JPS6361194B2 - - Google Patents
Info
- Publication number
- JPS6361194B2 JPS6361194B2 JP56108119A JP10811981A JPS6361194B2 JP S6361194 B2 JPS6361194 B2 JP S6361194B2 JP 56108119 A JP56108119 A JP 56108119A JP 10811981 A JP10811981 A JP 10811981A JP S6361194 B2 JPS6361194 B2 JP S6361194B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- color
- electron
- microcapsules
- solvent
- 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
Links
- 239000003094 microcapsule Substances 0.000 claims description 16
- 238000004040 coloring Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002775 capsule Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229920005597 polymer membrane Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- -1 rhodamine lactam Chemical class 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 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
- 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
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- GPYLCFQEKPUWLD-UHFFFAOYSA-N 1h-benzo[cd]indol-2-one Chemical compound C1=CC(C(=O)N2)=C3C2=CC=CC3=C1 GPYLCFQEKPUWLD-UHFFFAOYSA-N 0.000 description 1
- UYMBCDOGDVGEFA-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3h-2-benzofuran-1-one Chemical compound C12=CC=CC=C2C(=O)OC1C1=CC2=CC=CC=C2N1 UYMBCDOGDVGEFA-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229960000829 kaolin Drugs 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- AYNNSCRYTDRFCP-UHFFFAOYSA-N triazene Chemical compound NN=N AYNNSCRYTDRFCP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite 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
Landscapes
- Color Printing (AREA)
Description
【発明の詳細な説明】
本発明は、鉛筆・ボールペン・万年筆などによ
る筆記や、タイプライターなどによる印書の局部
圧力でマイクロカプセルを破壊し、そのマイクロ
カプセル内の溶剤が気化し、加圧を受けた部分の
みが発色する感圧記録紙に関するものである。Detailed Description of the Invention The present invention destroys microcapsules by local pressure when writing with a pencil, ballpoint pen, fountain pen, etc. or printing with a typewriter, etc., and the solvent inside the microcapsules evaporates and pressurizes. This relates to pressure-sensitive recording paper in which only the exposed area develops color.
一般に感圧記録紙は、無色の発色性色素を不揮
発性オイルに溶解し、それを高分子皮膜で包んだ
直径数ミクロンないし十数ミクロンのマイクロカ
プセルを支持体上に塗布したもので、発色させる
時上記の感圧色素と接触すると反応を起し発色さ
せる性質のある白土やフエノール樹脂などの顕色
剤を含んだ塗料が塗布されている層と接触させ、
局部的圧力でその部分のマイクロカプセルが破壊
され、感圧色素溶液が顕色層に転移し、発色して
記録が得られるものや、または支持体表面にマイ
クロカプセル層と顕色剤層を二層に重ねるか、あ
るいは両者を混合して塗布しておいて加圧して発
色する機能を有するものである。 In general, pressure-sensitive recording paper is made by dissolving a colorless color-forming dye in non-volatile oil and coating it on a support with microcapsules with a diameter of several microns to more than ten microns, which are wrapped in a polymer film to create color. When it comes into contact with a layer coated with a paint containing a color developer such as white clay or phenolic resin, which has the property of causing a reaction and coloring when it comes into contact with the above pressure-sensitive dye,
The microcapsules in that area are destroyed by local pressure, and the pressure-sensitive dye solution is transferred to the color developer layer, producing color and recording, or the support has two layers, a microcapsule layer and a color developer layer, on the surface of the support. It has the function of developing color by applying a layer or by applying a mixture of the two and applying pressure.
上記の方法においては、記録を得る時に顕色剤
を塗布した支持体が必要であり、またこれらの記
録紙の製造においては色素を含有するマイクロカ
プセル層と顕色剤層の二度塗工、またはマイクロ
カプセルと顕色剤とを混合させるなどの時間と手
間が必要であり、コスト高となるものであつた。 In the above method, a support coated with a color developer is required to obtain a record, and in the production of these recording papers, a microcapsule layer containing a dye and a color developer layer are coated twice. Alternatively, it requires time and effort to mix the microcapsules and the color developer, resulting in high costs.
本発明は感圧色素とその色素と反応して発色せ
しめる顕色剤を同時に溶媒に溶解させた溶液を高
分子膜で包んだマイクロカプセルを支持体に一回
の塗布で感圧記録紙を得るもので、その製造プロ
セスをより簡単にさせ、コスト低減に導くもので
ある。 In the present invention, pressure-sensitive recording paper can be obtained by applying microcapsules in which a pressure-sensitive dye and a color developer that reacts with the dye and a developer that reacts with the dye are simultaneously dissolved in a solvent and wrapped in a polymer membrane to a support once. This simplifies the manufacturing process and reduces costs.
