JPS6359879B2 - - Google Patents
Info
- Publication number
- JPS6359879B2 JPS6359879B2 JP55154947A JP15494780A JPS6359879B2 JP S6359879 B2 JPS6359879 B2 JP S6359879B2 JP 55154947 A JP55154947 A JP 55154947A JP 15494780 A JP15494780 A JP 15494780A JP S6359879 B2 JPS6359879 B2 JP S6359879B2
- Authority
- JP
- Japan
- Prior art keywords
- microcapsules
- paper
- formalin resin
- parts
- melamine
- 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 42
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000002775 capsule Substances 0.000 claims description 14
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 14
- 239000011247 coating layer Substances 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 239000004816 latex Substances 0.000 description 15
- 229920000126 latex Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 108010010803 Gelatin Proteins 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 238000005354 coacervation Methods 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 5
- 241000272165 Charadriidae Species 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007903 gelatin capsule Substances 0.000 description 2
- 239000000203 mixture 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
- 229920003169 water-soluble polymer Polymers 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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004078 waterproofing Methods 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)
- Manufacturing Of Micro-Capsules (AREA)
Description
本発明はノーカーボン複写用カプセルシートに
関するものであり、更にくわしくは、メラミンホ
ルマリン樹脂膜又は尿素ホルマリン樹脂膜よりな
るマイクロカプセルの全く新規な塗層構成に関す
るものである。
ノーカーボン複写紙は公知であり、通常電子供
与性無色有機化合物と高沸点有機溶剤を含むマイ
クロカプセルと、該無色有機化合物を発色させる
酸性物質との組み合わせより成つており、その有
用性より近年益々その需要も増大している。
ノーカーボン複写紙に於て、その技術の中心と
なるのはマイクロカプセル化法であり、その特性
がノーカーボン複写紙の性能を大きく左右する。
従来より、ノーカーボン複写紙のマイクロカプセ
ル化は、ゼラチンを使用したコアセルベーシヨン
法が中心となつていた。
この方法は、低濃度のマイクロカプセルしか得
られない、複雑な工程を必要とし、安定して得ら
れ難い、腐敗しやすい、耐水性が悪く高湿度の条
件でこわれ易い、界面活性剤等により容易に内相
物質が抽出される、等の欠点があり、その改良が
望まれていたが、かわり得るマイクロカプセル化
法が見出されなかつた。
最近になつて、ポリウレタンやポリ尿素等の膜
をもつ界面重合法マイクロカプセル或いはメラミ
ンホルマリン樹脂や尿素ホルマリン樹脂の膜をも
つインサイチユ（in situ）法マイクロカプセル
が実用化される様になつてきた。
この界面重合法マイクロカプセル化技術では高
濃度で、比較的容易にマイクロカプセルが得ら
れ、腐敗の必配もないが、極性溶剤や薬品に対す
る耐性が優れているとはいいがたい。
また、反応性の高い原料薬品を使う為に副反応
が起り易く取り扱い上、難があり、細かな均一な
