JPS6292887A - Surface protective agent for thermal recording paper - Google Patents
Surface protective agent for thermal recording paperInfo
- Publication number
- JPS6292887A JPS6292887A JP60233168A JP23316885A JPS6292887A JP S6292887 A JPS6292887 A JP S6292887A JP 60233168 A JP60233168 A JP 60233168A JP 23316885 A JP23316885 A JP 23316885A JP S6292887 A JPS6292887 A JP S6292887A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- water
- recording paper
- resistance
- acid
- 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.)
- Granted
Links
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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は感熱層上に保護皮膜を形成することによりサー
マルヘッドとのヘッドマツチング性９発色感度の良い、
耐油、耐水性に優れた感熱記録紙を提供するための水性
感熱記録紙用表面保護剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention forms a protective film on a heat-sensitive layer to improve head matching with a thermal head.
The present invention relates to a surface protective agent for water-based thermosensitive recording paper for providing thermosensitive recording paper with excellent oil resistance and water resistance.
従来の技術
従来、感熱記録体の感熱層の上に保護層を設けて薬品、
油、可塑剤、水等が直接感熱層に接触しないようにして
感熱記録体の耐薬品、耐油、耐可盟剤並びに保存安定性
を向上させる方法として。Conventional technology Conventionally, a protective layer is provided on the heat-sensitive layer of a heat-sensitive recording medium to prevent chemicals,
As a method for improving the chemical resistance, oil resistance, plasticizing agent resistance, and storage stability of a heat-sensitive recording material by preventing oil, plasticizer, water, etc. from coming into direct contact with the heat-sensitive layer.
（メタ）アクリルアミド、（メタ）アクリル酸の低級ア
ルキルエステル及びカルボキシル基を有するビニル単量
体からなる共重合物のアルカリ水溶液にエポキシ基を有
する架橋剤を配合したちのく特開昭６０−５９１９３）
、カルボキシル基変性ポリビニルアルコールとポリアミ
ドエポキシ樹脂を主成分とするもの（特開昭５９−１６
２０８８）、あるいはジイソブチレン／無水マレイン酸
共重合物の水溶性塩とカルボキシル基変性ポリビニルア
ルコールとを含有するもの（特開昭６Ｏ−１５１９０）
等がある。Chinoku JP-A-60-59193 in which a crosslinking agent having an epoxy group is blended into an alkaline aqueous solution of a copolymer consisting of (meth)acrylamide, a lower alkyl ester of (meth)acrylic acid, and a vinyl monomer having a carboxyl group. )
, whose main components are carboxyl group-modified polyvinyl alcohol and polyamide epoxy resin (Japanese Unexamined Patent Publication No. 59-16
2088), or one containing a water-soluble salt of diisobutylene/maleic anhydride copolymer and carboxyl group-modified polyvinyl alcohol (JP-A-6O-15190)
etc.
発明が解決しようとする問題点
従来、感熱記録体としては、ロイコ染料および加熱によ
って融解しロイコ染料を発色させろ顕色剤を主成分とす
る記録材料を支持体に結着させたもの１例えばクリスタ
ルバイオレットラクトンの如きロイコ染料とフェノール
性化合物の如き何機酸との紺み合わせが公知である（特
公昭４５−１４０３９など）。この種の感熱記録体は印
字が容易であり、得られた記録が鮮明であることから。Problems to be Solved by the Invention Conventionally, thermal recording materials have been made by bonding to a support a recording material containing a leuco dye and a color developer that is melted by heating to develop a color from the leuco dye (for example, crystal). The combination of a leuco dye such as violet lactone and a phenolic acid such as a phenolic compound to create a deep blue color is known (Japanese Patent Publication No. 14039/1983, etc.). This type of thermal recording material is easy to print on, and the resulting records are clear.
プリンターやファクシミリ用の記録体として広く利用さ
れている。最近ではその特徴を主力）シ、定期券１乗車
券、カート、ラヘル類への利用とその用途も拡大してき
ている。It is widely used as a recording medium for printers and facsimiles. Recently, its use has been expanding as its main feature has been used for bicycles, commuter passes, single-ride tickets, carts, and racks.
