JPH0227158B2 - - Google Patents
Info
- Publication number
- JPH0227158B2 JPH0227158B2 JP56183645A JP18364581A JPH0227158B2 JP H0227158 B2 JPH0227158 B2 JP H0227158B2 JP 56183645 A JP56183645 A JP 56183645A JP 18364581 A JP18364581 A JP 18364581A JP H0227158 B2 JPH0227158 B2 JP H0227158B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- sheet
- coloring
- parts
- forming
- 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
- 238000004040 coloring Methods 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 15
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 claims description 14
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Natural products C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- XWFXPIVEJIXOOD-UHFFFAOYSA-L zinc;2,2-diphenylacetate Chemical compound [Zn+2].C=1C=CC=CC=1C(C(=O)[O-])C1=CC=CC=C1.C=1C=CC=CC=1C(C(=O)[O-])C1=CC=CC=C1 XWFXPIVEJIXOOD-UHFFFAOYSA-L 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 239000000975 dye Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003094 microcapsule Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004927 clay Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- -1 barium Chemical class 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- PYHXGXCGESYPCW-UHFFFAOYSA-M 2,2-diphenylacetate Chemical compound C=1C=CC=CC=1C(C(=O)[O-])C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-M 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 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 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000000945 filler Substances 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
- 239000000499 gel Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide 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
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
Description
本発明の分野
本発明は、記録用呈色シートに関するものであ
る。更に詳しく述べるならば、本発明は、無色の
発色性染料と接触して鮮明でかつ性水性のすぐれ
た着色像を形成することのできる記録用呈色シー
トに関するものである。
本発明の背景
無色の発色性染料と、それと接触したとき、着
色像を形成することのできる呈色性酸性物質とを
利用した記録用シートは既に広く実用されてい
る。この記録用シートは、１対のシートからな
り、１枚のシートには、無色の発色染料を含有す
るマイクロカプセルが塗布されており、他方のシ
ートには、呈色性物質が塗布されていて、上記の
マイクロカプセル層と呈色性物質層とを重ね合せ
て、これに所望のパターンに従つて加圧操作を施
すと、マイクロカプセルが破裂し、発色性染料が
呈色性物質と接触して前記パターンの着色像を形
成するのである。（米国特許第2730457号および第
2730456号）
上述のような呈色シートにおいて、呈色性物質
として、活性白土、酸性白土、アタパルジヤイ
ト、カオリン、ゼオライト、或はこれらを化学
的、又は物理的に酸又はアルカリで処理した生成
物、或はフエノール化合物、フエノールボラツク
樹脂、サリチル酸、安息香酸、ナフトエ酸又はこ
れらの誘導体又は塩類などが用いられている。し
かし、従来の呈色性物質のみでは、着色像の鮮明
度および耐水性に不満があつた。
本発明の概要
本発明の目的は、鮮明で、かつ、耐水性の良好
