in Example 1. At this time, if the dispersion liquid had a pH of 5.0 or less, the pH was adjusted to 5.0 with sodium hydroxide before emulsification. The dispersion was slowly heated at 30℃, adjusted to pH 3.8 with 10% citric acid aqueous solution while stirring, and after 1 hour was added with 30ml of water.
was added and stirring was continued for an additional 2 hours to complete the encapsulation. An attempt was made to wash these capsule slurries with water using a membrane filter and dry them, but this was not possible in the case of Comparative Examples 2 and 3.
A free-flowing powder was not obtained, but a dry block-like product was obtained. Therefore, although the above capsule slurry was directly pulverized by a spray drying method, dry capsules having a particle size of 1 to 20 μm, which is preferable for use in pressure-sensitive paper, could not be obtained. However, when these were also subjected to the same solvent resistance test as the microcapsules of the present invention in Example 16 described below,
As shown in Table 4, the results were very poor, and it was found that it was impossible to use these with an organic solvent as a dispersion medium.
【表】
実施例 16
耐溶剤性試験
粉末状微小カプセル10ｇを精秤し、乳鉢にてよ
くすりつぶし、そこに200mlのトルエンを加え混
合した後静置し上澄液を500mlのメスフラスコに
入れる。残存した微小カプセルは再度乳鉢にてよ
くすりつぶし200mlのトルエンを加え混合後前記
500mlメスフラスコに全量を加え、乳鉢、乳棒を
トルエンでよく洗浄し洗液も前記500mlメスフラ
スコに加え、全量が500mlになるようトルエンを
加える。この溶液中のジイソプロピルナフタレン
量をガスクロマトグラフイーにより求め、その量
をＡとする。
別に微小カプセル10ｇを精秤し、100ml共栓三
角フラスコに入れ、これに50ｇの溶剤を加え密栓
混合後、室温中に24時間放置する。その後混合物
中の微小カプセルを別し、使用した溶剤でよく
洗浄した後別された微小カプセルを乳鉢に移
し、以後上記Ａを求める手順と同様な手順で、
別された微小カプセル中のジイソプロピルナフタ
レン量をガスクロマトグラフイーにより求め、そ
の量をＢとする。溶剤浸漬後の芯物質の保持率を
次式により求めた。
保持率（％）＝Ｂ／Ａ×100
保持率の高いもの程耐溶剤性が良好なものであ
る。
前記各実施例１乃至12及び比較例１乃至３によ
り得られた微小カプセルにつき、溶剤としてエチ
ルアルコール、トルエン及びイソプロピルアルコ
ールを用いて試験した結果を第４表に示した。[Table] Example 16 Solvent Resistance Test Precisely weigh 10 g of powdered microcapsules, grind well in a mortar, add 200 ml of toluene, mix and leave to stand, and pour the supernatant into a 500 ml volumetric flask. Grind the remaining microcapsules again in a mortar, add 200ml of toluene, mix, and mix as above.
Add the entire amount to a 500 ml volumetric flask, wash the mortar and pestle thoroughly with toluene, add the washing liquid to the 500 ml volumetric flask, and add toluene so that the total volume is 500 ml. The amount of diisopropylnaphthalene in this solution is determined by gas chromatography, and the amount is designated as A. Separately, accurately weigh 10 g of microcapsules, place in a 100 ml stoppered Erlenmeyer flask, add 50 g of solvent, mix tightly, and leave at room temperature for 24 hours. After that, the microcapsules in the mixture are separated, and after being thoroughly washed with the solvent used, the separated microcapsules are transferred to a mortar, and then in the same procedure as for obtaining A above,
The amount of diisopropylnaphthalene in the separated microcapsules is determined by gas chromatography, and the amount is designated as B. The retention rate of the core substance after immersion in the solvent was determined using the following formula. Retention rate (%)=B/A×100 The higher the retention rate, the better the solvent resistance. The microcapsules obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were tested using ethyl alcohol, toluene, and isopropyl alcohol as solvents, and the results are shown in Table 4.