しかし、この感熱記録体は耐水性や耐酸性等の耐薬品性
や耐油性、耐可塑剤性等の耐溶剤性が悪く、記録体の発
色部分が可塑剤や、油に接触するような用途に用いられ
た場合、その可塑剤や油が発色した発色剤と反応してこ
れを消失させる難点がある。また、水や水性液に接触す
る用途に用いられた場合は、水が感熱層に浸透してバイ
ンダーが溶解し２発色部が剥がれることがある。However, this heat-sensitive recording material has poor chemical resistance such as water resistance and acid resistance, and solvent resistance such as oil resistance and plasticizer resistance, and is not suitable for applications where the colored portion of the recording material comes into contact with plasticizers or oil. When used for coloring, the problem is that the plasticizer or oil reacts with the coloring agent and causes it to disappear. Furthermore, when used in applications that come into contact with water or aqueous liquids, the water may penetrate into the heat-sensitive layer, dissolve the binder, and cause the two color-developing parts to peel off.
感熱記録紙に於けるこのような難点を克服するため従来
は耐油、耐水性を向上させる手段として感熱塗被液の配
合時に耐水バインダー、ワックス等の使用量を発色性を
損ねない程度に増加して感熱層を作ることが試みられた
。しかし、このような方法では一応の成果は見られるが
、耐薬品性。In order to overcome these difficulties in thermal recording paper, the amount of water-resistant binders, waxes, etc. used in the formulation of thermal coating liquids has been increased to an extent that does not impair color development as a means of improving oil and water resistance. Attempts were made to create a heat-sensitive layer. However, although some results have been seen with this method, chemical resistance is limited.
耐可塑剤性等の向上は小さく、実用上充分であるとは言
い雅い。The improvement in plasticizer resistance, etc. is small, and it would be unfair to say that it is sufficient for practical use.
さらに前記欠点を解決する方法として、感熱層の上に保
護層を設けて直接薬品、油、可塑剤、水等が感熱層に接
触しない様にすることが提案されている。耐薬品性、耐
可塑剤性に優れ、地肌のかぶり、スティッキングを生じ
ることなく２発色感度を低下させない保護層としては水
溶性高分子を主体としてものが提案されているが、水溶
性であるが故に耐水性が不充分であり、耐水１ヒ剤との
併用が必要となり、２液化、可使時間、硬化条件等の問
題が生じてくる。また、このようにして得られたものに
ついてもステイキング、発色感度についてはいまだ充分
とは言えない。Furthermore, as a method for solving the above-mentioned drawbacks, it has been proposed to provide a protective layer on the heat-sensitive layer to prevent chemicals, oil, plasticizers, water, etc. from coming into direct contact with the heat-sensitive layer. A protective layer based on water-soluble polymers has been proposed as a protective layer that has excellent chemical resistance and plasticizer resistance, does not cause background fogging or sticking, and does not reduce the two-color development sensitivity. Therefore, the water resistance is insufficient, and it is necessary to use a water-resistant agent in combination, which causes problems such as two-component composition, pot life, and curing conditions. Moreover, the staking and coloring sensitivity of the products obtained in this way are still not satisfactory.
特に、近年サーマルファクシミリ分野での高速化が進み
、サーマルヘッドを高速駆動させることが一般化しつつ
あり、またＰＯＳ化の中でスーパーマーケットのバーコ
ードをプリンターで印字する方式に感熱方式を採用する
場合９発色感度、印字画像の保存性に更に高い信頼性が
要求されている。本発明は感熱層上に保護皮膜を形成す
ることによりサーマルヘッドとのヘッドマツチング性。In particular, the thermal facsimile field has become faster in recent years, and it is becoming common to drive thermal heads at high speed.Also, with the shift to POS, thermal methods are being used to print supermarket barcodes on printers9. Higher reliability is required in color development sensitivity and print image storage stability. The present invention improves head matching with a thermal head by forming a protective film on the heat-sensitive layer.
発色感度の良い、耐油、耐水性に優れた感熱記録紙を提
供する。常温または低温短時間乾燥可能な−？＆型氷水
性感熱記録紙用表面保護剤関するものである。To provide a heat-sensitive recording paper with good coloring sensitivity and excellent oil resistance and water resistance. Is it possible to dry at room temperature or low temperature for a short time? The present invention relates to a surface protective agent for & type ice-water-based thermal recording paper.