な着色像を形成することのできる記録用呈色シー
トを提供することである。
上記目的を達成する本発明の記録用呈色シート
は、支持体と、この支持体の１面上に形成され、
無色の発色性染料と反応して着色像を形成する呈
色剤と、バインダーとを含む呈色層とを有し、前
記呈色剤が少くとも１種のジフエニル酢酸の多価
金属塩を含有することを特徴とするものである。
本発明の詳細な説明
本発明の記録用呈色シートは支持体と、その１
面上に形成された呈色層とを有している。支持体
は、紙、プラスチツクフイルム例えばポリエステ
ルフイルム、合成紙、などの従来支持体として使
用されている材料のいづれであつてもよいが、一
般には紙が用いられている。
呈色層は、呈色剤とバインダーとを含むもので
ある。本発明に用いられる呈色剤は少くともジフ
エニル酢酸の多価金属塩を含むものであり、上記
多価金属としては、マグネシウム、カルシウム、
バリウムなどのａ族金属、亜鉛、カドミウムな
どのｂ族金属、アルミニウムなどのａ族金
属、スズ、鉛などのａ族金属などが用いられる
が、最も好ましい多価金属は亜鉛である。
呈色層中におけるジフエニル酢酸多価金属塩の
量には、本発明の目的を達成し得る限り格別の限
定はないが一般には、呈色層の重量に対し、10％
以上、より好ましくは、30〜90％の範囲内にある
ことが好ましい。
ジフエニル酢酸多価金属塩は、予じめ調製した
ものをバインダーと混合してもよいし、或はジフ
エニル酢酸又は、そのアリカリ金属塩と、多価金
属の水酸化物、炭酸塩、又は塩化物と、バインダ
ーとを混合し、この混合物中でジフエニル酢酸多
価金属塩を生成させてもよい。
呈色層中の呈色剤は、ジフエニル酢酸多価金属
塩に加えて、その他の呈色性物質を含有していて
もよい。前記呈色性物質（固体酸）は、酸性白
土、アタパルジヤイト、ゼオライト、カオリン、
ベントナイト、活性白土などの粘土類を包含する
無機固体酸、並びに、酸性フエノール化合物、フ
エノールノボラツク樹脂類、および、カルボン酸
基、スルフオン酸基およびフエノール性水酸基か
ら選ばれた少くとも１個の酸性基を有する芳香族
酸、又はその重合体の多価金属塩などの有機固体
酸から選択されるものである。
上述のような呈色性物質は、ジフエニル酢酸多
価金属塩重量に対し５〜90％の割合で使用するこ
とができる。
本発明に係る呈色層は、バインダーと、ジフエ
ニル酢酸多価金属塩と、必要により、他の呈色性
物質とを含む混合物によつて形成される。バイン
ダーとしては、本発明の目的を達成し得る限り、
どのようなものを用いてもよいが、一般には、ア
ラビヤゴム、ポリビニルアルコール、デンプン、
カルボキシメチルセルロース、およびヒドロキシ
エチルセルロースなどの水溶性重合体、並びに、
スチレン−ブタジエン共重合体、メチルメタクリ
レート−ブタジエン共重合体、アクリル系重合体
などの水性エマルジヨン化可能な合成重合体、更
に、ポリビニルブチラール、およびエチルセルロ
ースなどの有機溶剤可溶な合成重合体から選択さ
れる。一般にバインダーは、呈色層重量に対し10
〜70％の範囲で用いられることが好ましい。
本発明の記録用呈色シートを製造するには、所
望量のジフエニル酢酸多価金属塩と、所望により
他の呈色性物質とを、水、および又は、有機溶剤
と混合し、次に、これにバインダーを混合して均
一な塗工液を調製し、この塗工液を、支持体の一
面に塗布し、これを乾燥する。このとき、塗工液
の塗布量は、乾燥固形分重量に換算して、２〜
12g／m2であることが好ましい。塗工液中に用い
られる有機溶剤としては、例えばメタノール、エ
タノール、アセトン、ベンゼン、トルエン、メチ
ルイソブチルケトン、シクロヘキサン、およびこ
れらの１種以上の混合物を用いることができる。
本発明の呈色層は、上記成分の他に、添加物と
して、クレー、炭酸カルシウム、タルクなどの充
填剤、着色剤、増白剤、酸化防止剤、紫外線吸収
剤などを含んでいてもよいし、更に、発色増進剤
として、亜鉛、スズ、マグネシウム、カルシウ
ム、バナジウム、マンガンなどの二価以上の金属
の、酸化物、炭酸塩、水酸化物、塩化物、および
硫酸塩などの少くとも１種を含んでいてもよい。
本発明の呈色シートは、無色の発色性染料と接
触すると、シート上に所望の着色像を形成するこ
とができる。発色性染料としては一般の感圧記録
シートに用いられるものであるならば、格別の限
定はなく、例えば、クリスタルバイオレツトラク
トン、ベンゾイルロイコメチレンブルー、マラカ
イトグリーンラクトン、ローダミンＢ−ラクタ
ム、および各種フルオラン系染料などの１種又
は、これらの２種以上の混合物を用いることがで
きる。
一般に感圧記録シートにおいては、発色性染料
は、マイクロカプセル中に含まれているが、この
ようなマイクロカプセルは、既知の方法のいづれ
で製造されたものであつてもよい。例えば、米国
特許許第2800457号記載の方法に従つて、酸処理
されたゼラチン16重量部とカルボキシメチルセル
ロース４重量部を40℃の水400部に溶解し、これ
に発色染料油110重量部を乳化分散する。上記発
色染料油としては、例えばアルキル化ナフタレン
油100重量部にクリスタルバイオレツトラクトン
５重量％を溶解したものなどが用いられる。
上記乳化分散工程において油滴の大きさが所望
のサイズ（例えば５〜10ミクロン）になつたら乳
化分散操作を中止し、これに40℃の水を加えて、
全量を1000重量部とし、撹拌操作を続けて施し、
これに５％酢酸を添加して液のPHを4.0に調節す
る。すると、液中でコアセルベーシヨンが生起す
る。撹拌を20分続けて施し、この液を氷水で冷却
し、油滴の周囲に沈着したコアセルベート膜をゲ
ル化する。
