JPS6347190A - Pressure sensitive recording sheet - Google Patents
Pressure sensitive recording sheetInfo
- Publication number
- JPS6347190A JPS6347190A JP61190626A JP19062686A JPS6347190A JP S6347190 A JPS6347190 A JP S6347190A JP 61190626 A JP61190626 A JP 61190626A JP 19062686 A JP19062686 A JP 19062686A JP S6347190 A JPS6347190 A JP S6347190A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive recording
- group
- colorants
- sheet
- recording sheet
- 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.)
- Pending
Links
- 239000003094 microcapsule Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000002252 acyl group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000004927 clay Substances 0.000 abstract description 4
- 239000002174 Styrene-butadiene Substances 0.000 abstract description 3
- 239000004816 latex Substances 0.000 abstract description 3
- 229920000126 latex Polymers 0.000 abstract description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005011 phenolic resin Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011115 styrene butadiene Substances 0.000 abstract description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical class C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007754 air knife coating Methods 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- -1 aromatic carboxylic acids Chemical class 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
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 125000005044 dihydroquinolinyl group Chemical class N1(CC=CC2=CC=CC=C12)* 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
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 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 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
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001568 phenolic resin Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は 感圧記録シートに関するものであり、特に発
色剤と顕色剤との発色反応を利用した感圧記録シートに
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a pressure-sensitive recording sheet, and particularly to a pressure-sensitive recording sheet that utilizes a color-forming reaction between a color former and a color developer.
本発明による感圧記録シートは 各種の複写用紙、記録
用紙などとして使用される。The pressure-sensitive recording sheet according to the present invention is used as various types of copy paper, recording paper, etc.
感圧記録シートは 無色あるいはほぼ無色の電子供与性
染料（発色剤）を適当な溶剤に溶解し、その油滴をマイ
クロカプセル化したマイクロカプセルを含むマイクロカ
プセル層を支持体上に塗布した上葉紙、電子受容性化合
物（顕色剤）を含む顕色剤層を他の支持体上に塗布した
下葉紙、及び場合によっては 一つの支持体の一面にマ
イクロカプセル層を、他面に顕色剤層を塗布した中葉紙
を組み合わせた構成、あるいは支持体の同一面に前記の
マイクロカプセルと顕色剤が含有されているもの、さら
に支持体中に前記のマイクロカブセルか顕色剤のいずれ
かが含有され、その他方のものがその支持体上に塗布さ
れたものなどがある。A pressure-sensitive recording sheet is an upper layer in which a colorless or almost colorless electron-donating dye (coloring agent) is dissolved in an appropriate solvent, and a microcapsule layer containing microcapsules containing oil droplets is coated on a support. paper, base paper with a color developer layer containing an electron-accepting compound (color developer) coated on another support, and in some cases, a microcapsule layer on one side of one support and a developer layer on the other side. A structure in which a medium paper coated with a colorant layer is combined, or a structure in which the above-mentioned microcapsules and a color developer are contained on the same side of the support, and a structure in which either the above-mentioned microcapsules or a color developer are contained in the support. There is one in which one is contained and the other is coated on the support.
これらの感圧記録シートについては 例えば米国特許第
２□５０５．４７０号、同第２．５０５．４８９号、同
第２゜５５０、４７１号、同第２，７１２，５０７号、
同第２．７３０．４５６号、同第２．７３０．４５７号
、同３．４１８．２５０号、同第３゜４３２．３２７号
、同第３，９８１．８２１号、同第３．９９３．８３１
号、同第３，９９６．１５６号、同第３，９９６，４０
５号及び同第４，０００，０８７号などの各明細書に詳
細に記載されている。Regarding these pressure-sensitive recording sheets, for example, U.S. Pat.
2.730.456, 2.730.457, 3.418.250, 3.432.327, 3.981.821, 3.993. 831
No. 3,996.156, No. 3,996,40
It is described in detail in various specifications such as No. 5 and No. 4,000,087.