カプセルが得にくい、使用薬品は安全上の問題が
ある、等、価格的に高いことも含めて、ゼラチン
コアセルベーシヨン法マイクロカプセル化に置き
かわるには、問題がある。
一方in situ法によるメラミンホルマリン樹脂
膜や尿素ホルマリン樹脂膜によるマイクロカプセ
ル化技術では新しい乳化剤（兼変性剤）との組み
合わせにより（例えば、特開昭51−9079号、同53
−84882号、同53−84883号、同53−84881号、同
54−49984号、等）高濃度で、容易にしかも安定
してマイクロカプセルが得られ、腐敗の必要もな
く、しかも耐熱性、耐容剤性、耐水性、耐薬品性
の強いマイクロカプセルが得られ、その安価さも
あり、ゼラチンコアセルベーシヨン法にとつてか
わりつつある。しかしながら、このin situ法で
得られるマイクロカプセルは、その膜材の特性よ
り非常に堅いマイクロカプセルであるので、筆圧
等により、こわれにくいマイクロカプセルとなり
やすい為、膜をうすくする事や、膜の変性をおこ
なう事等が検討されて来た。
しかし、例えば膜をうすくすると、マイクロカ
プセルは、たしかにこわれ易くなるが、不必要な
破壊が、おこりやすく汚れの原因となる。又、膜
を変性することによりマイクロカプセルを破壊し
やすくなることはある程度可能であるが、この場
合も不必要な破壊の原因となつたり、特有の性質
の耐熱性、耐溶剤性等をそこないやすく好ましく
なかつた。
尚これらの特徴は、尿素ホルマリン樹脂に比べ
てメラミン−ホルマリン樹脂膜のマイクロカプセ
ルに一層顕著である。
本発明は、マイクロカプセルの不必要な破壊に
よる汚れを防止したノーカーボン複写用カプセル
シートに関するものであり、耐水性、耐熱性が優
れ、またその発色性の良いカプセルシートを得る
ことにある。
本発明の目的はメラミンホルマリン樹脂膜又は
尿素ホルマリン樹脂膜から成るマイクロカプセル
の塗層にマイクロカプセルの５％乃至20％（重量
部）の量のラテツクスを含有させることにより達
成される。
これは、メラミンホルマリン樹脂膜又は尿素ホ
ルマリン樹脂膜の特徴である硬さ（見方を変えれ
ば脆さ）が当該樹脂膜より成るマイクロカプセル
の周囲に存在する軟かいラテツクスのために庇護
され覆いかくされることによると考えられる。
この為に、使用するラテツクスは軟かいものが
好ましく、その成膜温度も室温以下であることが
推奨される。
ラテツクスは、接着剤としては、きわめて普通
に使用されているもので、アクリルエステル系、
酢酸ビニル系、塩化ビニル系、スチレンブタジエ
ン系、天然ゴム等きわめて多数の市販品がある。
通常の紙加工にはこれらのうちからそれぞれの
特徴によつて選択されたラテツクスを使用するの
が、普通となつていたが、ただノーカーボン複写
紙用カプセルシートにおいては事情が異なりラテ
ツクス添加による好ましくない副作用が大きいた
めに従来よりラテツクスは、実質的には使用され
ていなかつた。即ち、発色能を阻害し、あまつさ
え汚れ（スマツジ）を助長する。（尚、ノーカー
ボン複写紙以外では、ゼラチンのコアセルベーシ
ヨンを利用した30μ程度以上の大きなマイクロカ
プセルに、水性エマルジヨンを付着性向上剤とし
て添加することが公知となつている（特開昭53−
11883号）。）
このノーカーボン複写紙用カプセルシートに従
来より、ラテツクスが使用されていなかつた理由
は、ゼラチンのコアセルベーシヨン法によるマイ
クロカプセルの分散液はそれ自体、平衝液成分と
してのコロイド等接着に寄与する水溶性高分子が
多く、他の接着剤をあまり多く必要としないばか
りでなく、前述した様に、界面活性剤等に膜が弱
い為に、ラテツクスを分散（乳化）、安定化する
のに使用される界面活性剤により、ラテツクスを
使用するとマイクロカプセル膜の性質が悪くな
る。
一方、尿素ホルマリン樹脂あるいは、特にメラ
ミンホルマリン樹脂膜よりなるマイクロカプセル
は、界面活性剤等に特に強い為に、ラテツクスと
共存できることがわかつた。しかしながら、ラテ
ツクスを添加しても接着剤としては充分役に立た
ずに、他の水溶性接着剤が必要であることが判明
したが、一方、これらマイクロカプセルの硬さ
（もろさ）を、塗層中のラテツクスの軟かさがお
ぎなうという事がわかり、本発明に到達したもの
である。本発明においてはカプセル量に対する添
加量が５％以下では顕著な効果がなく、20％以上
では、無駄であり、悪くする性質も出てくる。
本発明のメラミンホルマリン樹脂又は尿素ホル
マリン樹脂によるin situ法マイクロカプセル化
は、公知であり、基本的には高分子カルン酸の水
溶液中に、無色有機化合物の高沸点有機溶剤の溶
液を乳化し、尿素とホルマリンあるいはその初期
縮合物又は、メラミンホルマリン初期縮合物を加
えて、酸性加熱化で反応させることにより、きわ
めて容易に、高濃度マイクロカプセル分散液が生
成できる。代表的な公知の例として、次の公報を
上げる。特開昭54−49984号、同54−53679号、同
53−84881号、同53−84882号、同53−84883号、
同51−9079号。
本発明に使用されるマイクロカプセルの大きさ