液温が10℃に低下したら37％ホルムアルデヒド
水溶液７重量部を液に添加し、更に15％カセイソ
ーダ水溶液を添加し、液のPHを９に調節し24時間
撹拌するとマイクロカプセル分散液が得られる。
上記のマイクロカプセル分散液にバインダー
と、クツシヨン剤とを添加して、カプセル塗工液
を調製し、これを支持体、例えば重量40g／m2の
紙に塗布する。このときの塗布量は、一般には、
固形分換算量で２〜8g／m2、例えば4g／m2であ
ることが好ましい。上記のようにして発色染料マ
イクロカプセル層を有する発色剤シートが得られ
る。
本発明の好ましい態様を下記実施例によつて説
明する。
これら実施例において、得られた呈色シートの
性能は下記のようにして評価した。
１ 発色濃度
発色染料としてクリスタルバイオレツトラク
トンを含有するマイクロカプセル塗工シート
と、呈色シートとを重ね合わせ、これに所定パ
ターンに従つて加圧操作を施して、呈色シート
上に着色像を形成した。この着色像を24時間室
内に放置しその濃度をグレターク濃度計により
測定した。
２ 耐水性
呈色シート上の着色像上に水滴を滴下し、そ
の直後の着色度を評価した。
良好…消色が認められない。
不良…消色した。
３ 耐光性
呈色シート上の着色像に対し、フエードメー
ターにより４時間の光照射を施し、着色濃度の
変化を観察した。
評価 着色濃度の低下
Ａ… 小
Ｂ… 中
Ｃ… 大
実施例 １
水160部にジフエニル酢酸亜鉛40部を分散し、
これに10％でんぷん溶液20部、スチレン−ブタジ
エン共重合体のラテツクス（50％液）15部を加
え、十分に撹拌して塗工液を調製した。この塗工
液を40g／m2の原紙の片面に、塗布量が乾燥重量
で8g／m2になるように塗布乾燥した。得られた
発色シートの性能を第１表に示す。
実施例 ２
水340部に、ジフエニル酢酸亜鉛40部、活性白
土40部、酸化亜鉛２部、チオ尿素６部を加え、こ
れに分散剤として、ヘキサメタリリン酸ソーダ
0.4部を加えて分散液を調整し、これに10％でん
ぷん溶液40部、スチレン−ブタジエン共重合体の
ラテツクス（50％液）30部を加え十分撹拌して塗
工液を調製した。この塗工液を40g／m2の原紙の
片面に、塗布量が乾燥重量で8g／m2になるよう
に塗布乾燥した。得られた呈色シートの性能を第
１表に示す。
実施例 ３
水200部に、ジフエニル酢酸40部、および水酸
化亜鉛10部を混合分散後、これに10％でんぷん溶
液25部、およびスチレン−ブタジエン共重合体の
ラテツクス（50％液）18部を加え、十分に撹拌し
て塗工液を調製した。この塗工液を40g／m2の原
紙の片面に、塗布量が、乾燥重量で8g／m2にな
るように塗布乾燥した。得られた呈色シートの性
能を第１表に示す。
実施例 ４
エチルアルコール160部に、ジフエニル酢酸亜
鉛40部を混合分散後これに10％ポリビニルブチラ
ールエタノール溶液40部を加え、十分撹拌して塗
工液を調製した。この塗工液を40g／m2の原紙の
片面に、塗布量が乾燥重量で8g／m2になるよう
に塗布乾燥した。得られた呈色シートの性能を第
１表に示す。
実施例 ５
アセトトン160部に、ジフエニル酢酸亜鉛40部
を溶解し、これに10％エチルセルロースアセトン
溶液40部を加え、十分撹拌して塗工液を調製し
た。この塗工液を40g／m2の原紙の片面に、塗布
量が乾燥重量で8g／m2になるように塗布乾燥し
た。得られた呈色シートの性能を第１表に示す。
比較例 １
水130部に、活性白土40部を混合分散後、これ
に10％でんぷん溶液20部およびスチレン−ブタジ
エン共重合体のラテツクス（50％液）15部を加え
て比較塗工液を調製した。これを40g／m2原紙
に、塗布量が乾燥重量で8g／m2になるように塗
布した。得られた比較呈色シートの性能を第２表
に示す。
比較例 ２
比較例１の方法において活性白土の代わりにジ
フエニル酢酸40部を使用し、その他は比較例１と
同じ工程を繰り返した。得られた比較呈色シート
の性能を第２表に示す。
FIELD OF THE INVENTION The present invention relates to a color forming sheet for recording. More specifically, the present invention relates to a color-forming sheet for recording that can form a clear, water-based, and highly colored image when brought into contact with a colorless color-forming dye. BACKGROUND OF THE INVENTION Recording sheets that utilize a colorless color-forming dye and a color-forming acidic substance that can form a colored image when in contact with the color-forming dye have already been widely put into practical use. This recording sheet consists of a pair of sheets; one sheet is coated with microcapsules containing a colorless coloring dye, and the other sheet is coated with a coloring substance. When the above-mentioned microcapsule layer and color-forming substance layer are superimposed and pressurized according to a desired pattern, the microcapsules burst and the color-forming dye comes into contact with the color-forming substance. Then, a colored image of the pattern is formed. (U.S. Patent No. 2730457 and