しかしこれらの感圧記録シートにおいて、発色イネの日
光に対する耐久性（耐光性）は 十分ではなく、未だ実
用上の重大な欠点となっている。さらに支持体上の塗布
面が着色し、シートを裁断した場合 その裁断面に発色
汚れが生ずるなどの問題があった。However, in these pressure-sensitive recording sheets, the durability of colored rice against sunlight (lightfastness) is not sufficient, and this is still a serious drawback in practical use. Furthermore, there was a problem in that the coated surface on the support was colored, and when the sheet was cut, colored stains appeared on the cut surface.
〔問題点を解決するための手段及び作用〕本発明は 上
述した従来技術における問題点を解決し、さらにより優
れた特性を有する新規な感圧記録シートを提供すること
を目的とするものであって、その構成は 支持体上にほ
ぼ無色の発色剤を溶解した油滴をマイクロカプセル化し
たマイクロカプセルを含む発色剤層が設けられている感
圧記録シートにおいて 該マイクロカプセル中に下記の
一般式（Ｉ）によって表される化合物が含まれているこ
とを特徴とする感圧記録シートである。[Means and effects for solving the problems] It is an object of the present invention to solve the above-mentioned problems in the prior art and to provide a new pressure-sensitive recording sheet having even more excellent characteristics. The structure is as follows: In a pressure-sensitive recording sheet in which a color former layer containing microcapsules in which oil droplets in which an almost colorless color former is dissolved is provided on a support, the following general formula is contained in the microcapsules. This is a pressure-sensitive recording sheet characterized by containing a compound represented by (I).
一般式（Ｉ）
ＩＲ１
（式中、Ｘは 炭素原子数１〜１８のアルキレン基、Ｒ
１及びＲ２，は メチル基またはエチル基、Ｒ３は 炭
素原子数１〜１８のアルキル基、炭素原子数７〜１２の
１７−７）（、十ル基または炭素原子数１〜１８のアシ
ル基を表す。）
以下 本発明の詳細な説明する。General formula (I) IR1 (wherein, X is an alkylene group having 1 to 18 carbon atoms, R
1 and R2 are methyl or ethyl groups; R3 is an alkyl group having 1 to 18 carbon atoms; ) The present invention will be described in detail below.
上述したように本発明の最も特徴とするところは 発色
剤を含有するマイクロカプセル中に上記の特定の一般式
（Ｉ）によって表される化合物が含まれていることであ
る。この一般式（Ｉ）によって表される化合物の好まし
い具体例としては 下記の第１表に示されているものが
ある。As mentioned above, the most characteristic feature of the present invention is that the compound represented by the above specific general formula (I) is contained in microcapsules containing a color former. Preferred specific examples of the compound represented by the general formula (I) are shown in Table 1 below.
第１表
（第１表 続き）
勿論 上記の一般式（Ｉ）に包含される具体例以外の他
の化合物を使用してもよい。Table 1 (Continued from Table 1) Of course, compounds other than the specific examples included in the above general formula (I) may be used.
また発色春１としては 従来の感圧記録シートにおいて
使用されているトリアリールメタン系化合物、ジフェニ
ルメタン系化合物、キサンチン系化合物、チアジン系化
合物、スピロ系化合物、ジアリールアミノフルオラン誘
導体、あるいはこれらの混合物などがある。In addition, the color spring 1 includes triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, spiro compounds, diarylaminofluoran derivatives, or mixtures thereof, which are used in conventional pressure-sensitive recording sheets. There is.
前記一般式（Ｉ）によって表される化合物の添加量は
発色剤に対して５〜２００重量％の範囲内の量、特に好
ましくは２０〜１００重量％の範囲内の量である。The amount of the compound represented by the general formula (I) added is
The amount is in the range from 5 to 200% by weight, particularly preferably from 20 to 100% by weight, based on the color former.