は、平均粒子径が約2.0乃至8.0μであり、前記の
様に無色有機化合物を含む以外に、特殊な例とし
て、酸性物質（フエノール系樹脂又はサリチル酸
誘導体金属塩等）を含む場合も同様である。
通常のノーカーボン複写用カプセルシートは、
マイクロカプセル100部に対して、保護剤（スチ
ルト剤）20乃至250部、水溶性接着剤５乃至40部
程度の配合により塗抹される。
保護剤（スチルト剤）は、デンプン粒、セルロ
ース粉末、無機粉末、等のようなマイクロカプセ
ルより、やや大きな粒径の小粒体が使用されてお
り、通常の転写型の上用紙の場合は、20乃至80部
程度使用され、自己発色シート（セルフ・コンテ
インドペーパー）の場合には、150部程度を中心
に使用される場合が多い。
接着剤としては、（変性）デンプン、ポリビニ
ルアルコール、セルロース誘導体、カルボン酸系
ポリマー、等の水溶性高分子が使用されており、
必要な強度を出す量加えられる。その他消泡剤、
耐水化剤等各種添加剤が必要により添加される。
本発明のノーカーボン複写用カプセルシート
は、メラミンホルマリン樹脂膜又は尿素ホルマリ
ン樹脂膜よりなるマイクロカプセルに、マイクロ
カプセルの５％乃至20％の量のラテツクスを加え
るほかは、通常のノーカーボン複写用の配合と同
様に、保護剤（スチルト剤）、水溶性接着剤など
を用いる。
ここで使用するラテツクスは、マイクロカプセ
ルや特に保護剤（スチルト剤）を紙に接着するの
には、それ程の働きを示さないので、ノーカーボ
ン複写用上用紙の場合水溶性接着剤は、やはり、
10部乃至40部程度必要であり、保護剤は20乃至80
部が配合され、必要に応じ各種添加剤を配合す
る。
これらの塗液の調製には特に注意することはな
く通常の方法で良く、また塗抹方法についても特
に限定されることはない。
以下実験例により、特性の差異を説明する。
実験１ （ゼラチンコアセルベーシヨン法マイク
ロカプセル）
C.V.L（クリスタルバイオレツトラクトン＝呈
色性無色有機化合物）３部をＮ−296（日石化学(株)
製高沸点有機溶剤）100部に溶解した内相油を、
ゼラチン20部を溶解した水100部中に乳化し、こ
の乳化液を20部のアラビアゴムを溶解した温水
1480部中に加えて、PHを９とした。
次に撹拌しながら、酢酸にてPHを4.5まで下げ、
系の温度を10℃まで冷却し、グルタールアルデヒ
ド（50％）20部加えて、一昼夜後PHを９として、
ゼラチンコアセルベーシヨン法によるマイクロカ
プセルを作成した。
マイクロカプセルの平均粒径は9.5μであつた。
実験２ （in situ法によるメラミンホルマリン
樹脂マイクロカプセル）
CVL3部をＮ−296 100部に溶解した内相油を
スチレン無水マレイン酸共重合体５部を含む水性
液115部（PH5.0）中に乳化した。この乳化液中
に、SR613（住友化学(株)製メラミンホルマリン初
期縮合物）を、固型分20％とした水溶液50部を加
えて70℃とし、２時間反応させた後、PHを９とし
て、in situ法によるメラミンホルマリン樹脂に
よるマイクロカプセルを作成した。マイクロカプ
セルの平均粒径は4.0μであつた。
実験３ （ノーカーボン複写用上用紙の作成）
こうして得られたノーカーボン複写用マイクロ
カプセルを下記の配合にて、41ｇ／m2の上質紙
に、カプセル塗抹量で約2.3ｇ／m2となる様にエ
アーナイフコーターで塗抹し、Ａ（比較例１）、Ｂ
（比較例２）、Ｃ（比較例３）、Ｄ（実施例１）の４
種類のノーカーボン複写用上用紙を得た。
The present invention relates to a carbonless copying capsule sheet, and more particularly to a completely new coating layer structure of microcapsules made of a melamine-formalin resin film or a urea-formalin resin film. Carbonless copying paper is well known and usually consists of a combination of microcapsules containing an electron-donating colorless organic compound and a high-boiling organic solvent, and an acidic substance that causes the colorless organic compound to develop color. The demand for it is also increasing. The core technology of carbonless copying paper is the microencapsulation method, and its characteristics greatly influence the performance of carbonless copying paper.