No. 2730456) In the color-forming sheet as described above, the color-forming substance is activated clay, acid clay, attapulgite, kaolin, zeolite, or a product obtained by chemically or physically treating these with acid or alkali. Alternatively, phenol compounds, phenol volak resins, salicylic acid, benzoic acid, naphthoic acid, or derivatives or salts thereof are used. However, when using only conventional color-forming substances, there was dissatisfaction with the clarity and water resistance of colored images. SUMMARY OF THE INVENTION An object of the present invention is to provide a color-forming sheet for recording that can form a colored image that is clear and has good water resistance. The recording coloring sheet of the present invention that achieves the above object includes a support, a support formed on one side of the support,
It has a coloring layer containing a binder and a coloring agent that reacts with a colorless coloring dye to form a colored image, and the coloring agent contains at least one polyvalent metal salt of diphenylacetic acid. It is characterized by: DETAILED DESCRIPTION OF THE INVENTION The recording coloring sheet of the present invention comprises a support and a
It has a coloring layer formed on the surface. The support may be any of the materials conventionally used as supports, such as paper, plastic film such as polyester film, synthetic paper, etc., although paper is generally used. The coloring layer contains a coloring agent and a binder. The coloring agent used in the present invention contains at least a polyvalent metal salt of diphenylacetic acid, and the polyvalent metals include magnesium, calcium,
A-group metals such as barium, B-group metals such as zinc and cadmium, A-group metals such as aluminum, and A-group metals such as tin and lead are used, but the most preferred polyvalent metal is zinc. The amount of polyvalent metal salt of diphenylacetate in the coloring layer is not particularly limited as long as the object of the present invention can be achieved, but generally it is 10% based on the weight of the coloring layer.