これら発色剤成分の他に 例えば本発明者らの先行の発
明による２、２．６−チトラメチルピベラジン誘導体、
ジヒドロキノリン誘導体、ジフェニルアミン誘導体など
の化合物を併用、添加することができる。In addition to these color former components, for example, 2,2,6-titramethylpiverazine derivatives according to the previous invention of the present inventors,
Compounds such as dihydroquinoline derivatives and diphenylamine derivatives can be used or added.
これらの各成分は 適宜選択され、溶剤に溶解されてマ
イクロカプセル化されるが、その溶剤溶液中には所望に
よりベンゾトリアゾール系化合物、ベンゾフェノン系化
合物、サリチル酸系化合物、シアノアクリレート系化合
物などの紫外線吸収剤が添加される。Each of these components is appropriately selected, dissolved in a solvent, and microencapsulated. If desired, the solvent solution contains ultraviolet absorbing compounds such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, and cyanoacrylate compounds. agent is added.
上記の溶剤としては 天然油あるいは合成油が単独であ
るいは併用して用いられる。溶剤の具体例としては 綿
実油、灯油、パラフィン、ナフテン油、アルキル化ビフ
ェニル、アルキル化ターフェニル、塩素化パラフィン、
アルキル化ナフタレン、ジフェニルアルカンなどがある
。As the above solvent, natural oil or synthetic oil may be used alone or in combination. Specific examples of solvents include cottonseed oil, kerosene, paraffin, naphthenic oil, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins,
Examples include alkylated naphthalenes and diphenylalkanes.
このように各成分が適宜調合され、調製された溶液を用
いて発色剤含有マイクロカプセルを製造する方法として
は 界面重合法、内部重合法、相分離法、コアセルベー
ション法などがある。Methods for manufacturing color former-containing microcapsules using solutions in which each component is appropriately mixed and prepared include interfacial polymerization, internal polymerization, phase separation, and coacervation.
このようにして調製された発色剤含有マイクロカプセル
を用い、それを含む塗布液を調製する際には 通常その
塗布液中に水溶性バインダーやうテックス系バインダー
などのバインダー、さらにセルローズ粉末、澱粉粉末、
タルクなどのカプセル保護剤なども適宜添加され、これ
をもって塗布液が調製される。When preparing a coating solution containing the microcapsules containing a color former prepared in this way, the coating solution usually contains a binder such as a water-soluble binder or a tex-based binder, as well as cellulose powder, starch powder, etc.
A capsule protectant such as talc is also added as appropriate, and a coating solution is prepared using this.
塗布液は 所望の支持体上に塗布され、乾燥されてマイ
クロカプセル層を形成し、例えば上葉紙とされる。The coating solution is coated onto a desired support and dried to form a microcapsule layer, for example a topsheet.
他方、上記のマイクロカプセル層中の発色剤と反応する
顕色剤の例としては 酸性白土、活性白土、アタパルジ
ャイト、ゼオライト、ベントナイト、カオリンのごとき
粘土物質、芳香族カルボン酸の金属塩あるいはフェノー
ル樹脂などが挙げられる。これらの顕色剤は スチレン
ーブタジエンラテソクスのごときバインダーと共に÷分
溌升ソｅ÷＋（塗布液が調製され、紙などのごとき所望
の支持体に塗布、乾燥されて この支持体上に顕色剤層
を形成し、例えば下葉紙とされる。On the other hand, examples of color developers that react with the color former in the microcapsule layer include acid clay, activated clay, attapulgite, zeolite, bentonite, clay materials such as kaolin, metal salts of aromatic carboxylic acids, and phenolic resins. can be mentioned. These color developers are used together with a binder such as styrene-butadiene latex to form a coating solution, which is coated onto a desired support such as paper, dried, and developed on this support. It forms a coloring layer and is used as, for example, bottom paper.