問題を解決するための手段及び作用
本発明者等はカルボキシル基を含有するビニル系共重合
体の水溶液又は水分散液に対して多価金属化合物と揮発
性錯化剤を加え、金属錯体とすることにより、常温又は
低温乾燥で耐水性、耐油性。Means and Action for Solving the Problem The present inventors added a polyvalent metal compound and a volatile complexing agent to an aqueous solution or aqueous dispersion of a vinyl copolymer containing a carboxyl group to form a metal complex. As a result, it is water resistant and oil resistant when dried at room temperature or low temperature.
耐熱性に優れた保護層を形成する感熱紙用表面保護剤が
得られることを発見した。又、この保護剤は作業性良好
な一液型であって、長期保存安定性を有すると共に経時
の保護保持力も長時間異常なく優れたものであることを
見出した。It has been discovered that a surface protective agent for thermal paper that forms a protective layer with excellent heat resistance can be obtained. It has also been found that this protective agent is a one-component type with good workability, has long-term storage stability, and has excellent protective retention over a long period of time without any abnormalities.
即ち２本発明はエチレン性不飽和カルボン酸５〜８０重
量％及び共重合可能なビニルモノマー２０〜９５重量％
からなる共重合体の水溶液又は水分散液に対し、多価金
属化合物と揮発性錯化剤を加えてなる金属錯化合物を含
有す・る感熱記録紙用表面保護剤を提供するものである
。That is, the present invention contains 5 to 80% by weight of an ethylenically unsaturated carboxylic acid and 20 to 95% by weight of a copolymerizable vinyl monomer.
The present invention provides a surface protective agent for thermal recording paper, which contains a metal complex compound obtained by adding a polyvalent metal compound and a volatile complexing agent to an aqueous solution or aqueous dispersion of a copolymer.
本発明に用いられるエチレン性不飽和カルボン酸として
は例えば、アクリル酸、メタクリル酸。Examples of the ethylenically unsaturated carboxylic acid used in the present invention include acrylic acid and methacrylic acid.
マレイン酸、イタコン酸、クロトン酸、フマール酸等の
・エチレン性不飽和カルボン酸又はそれらの無水物があ
げられる。共重合可能なビニルモノマーとしては例えば
アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−
ブチル、アクリル酸イソ）ブチル、アクリル酸ｎ−ヘキ
シル、アクリル酸２−エチルヘキシル、アクリル酸ノニ
ル、アクリル酸ラウリル、アクリル酸ステアリル等のア
クリル酸アルキルエステル類、メタクリル酸メチル、メ
タクリル酸エチル、メタクリルＭｎ−ブチル、メタクリ
ル酸イソブチル、メタクリル酸ｎ−ヘキシル、メタクリ
ル酸２−エチルヘキシル、メタクリル酸ノニル、メタク
リル酸ラウリル、メタクリル酸ステアリル等のメタクリ
ル酸アルキルエステ類。Examples include ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, crotonic acid, and fumaric acid, or their anhydrides. Examples of copolymerizable vinyl monomers include methyl acrylate, ethyl acrylate, and n-acrylate.
Acrylic acid alkyl esters such as butyl, iso)butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic Mn- Alkyl methacrylates such as butyl, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and stearyl methacrylate.
アクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプ
ロピル、メタクリル酸ヒドロキシエチル。Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate.
メタクリル酸ヒドロキシプロピル等のヒドロキシル基含
有単量体、アクリロニトリル、メタシクロニトリル等の
ニトリル類、アクリルアミド、メタクリルアミド、ジア
セトンアクリルアミド、Ｎ−メチロールアクリルアミド
、Ｎ−メチロールメタクリルアミド、Ｎ−ブトキシメチ
ルアクリルアミド、Ｎ−ブトキシメチルメタクリルアミ
ド等のＮ−置換（メタ）アクリル系単量体、スチレン、
α又はβ−メチルスチレン、α又はβ−エチルスチレン
等のスチレン系単量体、酢酸ビニル、プロピオン酸ビニ
ル等の１種又は２種以上から選択することができる。Hydroxyl group-containing monomers such as hydroxypropyl methacrylate, nitriles such as acrylonitrile and methacyclonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-butoxymethylacrylamide, N -N-substituted (meth)acrylic monomers such as butoxymethylmethacrylamide, styrene,
It can be selected from one or more of styrenic monomers such as α- or β-methylstyrene, α- or β-ethylstyrene, vinyl acetate, vinyl propionate, and the like.