Above, it is more preferably within the range of 30 to 90%. The polyvalent metal salt of diphenylacetic acid may be prepared in advance and mixed with a binder, or it may be prepared by mixing diphenylacetic acid or an alkali metal salt thereof with a hydroxide, carbonate, or chloride of a polyvalent metal. and a binder, and a polyvalent metal salt of diphenylacetic acid may be produced in this mixture. The coloring agent in the coloring layer may contain other coloring substances in addition to the polyvalent metal salt of diphenylacetic acid. The color-forming substance (solid acid) is acid clay, attapulgite, zeolite, kaolin,
At least one acid selected from inorganic solid acids including clays such as bentonite and activated clay, acidic phenolic compounds, phenolic novolak resins, and carboxylic acid groups, sulfonic acid groups, and phenolic hydroxyl groups. It is selected from organic solid acids such as aromatic acids having groups or polyvalent metal salts of polymers thereof. The above-mentioned color-forming substance can be used in a proportion of 5 to 90% based on the weight of the polyvalent metal salt of diphenylacetic acid. The coloring layer according to the present invention is formed from a mixture containing a binder, a polyvalent metal salt of diphenylacetic acid, and, if necessary, other coloring substances. As the binder, as long as the purpose of the present invention can be achieved,
Any material may be used, but in general, gum arabic, polyvinyl alcohol, starch,
water-soluble polymers such as carboxymethylcellulose and hydroxyethylcellulose, and
Synthetic polymers that can be formed into aqueous emulsions, such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, and acrylic polymers, as well as organic solvent-soluble synthetic polymers such as polyvinyl butyral and ethyl cellulose. Ru. Generally, the binder is 10% of the weight of the coloring layer.
It is preferably used in a range of 70%. In order to produce the recording coloring sheet of the present invention, a desired amount of polyvalent metal salt of diphenylacetic acid and, if desired, other coloring substances are mixed with water and/or an organic solvent, and then, A binder is mixed with this to prepare a uniform coating solution, and this coating solution is applied to one surface of the support and dried. At this time, the coating amount of the coating liquid is 2 to 2 to
Preferably it is 12 g/m 2 . As the organic solvent used in the coating liquid, for example, methanol, ethanol, acetone, benzene, toluene, methyl isobutyl ketone, cyclohexane, and mixtures of one or more of these can be used. In addition to the above-mentioned components, the coloring layer of the present invention may contain fillers such as clay, calcium carbonate, and talc, colorants, brighteners, antioxidants, and ultraviolet absorbers as additives. Furthermore, as a color enhancer, at least one of oxides, carbonates, hydroxides, chlorides, and sulfates of divalent or higher metals such as zinc, tin, magnesium, calcium, vanadium, and manganese is used. May contain seeds. When the color-forming sheet of the present invention comes into contact with a colorless color-forming dye, a desired colored image can be formed on the sheet. The color-forming dye is not particularly limited as long as it is used in general pressure-sensitive recording sheets, and examples thereof include crystal violet lactone, benzoyl leucomethylene blue, malachite green lactone, rhodamine B-lactam, and various fluoran-based dyes. One type of dye or a mixture of two or more of these can be used. Generally, in a pressure-sensitive recording sheet, color-forming dyes are contained in microcapsules, but such microcapsules may be produced by any known method. For example, according to the method described in U.S. Patent No. 2,800,457, 16 parts by weight of acid-treated gelatin and 4 parts by weight of carboxymethyl cellulose are dissolved in 400 parts of water at 40°C, and 110 parts by weight of coloring dye oil is emulsified therein. Spread. As the above-mentioned coloring dye oil, for example, one in which 5% by weight of crystal violet lactone is dissolved in 100 parts by weight of alkylated naphthalene oil is used. In the above emulsification and dispersion process, when the size of the oil droplets reaches the desired size (for example, 5 to 10 microns), the emulsification and dispersion operation is stopped, and water at 40°C is added to it.