以上のごとく製造した例えば上葉紙及び下葉紙は 「従
来技術」の項において説明したように、重ね合わされて
”感圧記録シー１となり、この上葉紙に筆記により筆圧
を加えて上葉紙のマイクロカプセル層の内部のマイクロ
カプセルを破壊し、それによって内部の発色剤を放出し
、これを下葉紙の顕色剤と反応させ、その筆圧部分、つ
まり筆記跡に発色画像を形成し、これが筆記画像の複写
像となるのである。For example, the top sheet and bottom sheet produced as described above are stacked together to form a "pressure-sensitive recording sheet 1" as explained in the "Prior Art" section, and then pressure is applied to this top sheet by writing. The microcapsules inside the microcapsule layer of the leaf paper are destroyed, thereby releasing the coloring agent inside, which reacts with the color developer of the lower paper, creating a colored image on the pressure area of the writing, that is, the trace of the handwriting. This becomes a copy of the written image.
なお、本発明の感圧記録シートと組み合わせて使用され
る下葉紙は 例えば次のようにして製造することができ
る。Note that the bottom paper used in combination with the pressure-sensitive recording sheet of the present invention can be manufactured, for example, as follows.
顕色剤シート（下葉紙）の調製
水７０部（重量部。以下同じ。）に酸化亜鉛２部と炭酸
カルシウム１８部及び３，５−ジ−α−メチルベンジル
サリチル酸亜鉛４部を添加して混合し、次いでアトライ
ターにより３０分間分散処理したのち、カルボキシ変性
ＳＢＲラテックスを固形分で２．５部と１０重量％ポリ
ビニルアルコール（ケン化度９９％、重合度１０００）
水溶液１２部を添加し、均一に攪拝して塗布液とした。To 70 parts (parts by weight; the same applies hereinafter) of water prepared for a color developer sheet (lower paper), 2 parts of zinc oxide, 18 parts of calcium carbonate, and 4 parts of zinc 3,5-di-α-methylbenzylsalicylate were added. After dispersing for 30 minutes using an attritor, 2.5 parts of carboxy-modified SBR latex and 10% by weight polyvinyl alcohol (degree of saponification 99%, degree of polymerization 1000) were added.
12 parts of an aqueous solution was added and stirred uniformly to obtain a coating solution.
この塗布液を５０ｇ／ｍの固形分が塗布されるようなエ
アナイフ塗布機にて塗布、乾燥し、目的の顕色剤シート
が得られた。This coating liquid was applied using an air knife coating machine capable of applying a solid content of 50 g/m and dried to obtain the desired color developer sheet.
以下 本発明を実施例に基づいて詳細にかつ具体的に説
明する。Hereinafter, the present invention will be described in detail and specifically based on examples.
実施例１
ｐＨ６に調整されたポリビニルベンゼンスルホン酸の一
部ナトリウム塩（平均分子量５００．０００）の４．４
重量％水溶液１００（重量）部（以下”部”は すべて
”重量部”である。）に第２表に示されている発色剤３
，６−ピスージフエニルアミノフルオラン５部及び第１
表に記載されている化合物ａｗｄによって表される化合
物の各々、更に試料隘５では 紫外線吸収剤として２−
（３，５ｊ’−ｔ−ブチル−２−ヒドロキシフェニル）
−５−クロロベンゾトリアゾール２部を加え、これをジ
イソピルナフタレン１００部に溶解した発色剤油を乳化
分散して平均粒径４．５μｍの○／Ｗ型エマルジョンを
調製した。Example 1 Partial sodium salt of polyvinylbenzenesulfonic acid (average molecular weight 500.000) adjusted to pH 6.4.4
Add 3 parts of the coloring agent shown in Table 2 to 100 parts (by weight) of a wt% aqueous solution (all "parts" hereinafter refer to "parts by weight").
, 5 parts of 6-pis-diphenylaminofluorane and 1 part of
Each of the compounds represented by the compound awd listed in the table, and in addition, in sample column 5, 2-
(3,5j'-t-butyl-2-hydroxyphenyl)
2 parts of -5-chlorobenzotriazole was added, and a color former oil prepared by dissolving this in 100 parts of diisopyrnapthalene was emulsified and dispersed to prepare a ○/W type emulsion having an average particle size of 4.5 μm.