本発明に用いられる色素としての電子供与性発
色体としては、例えばトリフエニルメタンフタリ
ド系、フルオラン系、フエノチアジン系、インド
リルフタリド系、スピロピラン系、ロイコオーラ
ミン系、ローダミンラクタム系、トリフエニルメ
タン系、トリアゼン系、ナフトラクタム系、スピ
ロノタランキサンテン系、アゾメチン系、ベンゾ
ピラン系、ヒドロキシフタラン系、ロイコオーラ
ミン系などの群より選択される物質であり、また
顕色剤としての電子受容性発色助剤としては、フ
エノール化合物、フエノール−アルデヒド重合
体、フエノール−アセチレン重合体、ロジン変性
マレイン酸樹脂、スチレン−無水マレイン酸共重
合体加水分解物、カルボキシポリエチレン重合体
加水分解物、ビニルエチルエーテル−無水マレイ
ン酸共重合体加水分解物、エチレン−無水マレイ
ン酸共重合体加水分解物、あるいは酸性白土、ア
タパルガイド、ゼオライト、ベントナイト、カオ
リンの如き粘土鉱物、コハク酸、タンニン酸、没
食子酸などの群より選択される物質である。 Examples of the electron-donating coloring material as a pigment used in the present invention include triphenylmethanephthalide, fluoran, phenothiazine, indolyl phthalide, spiropyran, leucoolamine, rhodamine lactam, triphenyl It is a substance selected from the group such as methane type, triazene type, naphtholactam type, spironothalanxanthene type, azomethine type, benzopyran type, hydroxyphthalane type, leucoolamine type, and has electron-accepting properties as a color developer. Color development aids include phenol compounds, phenol-aldehyde polymers, phenol-acetylene polymers, rosin-modified maleic acid resins, styrene-maleic anhydride copolymer hydrolysates, carboxypolyethylene polymer hydrolysates, and vinyl ethyl ether. - Maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, or groups of clay minerals such as acid clay, attapulgite, zeolite, bentonite, kaolin, succinic acid, tannic acid, gallic acid, etc. It is a substance that is more selected.
上記の電子供与性発色体と電子受容性発色助剤
を溶解する溶剤としては、例えばアルキルナフタ
レン、ジアリルエタン、アルキルビフエニル、ト
リアリルジメタン、その他ケトン系、芳香族系の
溶剤がある。 Examples of the solvent for dissolving the electron-donating coloring material and electron-accepting coloring aid include alkylnaphthalene, diallylethane, alkylbiphenyl, triallyldimethane, and other ketone and aromatic solvents.
本発明のマイクロカプセルを製造する方法は、
種々の公知のカプセル化技術を利用することがで
きる。例えば、スプレードライ法、界面重合法、
コアセルベーシヨン法、相分離法、in−Situ重合
法など米国特許第3338991号明細書、同第3326848
号明細書、同第3502582号明細書などに記載され
ている方法などが使用できる。 The method for producing microcapsules of the present invention includes:
Various known encapsulation techniques can be utilized. For example, spray drying method, interfacial polymerization method,
Coacervation method, phase separation method, in-situ polymerization method, etc. U.S. Patent No. 3338991, U.S. Patent No. 3326848
The method described in the specification of No. 3,502,582, etc. can be used.
本発明におけるマイクロカプセルは、前記電子
供与性発色体と前記電子受容性発色助剤を溶媒に
溶解した溶液を含有するものである。このとき溶
液は未だ発色を示しておらず、無色乃至淡色の溶
液であり、この理由はかかる発色反応が平衡反応
であり、電子供与性発色体及び電子受容性発色助
剤の溶液においては溶解度の関係からこれらの濃
度が低いために発色反応が進行しないことによる
ものである。 The microcapsule in the present invention contains a solution in which the electron-donating coloring material and the electron-accepting coloring aid are dissolved in a solvent. At this time, the solution has not yet shown any color development and is a colorless to light-colored solution.The reason for this is that the color development reaction is an equilibrium reaction, and in the solution of the electron-donating color former and the electron-accepting color development aid, the solubility is low. This is because the coloring reaction does not proceed because these concentrations are low.
本発明のカプセルを形成する外殻物質として
は、例えばポリスチレン、ポリ−ｐ−クロルスチ
レン、ポリビニルトルエン、スチレン−ブタジエ
ン共重合体、スチレン−アクリル酸共重合体、ス
チレン−無水マレイン酸共重合体などのスチレン
又はその置換体の重合体又は共重合体、ポリエス
テル樹脂、アクリル系樹脂、キシレン系樹脂、ポ
リアミド樹脂、アイオノマー樹脂、フラン樹脂、
ケトン樹脂、テルペン樹脂、フエノール変性テル
ペン樹脂、ロジン、ロジン変性ペンタエリスリト
ールエステル、天然樹脂変性フエノール樹脂、天
然樹脂変性マレイン酸樹脂、クマロンインデン樹
脂、マレイン酸変性フエノール樹脂、脂環族炭化
水素樹脂、石油樹脂、フタル酸酢酸セルロース、
メチルビニルエーテル−無水マレイン酸共重合
体、澱粉グラフト重合体、ポリビニルブチラー
ル、ポリビニルアルコール、ポリビニルピロリド
ン、などが用いられる。 Examples of the shell material forming the capsule of the present invention include polystyrene, poly-p-chlorostyrene, polyvinyltoluene, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-maleic anhydride copolymer, etc. Polymers or copolymers of styrene or its substituted products, polyester resins, acrylic resins, xylene resins, polyamide resins, ionomer resins, furan resins,
Ketone resin, terpene resin, phenol-modified terpene resin, rosin, rosin-modified pentaerythritol ester, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, coumaron indene resin, maleic acid-modified phenolic resin, alicyclic hydrocarbon resin, Petroleum resin, cellulose acetate phthalate,
Methyl vinyl ether-maleic anhydride copolymer, starch graft polymer, polyvinyl butyral, polyvinyl alcohol, polyvinylpyrrolidone, etc. are used.