【表】【table】
Claims (1)
素ホルムアルデヒドプレポリマー及びメラミン尿
素ホルムアルデヒドプレポリマーから選択される
少なくとも２種のプレポリマー又はメラミン尿素
ホルムアルデヒドプレポリマーであるプレポリマ
ーと水溶性カチオニツク尿素樹脂とをアニオニツ
ク界面活性剤の存在のもとに重縮合させてなる樹
脂の膜壁をもつことを特徴とするカラーホーマー
溶液を内包した感圧記録紙用微小カプセル。 ２ プレポリマーにおける原料メラミンと原料尿
素の比が尿素１モルに対しメラミン0.05〜９モル
である特許請求の範囲第１項に記載の感圧記録紙
用微小カプセル。 ３ メラミンホルムアルデヒドプレポリマー及び
尿素ホルムアルデヒドプレポリマーの混合物、メ
ラミン尿素ホルムアルデヒドプレポリマー及びこ
れらの混合物からなるグループから選択されるプ
レポリマー、水溶性カチオニツク尿素樹脂及びア
ニオニツク界面活性剤を含有するカラーホーマー
溶液の水系分散液に酸触媒を加え、前記水溶性カ
チオニツク尿素樹脂と前記アニオニツク界面活性
剤によるコンプレツクスコアセルベーシヨンを起
させつつ、前記プレポリマー及び前記水溶性カチ
オニツク尿素樹脂を重縮合させることを特徴とす
る感圧記録紙用微小カプセルの製造方法。 ４ プレポリマーにおける原料メラミンと原料尿
素の比が尿素１モルに対しメラミン0.05〜９モル
である特許請求の範囲第３項に記載の感圧記録紙
用微小カプセルの製造方法。 ５ 水系分散液中の水溶性カチオニツク尿素樹脂
とアニオニツク界面活性剤の重量比が１：0.01〜
0.1であることを特徴とする特許請求の範囲第３
項又は第４項に記載の微小カプセルの製造方法。 ６ 水系分散液中のプレポリマーと水溶性カチオ
ニツク尿素樹脂の樹脂分重量比が１：0.01〜0.5
であることを特徴とする特許請求の範囲第３項乃
至第５項のいずれかに記載の微小カプセルの製造
方法。[Claims] 1. At least two prepolymers selected from melamine formaldehyde prepolymer, urea formaldehyde prepolymer, and melamine urea formaldehyde prepolymer, or a prepolymer that is a melamine urea formaldehyde prepolymer and a water-soluble cationic urea resin. A microcapsule for pressure-sensitive recording paper containing a color homer solution characterized by having a membrane wall made of a resin polycondensed in the presence of an anionic surfactant. 2. Microcapsules for pressure-sensitive recording paper according to claim 1, wherein the ratio of raw material melamine to raw material urea in the prepolymer is 0.05 to 9 moles of melamine to 1 mole of urea. 3. An aqueous color homer solution containing a prepolymer selected from the group consisting of a mixture of a melamine formaldehyde prepolymer and a urea formaldehyde prepolymer, a melamine urea formaldehyde prepolymer and a mixture thereof, a water-soluble cationic urea resin, and an anionic surfactant. The method is characterized in that an acid catalyst is added to the dispersion liquid, and the prepolymer and the water-soluble cationic urea resin are polycondensed while causing complex coacervation by the water-soluble cationic urea resin and the anionic surfactant. A method for producing microcapsules for pressure-sensitive recording paper. 4. The method for producing microcapsules for pressure-sensitive recording paper according to claim 3, wherein the ratio of raw material melamine to raw material urea in the prepolymer is 0.05 to 9 moles of melamine to 1 mole of urea. 5 The weight ratio of water-soluble cationic urea resin and anionic surfactant in the aqueous dispersion is 1:0.01~
Claim 3 characterized in that 0.1
The method for producing microcapsules according to item 1 or 4. 6 The resin weight ratio of the prepolymer and water-soluble cationic urea resin in the aqueous dispersion is 1:0.01 to 0.5.
A method for producing microcapsules according to any one of claims 3 to 5, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56132542A JPS5833492A (en) | 1981-08-24 | 1981-08-24 | Microcapsule for pressure sensitive recording material and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56132542A JPS5833492A (en) | 1981-08-24 | 1981-08-24 | Microcapsule for pressure sensitive recording material and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5833492A JPS5833492A (en) | 1983-02-26 |
| JPH0229032B2 true JPH0229032B2 (en) | 1990-06-27 |
Family
ID=15083709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56132542A Granted JPS5833492A (en) | 1981-08-24 | 1981-08-24 | Microcapsule for pressure sensitive recording material and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5833492A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586364B2 (en) | 1999-12-08 | 2003-07-01 | Pentax Corporation | Heat-sensitive microcapsule and recording medium using same |
| US6746984B2 (en) | 1999-12-08 | 2004-06-08 | Pentax Corporation | Image-forming medium coated with microcapsule layer for forming image |
| ATE235960T1 (en) * | 2000-01-13 | 2003-04-15 | Kureha Chemical Ind Co Ltd | MICRO CAPSULE AND ITS PRODUCTION PROCESS |
| JP2001240782A (en) | 2000-02-29 | 2001-09-04 | Asahi Optical Co Ltd | Oil based ink for thermal type ink-jet printer and ink transfer printer |
| US6579827B2 (en) | 2000-04-28 | 2003-06-17 | Pentax Corporation | Multi-color image-forming medium |
| US6869907B2 (en) | 2000-05-02 | 2005-03-22 | Pentax Corporation | Color-image-forming medium |
| KR100854530B1 (en) * | 2000-06-05 | 2008-08-26 | 신젠타 리미티드 | Novel microcapsules |
| JP4527962B2 (en) * | 2003-10-31 | 2010-08-18 | トッパン・フォームズ株式会社 | Method for producing microcapsule-containing oil-based ink |
-
1981
- 1981-08-24 JP JP56132542A patent/JPS5833492A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5833492A (en) | 1983-02-26 |
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