別途、メラミン６部、３７重量％ホルムアルデヒド水溶
液１１部、水８３部を温度６０℃、３０分間加熱攪拌し
、透明なメラミンとホルムアルデヒド及びメラミン−ホ
ルムアルデヒド初期縮合物の混合水溶液を調製した。Separately, 6 parts of melamine, 11 parts of a 37% by weight formaldehyde aqueous solution, and 83 parts of water were heated and stirred at a temperature of 60° C. for 30 minutes to prepare a transparent mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate.
このようにして調製した混合水溶液を前記のエマルジョ
ンに添加し、混合、攪耕しながら２０重量％酢酸水溶液
を添加してｐＨを６．０に調節し、さらに液温を６５°
Ｃに昇温させて３０分間保持し、カプセル化を行った。The mixed aqueous solution prepared in this way was added to the above emulsion, and while mixing and stirring, a 20% by weight acetic acid aqueous solution was added to adjust the pH to 6.0, and the liquid temperature was adjusted to 65°C.
The temperature was raised to C and held for 30 minutes to perform encapsulation.
この液にポリビニルアルコール（ケン化度８８モル％、
重合度５００）の２０重量％水溶液２００部、澱粉（平
均粒径１５μｍ）４７部及びタルク１０部を添加した。Add polyvinyl alcohol (saponification degree 88 mol%,
200 parts of a 20% by weight aqueous solution with a degree of polymerization of 500), 47 parts of starch (average particle size 15 μm), and 10 parts of talc were added.
次いで水を添加して固形分濃度を２０重量％に調節し、
マイクロカプセル液を調製した。Then water was added to adjust the solids concentration to 20% by weight,
A microcapsule liquid was prepared.
このマイクロカプセル液をエアーナイフ塗布機によって
原紙（坪量４０ ｇ／ｒｎ”）上に乾燥重量で５ｇ／ｆ
ｆｌとなるように塗布し乾燥せしめ、′感圧記録シービ
試料阻１〜５を作成した。This microcapsule liquid was coated onto a base paper (basis weight 40 g/rn") using an air knife coating machine at a dry weight of 5 g/f.
It was coated and dried to give a pressure-sensitive recording sample of 1 to 5.
比較例 １
実施例１において 一般式（Ｉ）によって表される化合
物を添加せず、他は 実施例１の試料ＮＯ，１〜試料階
４試料台と同様にして実施し、同様に”感圧記録シート
”試料眞６を作成した。Comparative Example 1 In Example 1, the compound represented by the general formula (I) was not added, and the rest was carried out in the same manner as in Sample No. 1 to Sample Floor 4 of Example 1. A recording sheet "Sample Shin 6" was created.
実施例 ２
実施例１において 発色剤を２−アニリノ−３−メチル
−６−Ｎ−エチル−Ｎ−イソペンチルアミノフルオラン
及び２−ベンジルアミノ−６−ジエチルアミノフルオラ
ンを、一般式（Ｉ）によって表される化合物として第１
表中の化合物ａ、同Ｃ及び同ｅを使用し、その他は 実
施例１における試料１Ｖｋ１１〜試料阻４の場合と同様
にして実施し、”感圧記録シート”試料■６〜隘９を作
成した。Example 2 In Example 1, the color former was 2-anilino-3-methyl-6-N-ethyl-N-isopentylaminofluorane and 2-benzylamino-6-diethylaminofluorane according to general formula (I). The first compound represented by
Compounds a, C, and e in the table were used, and the rest was carried out in the same manner as in Example 1 for samples 1Vk11 to 4 to prepare "pressure-sensitive recording sheets" samples 6 to 9. did.
比較例 ２
実施例２において一般式（Ｉ）によって表される化合物
を添加せず、他は 実施例２の場合と同様にして実施し
、同様に”感圧記録シート”試料階１０を作成した。Comparative Example 2 The same procedure as in Example 2 was carried out except that the compound represented by the general formula (I) in Example 2 was not added, and "pressure-sensitive recording sheet" sample floor 10 was prepared in the same manner. .