Conventionally, microencapsulation of carbonless copying paper has been centered on the coacervation method using gelatin. This method yields only low-concentration microcapsules, requires a complicated process, is difficult to obtain stably, is easily perishable, has poor water resistance and easily breaks under high humidity conditions, and is difficult to use due to the presence of surfactants, etc. However, an alternative microencapsulation method has not been found, although improvements have been desired. Recently, interfacial polymerization microcapsules having a film of polyurethane, polyurea, etc., or in situ microcapsules having a film of melamine-formalin resin or urea-formalin resin have come into practical use. This interfacial polymerization microencapsulation technology allows microcapsules to be obtained at high concentrations with relative ease, and there is no risk of spoilage, but it cannot be said to have excellent resistance to polar solvents and chemicals. In addition, because highly reactive raw materials are used, side reactions are likely to occur, making them difficult to handle, making it difficult to obtain fine, uniform capsules, and the chemicals used have safety issues, and are expensive. There are problems with replacing gelatin coacervation microencapsulation, including microencapsulation. On the other hand, microencapsulation technology using a melamine-formalin resin film or a urea-formalin resin film by in situ method uses a combination with a new emulsifier (cum-denaturing agent) (for example, JP-A-51-9079, JP-A-51-9079;
−84882, No. 53-84883, No. 53-84881, No.
No. 54-49984, etc.) Microcapsules can be obtained easily and stably at high concentrations, and there is no need for putrefaction, and microcapsules with strong heat resistance, tolerability, water resistance, and chemical resistance can be obtained. Due to its low cost, it is gradually replacing the gelatin coacervation method. However, the microcapsules obtained by this in situ method are very hard microcapsules due to the characteristics of the membrane material, so they tend to become microcapsules that are difficult to break due to pen pressure, etc. The use of denaturation, etc. has been considered. However, if the membrane is made thinner, for example, the microcapsules will certainly become more fragile, but unnecessary destruction will easily occur and cause stains. In addition, it is possible to some extent to make microcapsules easier to destroy by modifying the membrane, but in this case, it may not cause unnecessary destruction or impair their specific properties such as heat resistance and solvent resistance. It was easy and undesirable. These characteristics are more remarkable in microcapsules made of melamine-formalin resin membranes than in urea-formalin resins. The present invention relates to a carbonless copying capsule sheet that prevents staining due to unnecessary destruction of microcapsules, and an object of the present invention is to obtain a capsule sheet that has excellent water resistance, heat resistance, and good color development. The object of the present invention is achieved by incorporating latex in an amount of 5% to 20% (parts by weight) of the microcapsules in the coating layer of the microcapsules made of a melamine-formalin resin film or a urea-formalin resin film. This is because the hardness (or brittleness) characteristic of the melamine-formalin resin film or the urea-formalin resin film is protected and hidden by the soft latex that exists around the microcapsules made of the resin film. This may be possible. For this reason, it is preferable that the latex used be soft, and it is recommended that the film forming temperature be below room temperature. Latex is a very commonly used adhesive, including acrylic ester,
There are a large number of commercially available products such as vinyl acetate, vinyl chloride, styrene butadiene, and natural rubber. For ordinary paper processing, it has become common to use latexes selected from among these based on their respective characteristics, but the situation is different for capsule sheets for carbonless copying paper. Conventionally, latex has not been used substantially because of its large side effects. That is, it inhibits color development ability and promotes smudging. (In addition to carbonless copying paper, it is known that an aqueous emulsion is added as an adhesion improver to large microcapsules of about 30μ or more using gelatin coacervation (Japanese Patent Application Laid-Open No. 1983-1993). −