本発明の感圧記録紙は、上記マイクロカプセル
を例えばポリビニルアルコール、スチレン−ブタ
ジエンラテックス、ゼラチン、カゼイン、ヒドロ
キシエチルセルロース等の適当な結着剤中に分散
した塗液を支持体上に塗布・乾燥することによつ
て得ることができる。このようにして得られる感
圧記録紙は、圧力を加えられてプセルが破壊され
ることにより、カプセル中の溶媒が気化して発色
を生じるものである。 The pressure-sensitive recording paper of the present invention can be produced by applying a coating liquid on a support, in which the above microcapsules are dispersed in a suitable binder such as polyvinyl alcohol, styrene-butadiene latex, gelatin, casein, hydroxyethyl cellulose, etc., and drying. It can be obtained by In the pressure-sensitive recording paper thus obtained, the capsules are destroyed by applying pressure, and the solvent in the capsules evaporates, producing color development.
次に実施例にて本発明を説明する。 Next, the present invention will be explained with reference to Examples.
実施例
マイクロカプセルの芯物質としてクリスタルバ
イオレツトラクトン60重量部とビスフエノール
A40重量部とからなる発色材料をベンジントルエ
ンに固形分濃度５％になるよう溶解し、無色の溶
液を得た。次にスチレンモノマー80重量部、メチ
ルメタアクリレートモノマー20重量部からなる外
殻材料にこの芯物質を適用し、in−Situ法により
マイクロカプセルを作製した。このマイクロカプ
セル分散液にバインダーとしてポニビニルアルコ
ールを加え紙に塗布し、乾操して感圧記録紙を得
た。この感圧記録紙に部分的圧力を加えてマイク
ロカプセルを破壊したところ、鮮明なブルーの記
録が得られた。Example 60 parts by weight of crystal violet lactone and bisphenol as core material of microcapsules
A color forming material consisting of 40 parts by weight of A was dissolved in benzene toluene to a solid content concentration of 5% to obtain a colorless solution. Next, this core material was applied to a shell material consisting of 80 parts by weight of styrene monomer and 20 parts by weight of methyl methacrylate monomer, and microcapsules were produced by an in-situ method. Ponyvinyl alcohol was added as a binder to this microcapsule dispersion, and the mixture was coated on paper and dried to obtain pressure-sensitive recording paper. When partial pressure was applied to this pressure-sensitive recording paper to destroy the microcapsules, a clear blue record was obtained.
Claims (1)
発色助剤とを溶媒中に溶解させた無色乃至淡色の
溶液からなる芯物質を高分子膜で包んだマイクロ
カプセルを結着剤中に分散した塗液を塗布し、圧
力により該カプセルを破壊させ、カプセル中の溶
媒を気化させると同時に発色させることを特徴と
する感圧記録紙。1 Microcapsules in which a core substance consisting of a colorless to light-colored solution in which an electron-donating coloring material and an electron-accepting coloring aid are dissolved in a solvent are wrapped in a polymer membrane are placed on a support in a binder. A pressure-sensitive recording paper characterized in that a dispersed coating liquid is applied, the capsules are destroyed by pressure, the solvent in the capsules is vaporized, and color is developed at the same time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56108119A JPS5811190A (en) | 1981-07-13 | 1981-07-13 | Pressure sensitive recording paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56108119A JPS5811190A (en) | 1981-07-13 | 1981-07-13 | Pressure sensitive recording paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5811190A JPS5811190A (en) | 1983-01-21 |
| JPS6361194B2 true JPS6361194B2 (en) | 1988-11-28 |
Family
ID=14476396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56108119A Granted JPS5811190A (en) | 1981-07-13 | 1981-07-13 | Pressure sensitive recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5811190A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242885A (en) * | 1988-10-14 | 1993-09-07 | Kanzaki Paper Manufacturing Co., Ltd. | Pressure sensitive recording sheet with a layer containing microcapsules each containing color former and benzyl toluene |
| JPH02106387A (en) * | 1988-10-14 | 1990-04-18 | Kanzaki Paper Mfg Co Ltd | Pressure sensitive copying sheet |
| JP2009121526A (en) * | 2007-11-12 | 2009-06-04 | Otics Corp | Hydraulic automatic tensioner |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57142388U (en) * | 1981-03-04 | 1982-09-07 |
-
1981
- 1981-07-13 JP JP56108119A patent/JPS5811190A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5811190A (en) | 1983-01-21 |
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