実施例 ３
実施例１において 発色剤としてクリスタルバイオレッ
トラクトンを、一般式（Ｉ）によって表さく１２）
れる化合物として第１表中の化合物ａ及び同Ｃを使用し
、その他は 実施例１における試料ｒｌｋ１１〜試料Ｎ
１１４の場合と同様にして実施し、”感圧記録シービ試
料Ｎα１１及び試料ＮｃＬ１２を作成した。Example 3 In Example 1, crystal violet lactone was used as the coloring agent, compounds a and C in Table 1 were used as the compounds represented by the general formula (I), and the rest were the sample rlk11 in Example 1. ~Sample N
The procedure was carried out in the same manner as in the case of No. 114, and pressure-sensitive recording CIV sample Nα11 and sample NcL12 were created.
比較例 ３
実施例３において一般式（Ｉ）によって表される化合物
を添加せず、他は 実施例３の場合と同様にして実施し
、同様に”感圧記録シービ試料隘１３を作成した。Comparative Example 3 The same procedure as in Example 3 was carried out except that the compound represented by the general formula (I) in Example 3 was not added, and "Pressure-sensitive recording CIV sample No. 13" was prepared in the same manner.
以上の実施例及び比較例において作成された感圧記録シ
ートの各試料について 下記の方法により■塗布面の着
色、■裁断面の発色汚れ及び■発色剤の耐光性の各性能
の比較試験を行った。For each sample of the pressure-sensitive recording sheet prepared in the above Examples and Comparative Examples, comparative tests were conducted on the performance of (coloring of coated surface), (coloring stains on cut surface), and (lightfastness of coloring agent) the following methods. Ta.
■塗布面の着色
”日立カラーアナライザー３０７型”を用い、各試料の
マイクロカプセル層の波長５５０〜７００ ｎｍ間の分
光吸収曲線を測定し、吸収極大における濃度（Ｄ）を測
定した。(2) Coloring of Coated Surface Using a Hitachi Color Analyzer Model 307, the spectral absorption curve of the microcapsule layer of each sample was measured in the wavelength range of 550 to 700 nm, and the concentration (D) at the absorption maximum was measured.
■裁断面の発色汚れ
各試料を１００枚重ね合わせてギロチンにより裁断し、
裁断面の発色汚れを目視で判定した。■Colored stains on the cut surface 100 sheets of each sample were stacked and cut using a guillotine.
Colored stains on the cut surface were visually determined.
■発色供功耐光性
試料のマイクロカプセル層を顕色剤シート上に重ね、３
００ ｋｇ／ｃＪの荷重圧をかけて発色させた。■Layer the microcapsule layer of the color development light resistance sample on the developer sheet,
Color was developed by applying a load pressure of 0.00 kg/cJ.
これを暗所にて２４時間放置した後、波長３８０〜７８
０ ｎｍ間の発色体の分光吸収曲線を測定し、吸収極大
における濃度（フレッシュ濃度Ｄｏ）を測定した。After leaving this in a dark place for 24 hours, the wavelength of 380-78
The spectral absorption curve of the color former between 0 nm and 0 nm was measured, and the concentration at the absorption maximum (fresh concentration Do) was measured.
このようにして発色させた試料を”キセノンフェトメー
ター（ＦＡＬ−２５ＡＸ−ＨＣ型）”（スガ試験機製）
により４時間照射した後、発色停の分光吸収曲線を測定
し、吸収極大における濃度りを測定した。The sample colored in this way was measured using a "xenon fetometer (model FAL-25AX-HC)" (manufactured by Suga Test Instruments).
After 4 hours of irradiation, the spectral absorption curve at the stop of color development was measured, and the density at the absorption maximum was measured.