No. 11883). ) The reason why latex has not traditionally been used in capsule sheets for carbonless copying paper is that the dispersion of microcapsules produced by the gelatin coacervation method itself contributes to colloid adhesion as a balance liquid component. Not only does it contain many water-soluble polymers that do not require a large amount of other adhesives, but also, as mentioned above, the film is weak against surfactants, etc., so it is difficult to disperse (emulsify) and stabilize latex. Depending on the surfactant used, the properties of the microcapsule membrane deteriorate when latex is used. On the other hand, it has been found that microcapsules made of urea-formalin resin or especially melamine-formalin resin membranes are particularly resistant to surfactants and can coexist with latex. However, it was found that the addition of latex was not sufficiently useful as an adhesive and that other water-soluble adhesives were required. It was discovered that the softness of latex was achieved, and the present invention was developed. In the present invention, if the amount added to the capsule amount is less than 5%, there will be no significant effect, and if it is more than 20%, it will be wasteful and may have adverse properties. The in situ microencapsulation using melamine-formalin resin or urea-formalin resin of the present invention is known, and basically involves emulsifying a solution of a colorless organic compound in a high-boiling organic solvent in an aqueous solution of high-molecular carunic acid. A highly concentrated microcapsule dispersion can be produced very easily by adding urea and formalin or an initial condensate thereof, or a melamine-formalin initial condensate and reacting with acidic heating. The following publication is cited as a typical known example. JP-A-54-49984, JP-A No. 54-53679, JP-A No. 54-53679,
No. 53-84881, No. 53-84882, No. 53-84883,
No. 51-9079. The average particle size of the microcapsules used in the present invention is about 2.0 to 8.0μ, and in addition to containing colorless organic compounds as mentioned above, they also contain acidic substances (phenolic resins or salicylic acid) as special examples. The same applies to the case where a derivative metal salt, etc.) is included. Ordinary carbonless copying capsule sheets are
It is smeared by mixing 20 to 250 parts of a protective agent (stilt agent) and 5 to 40 parts of a water-soluble adhesive to 100 parts of microcapsules. The protective agent (stilt agent) is a small particle with a slightly larger particle size than microcapsules such as starch granules, cellulose powder, inorganic powder, etc. Approximately 80 copies are used, and in the case of self-coloring sheets (self-contained paper), approximately 150 copies are often used. Water-soluble polymers such as (modified) starch, polyvinyl alcohol, cellulose derivatives, and carboxylic acid polymers are used as adhesives.
Add the amount needed to achieve the required strength. Other antifoaming agents,
Various additives such as waterproofing agents are added as necessary. The capsule sheet for carbonless copying of the present invention is similar to the conventional capsule sheet for carbonless copying, except that latex is added in an amount of 5% to 20% of the microcapsules to the microcapsules made of a melamine-formalin resin film or a urea-formalin resin film. Similar to the formulation, a protective agent (stilt agent), water-soluble adhesive, etc. are used. The latex used here does not show much effect in adhering microcapsules and especially protective agents (stilt agents) to paper, so in the case of carbonless copy paper, water-soluble adhesives are still used.
Approximately 10 to 40 parts are required, and the protective agent is 20 to 80 parts.
parts are blended, and various additives are blended as necessary. These coating liquids may be prepared by conventional methods without any particular precautions, and there are no particular limitations on the smearing method. The differences in characteristics will be explained below using experimental examples. Experiment 1 (Gelatin coacervation method microcapsules) 3 parts of CVL (crystal violet lactone = color-forming colorless organic compound) was mixed with N-296 (Nisseki Chemical Co., Ltd.)