エチレン性不飽和カルボン酸と共重合可能なモノマーの
重量比率は、エチレン性不飽和カルボン酸５〜８０重量
％、共重合可能なビニルモノマー２０〜９５重量％の範
囲内で使用される。エチレン性不飽和カルボン酸が５重
量％未満では、得られたポリマーの造膜性、耐溶剤性が
劣り耐油・耐可塑剤性が不充分である。耐熱性も不充分
でスティッキングを生じ易い。また、８０重量％を越え
ると得られたポリマーの浸水性が大き過ぎ、耐水性が悪
く、粘度が高くなり過ぎコーティング適性が悪くなる。The weight ratio of the monomer copolymerizable with the ethylenically unsaturated carboxylic acid is 5 to 80% by weight of the ethylenically unsaturated carboxylic acid and 20 to 95% by weight of the copolymerizable vinyl monomer. If the amount of ethylenically unsaturated carboxylic acid is less than 5% by weight, the resulting polymer will have poor film-forming properties and solvent resistance, and will have insufficient oil and plasticizer resistance. It also has insufficient heat resistance and tends to cause sticking. On the other hand, if the amount exceeds 80% by weight, the water permeability of the resulting polymer is too high, the water resistance is poor, and the viscosity is too high, resulting in poor coating suitability.
また、得られた皮膜が柔軟性に乏しく割れ易い等の問題
を生ずる。更に好ましくはエチレン性不飽和カルボン酸
のｆｆ１ｌ比率が２０〜６０重量％が望ましい。これら
のモノマー組成を通常の溶液重合あるいは乳化重合条件
て共重合させてカルボキシル基を含有するビニル系共重
合体を得る。 これらの共重合体は各種溶剤２例えばア
ルコール類、グリコールエーテル類、ケトン類、ホルム
アルデヒド類、トロール、キジロール、酢酸エステル類
等の１種又は２種以上を含有する水溶液又は水分散液に
も適用できる。又共重合体中のカルボキシル基と揮発性
塩基性塩を形成する揮発性塩基を添加することもてきる
。揮発性塩基としては例えば、アンモニア、ヒドロキシ
アミン等の無機塩基、メチルアミン、エチルアミン等の
アルキルアミン、シクロヘキシルアミン、ジエチルアミ
ン、ジプロピルアミン、トリメチルアミン、ピペリジン
等の有機塩基があげられる。Further, problems such as the resulting film having poor flexibility and being easily broken occur. More preferably, the ff1l ratio of ethylenically unsaturated carboxylic acid is 20 to 60% by weight. These monomer compositions are copolymerized under conventional solution polymerization or emulsion polymerization conditions to obtain a vinyl copolymer containing carboxyl groups. These copolymers can also be applied to aqueous solutions or aqueous dispersions containing one or more of various solvents 2, such as alcohols, glycol ethers, ketones, formaldehydes, trols, quidylols, acetic esters, etc. . It is also possible to add a volatile base that forms a volatile basic salt with the carboxyl group in the copolymer. Examples of volatile bases include inorganic bases such as ammonia and hydroxyamine, alkylamines such as methylamine and ethylamine, and organic bases such as cyclohexylamine, diethylamine, dipropylamine, trimethylamine and piperidine.
多価金属化合物としては亜鉛、カドミウム、コバルト、
ニッケル、銅、ジルコニウム等の無機酸塩、有機酸塩、
酸化物、水酸化物等があげられ特に亜鉛及びジルコニウ
ムの無機酸塩、有機酸塩。Polyvalent metal compounds include zinc, cadmium, cobalt,
Inorganic acid salts and organic acid salts of nickel, copper, zirconium, etc.
Examples include oxides, hydroxides, etc., especially inorganic and organic acid salts of zinc and zirconium.