The total amount was 1000 parts by weight, and the stirring operation was continued.
Add 5% acetic acid to this to adjust the pH of the liquid to 4.0. Then, coacervation occurs in the liquid. Stirring is continued for 20 minutes, and the liquid is cooled with ice water to gel the coacervate film deposited around the oil droplets. When the liquid temperature drops to 10°C, 7 parts by weight of a 37% formaldehyde aqueous solution is added to the liquid, followed by a 15% caustic soda aqueous solution, the pH of the liquid is adjusted to 9, and the mixture is stirred for 24 hours to obtain a microcapsule dispersion. A binder and a cushioning agent are added to the above microcapsule dispersion to prepare a capsule coating solution, which is coated on a support, for example, paper having a weight of 40 g/m 2 . The amount of coating at this time is generally
It is preferably 2 to 8 g/m 2 , for example 4 g/m 2 in terms of solid content. A coloring agent sheet having a coloring dye microcapsule layer is obtained as described above. Preferred embodiments of the invention will be illustrated by the following examples. In these Examples, the performance of the obtained colored sheets was evaluated as follows. 1 Coloring density A microcapsule coated sheet containing crystal violet lactone as a coloring dye and a coloring sheet are superimposed, and a pressure operation is applied to this according to a predetermined pattern to form a colored image on the coloring sheet. Formed. This colored image was left indoors for 24 hours, and its density was measured using a Greetak densitometer. 2 Water Resistance Water droplets were dropped onto the colored image on the colored sheet, and the degree of coloration immediately after that was evaluated. Good...No discoloration observed. Defective... Discolored. 3. Light resistance The colored image on the colored sheet was irradiated with light for 4 hours using a fade meter, and changes in color density were observed. Decrease in evaluated coloring density A... Small B... Medium C... Large Example 1 Disperse 40 parts of zinc diphenyl acetate in 160 parts of water,
To this were added 20 parts of a 10% starch solution and 15 parts of a styrene-butadiene copolymer latex (50% liquid) and thoroughly stirred to prepare a coating solution. This coating solution was applied to one side of a 40 g/m 2 base paper so that the dry weight was 8 g/m 2 and dried. Table 1 shows the performance of the obtained coloring sheet. Example 2 40 parts of zinc diphenyl acetate, 40 parts of activated clay, 2 parts of zinc oxide, and 6 parts of thiourea were added to 340 parts of water, and sodium hexametalyphosphate was added as a dispersant.
0.4 part was added to prepare a dispersion liquid, and 40 parts of a 10% starch solution and 30 parts of a styrene-butadiene copolymer latex (50% liquid) were added thereto and thoroughly stirred to prepare a coating liquid. This coating solution was applied to one side of a 40 g/m 2 base paper so that the dry weight was 8 g/m 2 and dried. The performance of the obtained colored sheet is shown in Table 1. Example 3 After mixing and dispersing 40 parts of diphenyl acetic acid and 10 parts of zinc hydroxide in 200 parts of water, 25 parts of a 10% starch solution and 18 parts of styrene-butadiene copolymer latex (50% liquid) were added thereto. The mixture was added and thoroughly stirred to prepare a coating solution. This coating solution was applied to one side of a 40 g/m 2 base paper so that the coating amount was 8 g/m 2 in terms of dry weight and dried. The performance of the obtained colored sheet is shown in Table 1. Example 4 After mixing and dispersing 40 parts of zinc diphenyl acetate in 160 parts of ethyl alcohol, 40 parts of a 10% polyvinyl butyral ethanol solution was added thereto and thoroughly stirred to prepare a coating liquid. This coating solution was applied to one side of a 40 g/m 2 base paper so that the dry weight was 8 g/m 2 and dried. The performance of the obtained colored sheet is shown in Table 1. Example 5 40 parts of zinc diphenyl acetate was dissolved in 160 parts of acetotone, 40 parts of a 10% ethyl cellulose acetone solution was added thereto, and the mixture was sufficiently stirred to prepare a coating solution. This coating solution was applied to one side of a 40 g/m 2 base paper so that the dry weight was 8 g/m 2 and dried. The performance of the obtained colored sheet is shown in Table 1. Comparative Example 1 A comparative coating liquid was prepared by mixing and dispersing 40 parts of activated clay in 130 parts of water, and then adding 20 parts of a 10% starch solution and 15 parts of styrene-butadiene copolymer latex (50% liquid). did. This was applied to 40 g/m 2 base paper at a dry weight of 8 g/m 2 . Table 2 shows the performance of the comparative colored sheets obtained. Comparative Example 2 The same process as in Comparative Example 1 was repeated except that 40 parts of diphenyl acetic acid was used instead of activated clay in the method of Comparative Example 1. Table 2 shows the performance of the comparative colored sheets obtained.