Internal phase oil dissolved in 100 parts of high boiling point organic solvent)
Emulsify 20 parts of gelatin in 100 parts of water, and add this emulsion to warm water with 20 parts of gum arabic dissolved in it.
It was added to 1480 copies and the pH was adjusted to 9. Next, while stirring, lower the pH to 4.5 with acetic acid.
Cool the temperature of the system to 10℃, add 20 parts of glutaraldehyde (50%), and after one day and night, adjust the pH to 9.
Microcapsules were created using the gelatin coacervation method. The average particle size of the microcapsules was 9.5μ. Experiment 2 (Melamine-formalin resin microcapsules by in situ method) Internal phase oil in which 3 parts of CVL was dissolved in 100 parts of N-296 was added to 115 parts of an aqueous liquid (PH5.0) containing 5 parts of styrene-maleic anhydride copolymer. Emulsified. To this emulsion, 50 parts of an aqueous solution of SR613 (melamine formalin initial condensate manufactured by Sumitomo Chemical Co., Ltd.) with a solid content of 20% was added, the temperature was raised to 70°C, and after reacting for 2 hours, the pH was adjusted to 9. , microcapsules were created using melamine-formalin resin using an in situ method. The average particle size of the microcapsules was 4.0μ. Experiment 3 (Preparation of top paper for carbonless copying) The thus obtained microcapsules for carbonless copying were coated on high-quality paper of 41 g/m 2 with the following composition, giving a capsule coating amount of approximately 2.3 g/m 2 A (comparative example 1), B
(Comparative Example 2), C (Comparative Example 3), D (Example 1) 4
Various types of carbonless copy paper were obtained.
【表】【table】
【表】
実験４
こうして得られた、Ａ、Ｂ、Ｃ、Ｄ、の４種類
の上用紙について、下記の項目についてテストを
おこなつた。尚、酸性物質塗抹シートとしては市
販品下用紙（三菱NCR紙レジンＮ−40下用紙三
菱製紙(株)製）を使用した。
() 発色性
上用紙と下用紙とをかさねて、スーパカーレ
ンダーにて発色させ、１時間後にその発色濃度
を色差計で測定し、反射率で示した。
() 耐熱性
上用紙と下用紙とをかさね合わせて、105℃
のオープン中に６時間置き、マイクロカプセル
の熱による破壊を、下用紙の汚れ（反射率）を
測定することにより評価した。
() 耐水性
上用紙と下用紙とをかさね、水に浸し、オー
ブンにて乾燥させ、下用紙の汚れ（反射率）を
測定した。
() まさつ汚れ
上用紙の上に下用紙をのせ（発色する様に）
下用紙の上に３Kgの錘りをのせて、上用紙の上
を50cmすべらせ、まさつに対するマイクロカプ
セルの破壊を、下用紙の汚れ（反射率）で測
定。
() 圧汚れ
上用紙と下用紙とをかさねて、ギロチンにて
裁断し、切り口の周辺のおさえ圧等による下用
紙の汚れ（反射率）を測定した。[Table] Experiment 4 The four types of paper sheets A, B, C, and D thus obtained were tested for the following items. As the acidic substance smearing sheet, a commercially available base paper (Mitsubishi NCR Paper Resin N-40 base paper manufactured by Mitsubishi Paper Mills Co., Ltd.) was used. () Color development The upper paper and the lower paper were stacked and colored using a super color renderer, and 1 hour later, the color density was measured using a color difference meter and expressed as reflectance. () Heat resistance Upper paper and lower paper stacked together at 105℃
The microcapsules were left open for 6 hours, and the destruction of the microcapsules due to heat was evaluated by measuring the dirt (reflectance) on the bottom paper. () Water resistance The top paper and the bottom paper were stacked, soaked in water, dried in an oven, and the stain (reflectance) on the bottom paper was measured. () Masatsu dirt Place the bottom paper on top of the top paper (so that the color develops)
A 3Kg weight is placed on top of the bottom paper, and it is slid 50cm over the top paper, and the destruction of microcapsules against Masatsu is measured by the dirt (reflectance) on the bottom paper. () Pressure stains The top paper and bottom paper were overlapped and cut using a guillotine, and the dirt (reflectance) on the bottom paper due to pressing pressure etc. around the cut edges was measured.