酸化物、水酸化物が好ましい。又、これらの多価金属化
合物とポリマー中のカルボキシル基と錯体を形成する揮
発性錯化剤としてはアンモニア、メチルアミン、エチル
アミン、ジメチルアミン、ジエチルアミン、トリエチル
アミン、モルホリン。Oxides and hydroxides are preferred. Further, volatile complexing agents that form complexes with these polyvalent metal compounds and carboxyl groups in polymers include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, and morpholine.
エタノールアミン、ジェタノールアミン、トリエタノー
ルアミン等の如き揮発性アミンで、その中でもアンモニ
アが好ましい。Volatile amines such as ethanolamine, jetanolamine, triethanolamine, etc., among which ammonia is preferred.
これらの錯体はポリマー中のカルボキシル基と多価金属
化合物及び揮発性錯化剤とにより形成することもてきる
が、前もって多価金属化合物と揮発性錯化剤とにより錯
体を形成したものを添加することもてきる。又この両者
の併用も可能である。These complexes can be formed by the carboxyl group in the polymer, a polyvalent metal compound, and a volatile complexing agent; You can also do that. It is also possible to use both of them together.
その無８１酸塩としては例えば、炭酸塩、リン酸塩。Examples of non-81 acid salts include carbonates and phosphates.
硫酸塩等があげられ、有機塩酸としては例えば。Examples of organic hydrochloric acid include sulfates and the like.
酢酸塩、オキシカルボン酸塩等があげられるが中でも炭
酸塩が好ましい。Examples include acetate, oxycarboxylate, etc., but carbonate is preferred among them.
これらの多価金属化合物の使用量は共重合体のカルボキ
シル基に対し０．１〜２当量の範囲が好ましい。０．１
当量以下では耐水、耐油、耐熱性向上の効果が余りなく
、又２当量以上使用してもその効果が平衡状態に達っし
て不必要である。The amount of these polyvalent metal compounds used is preferably in the range of 0.1 to 2 equivalents based on the carboxyl group of the copolymer. 0.1
If the amount is less than one equivalent, the effect of improving water resistance, oil resistance, and heat resistance will not be so great, and if more than 2 equivalents are used, the effects will reach an equilibrium state and are unnecessary.
多価金属が無機酸塩又は有機酸塩（ポリマー中のカルボ
キシル基又は、前もって形成する錯体中の）と揮発性錯
化剤により可溶性錯塩を形成し。Polyvalent metals form soluble complex salts with inorganic or organic acid salts (in the carboxyl groups in the polymer or in the preformed complex) with volatile complexing agents.
錯化剤の蒸発ことよって実質上水不溶性の化合物を形成
する。上記方法により得られた皮膜は透明で耐水、耐油
、耐熱性に優れており、常温又は低温乾燥によりサーマ
ルヘッドマツチング性の良好な。Evaporation of the complexing agent forms a substantially water-insoluble compound. The film obtained by the above method is transparent, has excellent water resistance, oil resistance, and heat resistance, and has good thermal head matching properties when dried at room temperature or low temperature.
耐薬品性に優れた感熱記録紙用表面保護Ｎを形成する。Forms surface protection N for thermal recording paper with excellent chemical resistance.
以下９本発明の実施例をあげて具体的に説明するが９部
とは重量部を９％は重量％を表すものである。The present invention will be specifically explained below with reference to nine examples, where 9 parts means parts by weight and 9% means % by weight.
ス」１皿−−Ｌ 温度調節機、攪拌機、還流冷却器、供給容器。1 plate - L Temperature controller, stirrer, reflux condenser, supply vessel.
温度計を偏えた反応容器内に下記原料を装入する。Charge the following raw materials into a reaction vessel with a thermometer on the side.
水
４２９部エチレンオキシド２０モルと 。water
429 parts and 20 moles of ethylene oxide.
反応させたノニルフェノール
の硫酸エステルのナトリウム
塩（アニオン性乳化剤）の２
５％水溶液 １６部供給物■と
して下記の混合物を用いる。16 parts of a 25% aqueous solution of the reacted sodium salt of the sulfuric ester of nonylphenol (anionic emulsifier) The following mixture is used as feed (1).