【表】【table】
Claims (1)
無色の発色性染料と反応して着色像を形成する呈
色剤と、バインダーとを含む呈色層とを有する呈
色シートにおいて、 前記呈色剤が、少くとも１種のジフエニル酢酸
の多価金属塩を含有することを特徴とする、 記録用呈色シート。 ２ 前記ジフエニル酢酸の多価金属塩がジフエニ
ル酢酸亜鉛である、特許請求の範囲第１項記載の
記録用呈色シート。 ３ 前記呈色剤が、前記ジフエニル酢酸の多価金
属塩に加えて、少くとも１種の他の呈色性物質を
含む、特許請求の範囲第１項記載の記録用呈色シ
ート。 ４ 前記ジフエニル酢酸の多価金属塩の量が、前
記呈色層の重量に対し、10％から90％までの範囲
内にある、特許請求の範囲第１項記載の記録用呈
色シート。[Scope of Claims] 1. A support, formed on one surface of the support,
A color-forming sheet having a color-forming layer containing a binder and a color-forming agent that reacts with a colorless color-forming dye to form a colored image; A coloring sheet for recording, characterized by containing a metal salt. 2. The coloring sheet for recording according to claim 1, wherein the polyvalent metal salt of diphenylacetic acid is zinc diphenylacetate. 3. The color-forming sheet for recording according to claim 1, wherein the color-forming agent contains at least one other color-forming substance in addition to the polyvalent metal salt of diphenylacetic acid. 4. The color-changing sheet for recording according to claim 1, wherein the amount of the polyvalent metal salt of diphenylacetic acid is within the range of 10% to 90% based on the weight of the coloring layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56183645A JPS5887087A (en) | 1981-11-18 | 1981-11-18 | Coloring sheet for recording |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56183645A JPS5887087A (en) | 1981-11-18 | 1981-11-18 | Coloring sheet for recording |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5887087A JPS5887087A (en) | 1983-05-24 |
| JPH0227158B2 true JPH0227158B2 (en) | 1990-06-14 |
Family
ID=16139410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56183645A Granted JPS5887087A (en) | 1981-11-18 | 1981-11-18 | Coloring sheet for recording |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5887087A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020160939A1 (en) | 2019-02-07 | 2020-08-13 | Basf Se | Bismuth-containing catalyst comprising at least one aromatic substituent |
| WO2021148332A1 (en) | 2020-01-23 | 2021-07-29 | Basf Se | Mixtures comprising bismuth-containing catalysts and diols |
| WO2023247716A2 (en) | 2022-06-24 | 2023-12-28 | Basf Se | Bismuth-containing catalyst comprising a dicarboxylate ligand |
-
1981
- 1981-11-18 JP JP56183645A patent/JPS5887087A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5887087A (en) | 1983-05-24 |
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