【表】
○：合格 △：不満足 ×：不合格
以上の結果より、Ｄ（実施例１：本発明）のも
のがすべての点に於てすぐれており、ゼラチンカ
プセルの場合はラテツクス添加によりかえつて汚
れが悪化し、ラテツクスの添加の効果が、ゼラチ
ンカプセルと、メラミン樹脂カプセルとは全く逆
なことがわかつたのであり、本発明の有用な効果
はin situ法によるマイクロカプセルにおいて初
めて具現されたのである。[Table] ○: Pass △: Unsatisfactory ×: Fail From the above results, D (Example 1: the present invention) is excellent in all respects, and in the case of gelatin capsules, it can be improved by adding latex. It was found that the effect of adding latex was completely opposite to that of gelatin capsules and melamine resin capsules, and the useful effects of the present invention were realized for the first time in microcapsules produced by the in situ method. be.
Claims (1)
リン樹脂膜よりなるマイクロカプセルを含有する
塗層をもつノーカーボン複写用カプセルシートに
於て、塗層中にマイクロカプセルの５％乃至20％
（重量部）のアクリル酸エステル系、酢酸ビニル
系、塩化ビニル系、スチレンブタジエン系、天然
ゴムの群から選ばれる１以上のラテツクスを含有
することを特徴とするノーカーボン複写用カプセ
ルシート。1. In a carbonless copying capsule sheet having a coating layer containing microcapsules made of a melamine-formalin resin film or a urea-formalin resin film, 5% to 20% of the microcapsules are contained in the coating layer.
1. A carbonless copying capsule sheet comprising (parts by weight) of one or more latexes selected from the group consisting of acrylic esters, vinyl acetate, vinyl chloride, styrene butadiene, and natural rubber.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55154947A JPS5777589A (en) | 1980-11-04 | 1980-11-04 | Capsule sheet for non-carbon copying |
| GB8133068A GB2087942B (en) | 1980-11-04 | 1981-11-03 | Capsule sheet for no-carbon copying paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55154947A JPS5777589A (en) | 1980-11-04 | 1980-11-04 | Capsule sheet for non-carbon copying |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5777589A JPS5777589A (en) | 1982-05-14 |
| JPS6359879B2 true JPS6359879B2 (en) | 1988-11-21 |
Family
ID=15595394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55154947A Granted JPS5777589A (en) | 1980-11-04 | 1980-11-04 | Capsule sheet for non-carbon copying |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5777589A (en) |
| GB (1) | GB2087942B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190826A (en) * | 1984-03-10 | 1985-09-28 | Matsumoto Kosan Kk | Manufacture of temperature indicating sheet |
| JPS61211080A (en) * | 1985-03-15 | 1986-09-19 | Fuji Photo Film Co Ltd | Microcapsule sheet for pressure-sensitive copying |
| US4931422A (en) * | 1987-08-19 | 1990-06-05 | Mitsubishi Paper Mills Limited | No-carbon pressure-sensitive copying paper |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440711A (en) * | 1977-06-30 | 1979-03-30 | Mead Corp | Method of composite substance for coating radiationnhardened microcapsule |
| JPS5444919A (en) * | 1977-08-26 | 1979-04-09 | Bayer Ag | Pressureesensitive copying paper |
-
1980
- 1980-11-04 JP JP55154947A patent/JPS5777589A/en active Granted
-
1981
- 1981-11-03 GB GB8133068A patent/GB2087942B/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440711A (en) * | 1977-06-30 | 1979-03-30 | Mead Corp | Method of composite substance for coating radiationnhardened microcapsule |
| JPS5444919A (en) * | 1977-08-26 | 1979-04-09 | Bayer Ag | Pressureesensitive copying paper |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2087942B (en) | 1985-01-03 |
| GB2087942A (en) | 1982-06-03 |
| JPS5777589A (en) | 1982-05-14 |
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