スチレン ５０部メタクリル
酸メチル ３５部アクリル酸ｎ−ブチル
４５部メタクリル酸
７０部アクリルアミド ３
部供給物■として下記の溶液を調整する。Styrene 50 parts Methyl methacrylate 35 parts n-Butyl acrylate 45 parts Methacrylic acid
70 parts acrylamide 3
Prepare the following solution as part feed (■).
水
４０部過硫酸カリウム
２部反応容器内を窒素置換したのち、８０℃に昇温後。water
40 parts potassium persulfate
After purging the inside of the two-part reaction vessel with nitrogen, the temperature was raised to 80°C.
供給物■のＩ／２を注入した。次いで３時間かけて供給
物■及び、供給物Ｈの１７４を供給する・共給後、供給
物Ｈの】／４を注入し２時間８５°Ｃに昇温し重合反応
を完結せしめ冷却した。冷却後２５％アンモニア水１６
２．４部と炭酸ジルコニウム４４．２部を添加し、１時
間攪拌して、水性分散体を得た。I/2 of feed ■ was injected. Next, feed 1 and 174 of feed H were fed over a period of 3 hours. After co-feeding, ]/4 of feed H was injected, the temperature was raised to 85° C. for 2 hours, the polymerization reaction was completed, and the mixture was cooled. After cooling 25% ammonia water 16
2.4 parts of zirconium carbonate and 44.2 parts of zirconium carbonate were added thereto and stirred for 1 hour to obtain an aqueous dispersion.
比較例 ２
実施例１の組成物より炭酸ジルコニウムを除いた他は実
施例１と同じ方法で水性分散体を得た。Comparative Example 2 An aqueous dispersion was obtained in the same manner as in Example 1 except that zirconium carbonate was removed from the composition of Example 1.
実施例 ２
実施例１と同様に操作し、ただし下記の原料を反応容器
内に装入する。Example 2 The procedure is as in Example 1, except that the following raw materials are charged into the reaction vessel.
水 ４
１５．３ 部実施例１と同し乳化剤水溶ｔ？！１６
部供給物Ｉ
スチレン ５５ 部アクリル酸
２−エチルヘキシル ４５ 部メタクリル酸
１００ 部その他は実施例１と同様に操作し
２反応物を冷却後２５％アンモニア水１３９．２部と酸
化亜鉛２９．４部を添加し、水性分散体を得た。water 4
15.3 parts Same as Example 1 Emulsifier water-soluble t? ! 16
Part Feed I Styrene 55 parts 2-ethylhexyl acrylate 45 parts Methacrylic acid
100 parts Other operations were carried out in the same manner as in Example 1. After cooling the two reactants, 139.2 parts of 25% ammonia water and 29.4 parts of zinc oxide were added to obtain an aqueous dispersion.
比較ゆｊ２
実施例２０刊成物より酸化亜鉛を除いた他は実施例２と
同し方法で水性分散体を得た・実施例 ３
実施例１と同様に操作し、ただし下記の原料を反応容器
内に装入する。Comparison Yuj2 Example 20 An aqueous dispersion was obtained in the same manner as in Example 2 except that zinc oxide was removed from the published product.Example 3 The procedure was carried out in the same manner as in Example 1, except that the following raw materials were reacted. Charge into container.
水
４１５．３ 部実施例■と同し乳化剤水溶液 １６
部供給物■
スチレン ３０ 部アクリル酸
ｎ−ブチル ５０ 部アクリル酸２−エチル
ヘキシル ４０ 部メタクリル酸メチル
３０ 部メタクリル酸 ５０ 部
その他は実施例１と同様に操作し９反応物を冷却後下記
の錯体の水溶液を添加し、水分散体を得た。water
415.3 parts Emulsifier aqueous solution same as Example ■ 16
Parts Feed ■ Styrene 30 parts n-butyl acrylate 50 parts 2-ethylhexyl acrylate 40 parts Methyl methacrylate
30 parts methacrylic acid 50 parts Other operations were carried out in the same manner as in Example 1. After cooling the 9 reactants, an aqueous solution of the following complex was added to obtain an aqueous dispersion.