なお、分光吸収曲線の測定は”日立カラーアナライザー
３０７型″（＠日立製作新製）を用いて行いた。また次
式により耐光性を示す値（耐光値）を算出した。The spectral absorption curve was measured using a "Hitachi Color Analyzer Model 307" (manufactured by @Hitachi Seisakusho). Further, a value indicating light resistance (light resistance value) was calculated using the following formula.
キセノンフェトメーター照射後の 吸収極大における濃度り 耐光値＝ 吸収極大におけるフレッシュ濃度り。After xenon fetometer irradiation Concentration at absorption maximum Lightfastness = Fresh concentration at maximum absorption.
本式から得られる耐光値が大きいほど発色体の耐光性が
優れていることを示す。The larger the light fastness value obtained from this formula, the better the light fastness of the coloring material.
第２表には これらの比較試験の結果が表示されている
。第２表に示されているように、本発明による感圧記録
シート試料は 比較試料に比べて塗布面の着色、裁断面
の発色汚れ及び発色１）の耐光性のいずれも優れている
ことが分かる。Table 2 displays the results of these comparative tests. As shown in Table 2, the pressure-sensitive recording sheet samples according to the present invention are superior to the comparative samples in terms of coloration on the coated surface, colored stains on the cut surface, and light resistance of coloring 1). I understand.
本発明による感圧記録シートは 上記の実施例における
結果でも明らかにされたごとく、塗布面の着色、裁断面
の発色汚れ及び発色うヰの耐光性のいずれも優れており
、本発明は 実用的にきわめて有用な発明である。The pressure-sensitive recording sheet according to the present invention has excellent coloring on the coated surface, colored stains on the cut surface, and light fastness of the colored film, and the present invention is practical. This is an extremely useful invention.
Claims (1)
カプセル化したマイクロカプセルを含む発色剤層が設け
られている感圧記録シートにおいて、該マイクロカプセ
ル中に下記の一般式（ I ）によって表される化合物が
含まれていることを特徴とする感圧記録シート。 一般式（ I ）： ▲数式、化学式、表等があります▼（ I ） （式中、Ｘは炭素原子数１〜１８のアルキレン基、Ｒ＿
１及びＲ＿２はメチル基またはエチル基、Ｒ＿３は炭素
原子数１〜１８のアルキル基、炭素原子数７〜１２のア
ラルキル基または炭素原子数１〜１８のアシル基を表す
。）[Scope of Claims] A pressure-sensitive recording sheet in which a color former layer containing microcapsules in which oil droplets in which an almost colorless color former is dissolved is provided on a support, wherein the microcapsules contain the following: A pressure-sensitive recording sheet characterized by containing a compound represented by general formula (I). General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is an alkylene group having 1 to 18 carbon atoms, R_
1 and R_2 represent a methyl group or an ethyl group, and R_3 represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group having 1 to 18 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61190626A JPS6347190A (en) | 1986-08-15 | 1986-08-15 | Pressure sensitive recording sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61190626A JPS6347190A (en) | 1986-08-15 | 1986-08-15 | Pressure sensitive recording sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6347190A true JPS6347190A (en) | 1988-02-27 |
Family
ID=16261199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61190626A Pending JPS6347190A (en) | 1986-08-15 | 1986-08-15 | Pressure sensitive recording sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6347190A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11157208A (en) * | 1997-11-25 | 1999-06-15 | Nippon Paper Industries Co Ltd | Microcapsule dispersion for pressure-sensitive recording and manufacture thereof |
| US6622702B2 (en) * | 2000-03-14 | 2003-09-23 | Isuzu Motors Limited | Common rail fuel injection device |
-
1986
- 1986-08-15 JP JP61190626A patent/JPS6347190A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11157208A (en) * | 1997-11-25 | 1999-06-15 | Nippon Paper Industries Co Ltd | Microcapsule dispersion for pressure-sensitive recording and manufacture thereof |
| US6622702B2 (en) * | 2000-03-14 | 2003-09-23 | Isuzu Motors Limited | Common rail fuel injection device |
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