炭酸亜鉛 １９．６部２５％アン
モニア水 １１６ 部水
２７ 部比
較例 ３
実施例３の組成物より錯体水溶液を除いた他は実施例２
と同じ方法で水分散体を得た。Zinc carbonate 19.6 parts 25% ammonia water 116 parts Water
27 parts Comparative Example 3 Example 2 except that the complex aqueous solution was removed from the composition of Example 3.
An aqueous dispersion was obtained in the same manner.
実施例 ４ 温度調節機、攪拌機、還流冷却器、供給容器。Example 4 Temperature controller, stirrer, reflux condenser, supply vessel.
温度計を備えた反応容器内に下記原料を装入する。The following raw materials are charged into a reaction vessel equipped with a thermometer.
メタノール １２１．３部アゾビスイ
ソブチロニトリル ２ 部供給物■として下記の
混合物を用いる。Methanol 121.3 parts Azobisisobutyronitrile 2 parts The following mixture is used as feed (■).
スチレン ４５ 部アクリル酸
ｎ−ブチル ５０ 部アクリル酸２−エチル
ヘキシル ４０ 部メタクリル酸メチル
２０ 部メタクリル酸 ４５ 部
供給物■として下記の分散液を調整する。Styrene 45 parts n-butyl acrylate 50 parts 2-ethylhexyl acrylate 40 parts Methyl methacrylate
20 parts methacrylic acid 45 parts The following dispersion is prepared as Feed ■.
メタノール ９ 部アゾビスイ
ソブチロニトリル １ 部反応容器内を窒素置換
したのち、還流温度（６５±５℃）に昇温２時間かけて
供給物Ｉを注入した。9 parts of methanol 1 part of azobisisobutyronitrile After the inside of the reaction vessel was purged with nitrogen, the temperature was raised to reflux temperature (65±5°C) and feed I was injected over 2 hours.
注入後、供給物■を２回に分けて注入し３時間還流温度
に保持して重合反応を完結させた後、モノエタノールア
ミン４．２５部、２５％アンモニア水７部、水１５５．
４５部を添加後、メタノールを水との共沸化留去し、共
合体濃度が３０％となる様に水を添加し、冷却後酸化亜
鉛８．９部、２５％アンモニア水５２．２部を添加して
水性分散体を得た。After the injection, the feed (1) was injected in two portions and maintained at reflux temperature for 3 hours to complete the polymerization reaction, followed by 4.25 parts of monoethanolamine, 7 parts of 25% aqueous ammonia, and 155.5 parts of water.
After adding 45 parts, methanol was azeotropically distilled off with water, water was added so that the copolymer concentration was 30%, and after cooling, 8.9 parts of zinc oxide and 52.2 parts of 25% aqueous ammonia were added. was added to obtain an aqueous dispersion.
比較例 ４
実施例４の組成物より酸化亜鉛を除いた他は実施例４と
同じ方法で水性分散体を得た。Comparative Example 4 An aqueous dispersion was obtained in the same manner as in Example 4 except that zinc oxide was removed from the composition of Example 4.
試験例
（１）実施例及び参考例で得られた各塗工液を５〜１５
％濃度に調整し、これをロイコ染料系の感熱記録紙にワ
イヤーバーを用いて塗布し、５０℃で１分間乾燥して表
面保護層の厚さが２μｍの感熱記録紙を得た。各表面保
護剤ともに透明な表面保護層が得られた。Test example (1) Each coating liquid obtained in the example and reference example was
% concentration, was applied to a leuco dye-based thermal recording paper using a wire bar, and dried at 50° C. for 1 minute to obtain a thermal recording paper with a surface protective layer thickness of 2 μm. A transparent surface protective layer was obtained with each surface protective agent.
（２）耐油・耐水性試験
（１）で得た感熱記録紙をファクシミリ装置により印字
した。比較例１〜４はサーマルヘッドのスティッキング
を生じ、印字濃度が低かったが、実施例１〜４はスティ
ッキングを生しることなく。(2) Oil and water resistance test The heat-sensitive recording paper obtained in (1) was printed using a facsimile machine. Comparative Examples 1 to 4 caused sticking of the thermal head and the print density was low, but Examples 1 to 4 did not cause sticking.
印字濃度も高かった。塩ビラツブフィルムを重ね。Print density was also high. Layer the PVC film.
またサラダ油、大豆油を塗り、それぞれ２４時間後に印
字の濃度を測定した。比較例１〜４は消失してしまった
が実施例１〜４は変化なかった。Furthermore, salad oil and soybean oil were applied, and the density of the print was measured 24 hours later. Comparative Examples 1 to 4 disappeared, but Examples 1 to 4 remained unchanged.
また、同し感熱記録紙を水中に浸漬し指でなぞってみた
。比較例１，２は印字が剥げたが、実施例１〜４．比較
例３，４は剥げなかった。I also immersed the same thermal recording paper in water and traced it with my finger. In Comparative Examples 1 and 2, the printing peeled off, but in Examples 1 to 4. Comparative Examples 3 and 4 did not peel off.
発明の効果
以上の如く各試験により、夫々の場合の共重合体水溶液
又は分散液に金属錯化合物を含有する感熱記録紙用表面
保護剤は透明性が良く、サーマルヘッドのスティッキン
グを生ずることなく、耐油。Effects of the Invention As described above, various tests have shown that the surface protective agent for thermal recording paper containing a metal complex compound in the copolymer aqueous solution or dispersion in each case has good transparency and does not cause sticking of the thermal head. Oil resistant.
耐水性が優れていることが確認された。又、これらの性
能が感熱記録紙の特性上必要不可欠である常温もしくは
低温、短時間乾燥で得られ９作業性の良い一液型で長門
保存安定性も良好である。It was confirmed that it has excellent water resistance. In addition, these properties can be obtained by drying at room temperature or low temperature for a short time, which is essential for the properties of thermal recording paper.9 It is a one-component type with good workability and has good Nagato storage stability.
Claims (1)
合可能なビニルモノマー２０〜９５重量％からなる共重
合体の水溶液又は水分散液に対し、多価金属化合物と揮
発性錯化剤を加えてなる金属錯化合物を含有する感熱記
録紙用表面保護剤。A polyvalent metal compound and a volatile complexing agent are added to an aqueous solution or aqueous dispersion of a copolymer consisting of 5 to 80% by weight of an ethylenically unsaturated carboxylic acid and 20 to 95% by weight of a copolymerizable vinyl monomer. A surface protective agent for thermal recording paper containing a metal complex compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60233168A JPH06432B2 (en) | 1985-10-18 | 1985-10-18 | Surface protective agent for thermal recording paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60233168A JPH06432B2 (en) | 1985-10-18 | 1985-10-18 | Surface protective agent for thermal recording paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6292887A true JPS6292887A (en) | 1987-04-28 |
| JPH06432B2 JPH06432B2 (en) | 1994-01-05 |
Family
ID=16950787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60233168A Expired - Fee Related JPH06432B2 (en) | 1985-10-18 | 1985-10-18 | Surface protective agent for thermal recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06432B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0437584A (en) * | 1990-06-01 | 1992-02-07 | Fuji Photo Film Co Ltd | Thermal recording material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS496396A (en) * | 1972-04-28 | 1974-01-21 | ||
| JPS50146581A (en) * | 1974-05-16 | 1975-11-25 | ||
| JPS5423546A (en) * | 1977-07-25 | 1979-02-22 | Tomoegawa Paper Co Ltd | Heat sensitive recording medium |
| JPS5911289A (en) * | 1982-07-10 | 1984-01-20 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS6015190A (en) * | 1983-07-07 | 1985-01-25 | Ricoh Co Ltd | Thermographic material |
-
1985
- 1985-10-18 JP JP60233168A patent/JPH06432B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS496396A (en) * | 1972-04-28 | 1974-01-21 | ||
| JPS50146581A (en) * | 1974-05-16 | 1975-11-25 | ||
| JPS5423546A (en) * | 1977-07-25 | 1979-02-22 | Tomoegawa Paper Co Ltd | Heat sensitive recording medium |
| JPS5911289A (en) * | 1982-07-10 | 1984-01-20 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS6015190A (en) * | 1983-07-07 | 1985-01-25 | Ricoh Co Ltd | Thermographic material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0437584A (en) * | 1990-06-01 | 1992-02-07 | Fuji Photo Film Co Ltd | Thermal recording material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06432B2 (en) | 1994-01-05 |
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