JPS61244592A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS61244592A JPS61244592A JP60086539A JP8653985A JPS61244592A JP S61244592 A JPS61244592 A JP S61244592A JP 60086539 A JP60086539 A JP 60086539A JP 8653985 A JP8653985 A JP 8653985A JP S61244592 A JPS61244592 A JP S61244592A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- polymer
- ink
- sensitive
- recording
- 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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/3825—Electric current carrying heat transfer sheets
-
- 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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
- B41M5/395—Macromolecular additives, e.g. binders
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱ヘッド、レーザー、フラッシュ光或いは電気
信号を直接通電する等の手段Ｅこより、記録材料を印加
信号ｌこ対応して加熱して感熱転写記録を行う画像記録
材料に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a means for heating a recording material in response to an applied signal by a means such as a thermal head, laser, flash light, or direct application of an electric signal. The present invention relates to an image recording material that performs thermal transfer recording.
熱エネルギーの印加に対応する材料の物理的性質の変化
や化学反応性の変化を利用した感熱記録方式は、古（か
ら幾多の方法が提案されている。なかでもクリスタルバ
イオレットラクトン、フルオラン系、スピロピラン系等
の無色染料トビスフエノールＡ等のフェノール化合物や
その他の有機酸、無機酸との染料発色反応や有機酸金属
塩とフェノール類等の有機還元剤、金属硫化物、有機キ
レート剤、有機硫黄化合物との熱反応を利用した感熱発
色記録方式と、熱浴。Since ancient times, many methods have been proposed for thermal recording methods that utilize changes in the physical properties and chemical reactivity of materials in response to the application of thermal energy. Colorless dyes such as tobisphenol A, dye coloring reactions with phenolic compounds such as tobisphenol A, other organic acids, inorganic acids, organic acid metal salts and organic reducing agents such as phenols, metal sulfides, organic chelating agents, organic sulfur. A thermosensitive color recording method that utilizes a thermal reaction with a compound and a heat bath.
陽性、熱昇華性等の熱物性変化を利用してインクや色材
を紙等の被記録体に転移させる感熱転写記録法が、近年
盛んに研究され改良の努力がなされている。2. Description of the Related Art Thermal transfer recording methods, in which ink and coloring materials are transferred to a recording medium such as paper by utilizing changes in thermophysical properties such as positivity and heat sublimation, have been actively researched and efforts have been made to improve them in recent years.
特に、後者の感熱転写記録方式は普通紙への記録が可能
であること、記録画像の耐光性、安定性、保存性が良好
であること、記録機構が単純なため、信頼性が高いこと
等の利点を有するため、プリンター、ファクシミリ、複
写機等へ応用がされている。In particular, the latter thermal transfer recording method is capable of recording on plain paper, has good light resistance, stability, and storage stability of recorded images, and has a simple recording mechanism, so it is highly reliable. Because of these advantages, it has been applied to printers, facsimile machines, copying machines, etc.
しかしながら、染料を熱昇華させる方式の場合には、濃
度の連続階調性の再現が可能といった利点を有する反面
、記録感度、記録体の保存安定性、記録画像の定着安定
性、耐光性等に問題がある。又、インクを熱溶融させ紙
等に印加信号に対応したインクを転写記録する方式の場
合には上記問題は低減されるが、通常低融点の結晶性ワ
ックスを感熱インク層の結着剤として用いるため、記録
体中の熱拡散により、解像力が低下したり、転写、定着
画像の強度が弱いといった問題を有する。又、結晶性ワ
ックス類は結晶相の光散乱により鮮明な画像を得にくい
という欠点を有している。However, in the case of the method of thermally sublimating the dye, while it has the advantage of being able to reproduce continuous tone density, it has problems with recording sensitivity, storage stability of the recording medium, fixing stability of recorded images, light fastness, etc. There's a problem. In addition, in the case of a method of thermally melting the ink and transferring and recording the ink corresponding to the applied signal to paper etc., the above problem is reduced, but usually a crystalline wax with a low melting point is used as a binder for the heat-sensitive ink layer. Therefore, there are problems such as a decrease in resolution and weak strength of transferred and fixed images due to thermal diffusion in the recording medium. Furthermore, crystalline waxes have the disadvantage that it is difficult to obtain clear images due to light scattering of the crystalline phase.
すなわち、インク材料を数回にわたり重ね記録して鮮明
なカラー画像、特ｌこビクトリアルフルカラー再現像を
得るため（こは、通常マゼンタ、イエロー、シアン色の
インク材料が用いられ、それらのインク材料が重ね合わ
せられて２？′に色更には３次色が得られる。例えば２
種類のインク材料の重ね合せによって２次色を得る場合
（こ実際に得られる２次色と目的とする２次色との色差
はインク材料の透明性ｌこよって決定される。That is, in order to obtain a clear color image, especially a Victorian full-color reproduction image, by overlapping recording of ink materials several times (usually magenta, yellow, and cyan ink materials are used, and these ink materials are superimposed to obtain 2?' colors and even tertiary colors.For example, 2?'
When obtaining a secondary color by superimposing different types of ink materials, the color difference between the actually obtained secondary color and the intended secondary color is determined by the transparency of the ink material.
重ね記録を行う場合、少な（とも」二部層ζこ重ねられ
るインク材料の透明性、より厳密にいえばインク材料結
着層の透明性が良好であれば、重ねられたインク層から
の反射光は顔料そのものの特性による２次色反射光によ
り近いものとなり、それだけカラー再現性が良好となる
。When overlapping recording is performed, if the transparency of the overlapping ink material is good, or more precisely, the transparency of the ink material binding layer is good, the reflection from the overlapping ink layers can be reduced. The light becomes closer to the secondary color reflected light due to the characteristics of the pigment itself, and the color reproducibility is improved accordingly.
従来、感熱インク層の結着成分に樹脂を使用するものと
しては、特開昭５４−８７２３４号、同５６−９８２６
９号等が知られているが、これらはいずれも前記ワック
スを結着剤として用いる感熱インク材料に対して、印字
の定着性や耐久性の向上を目的としており、カラー再現
を目的として結着成分の透明性に着目した技術的な開示
はなされていない。Conventionally, examples of using resin as a binding component of a heat-sensitive ink layer include JP-A-54-87234 and JP-A-56-9826.
No. 9 etc. are known, but all of these are aimed at improving the fixation and durability of prints for thermal ink materials that use wax as a binder, and are used as a binder for the purpose of color reproduction. There is no technical disclosure focusing on the transparency of ingredients.
従って、本発明の目的は、鮮明なカラー再現を可能とす
る感熱転写記録材料を提供することにある。Therefore, an object of the present invention is to provide a heat-sensitive transfer recording material that enables clear color reproduction.
３一
本発明の他の目的は、解像性の良好な感熱転写記録材料
を提供することにある。31 Another object of the present invention is to provide a thermal transfer recording material with good resolution.
本発明の更に他の目的は、記録感度、転写、定着性の良
好な感熱転写記録材料を提供することにある。Still another object of the present invention is to provide a thermal transfer recording material with good recording sensitivity, transfer and fixing properties.
〔問題点を解するための手段及び作用］本発明者らは鋭
意検討の結果、感熱インク材料の結着剤を従来の結晶性
ワックス類を主成分としたちの７１１）ら実質的ｌこ非
晶質の透明高分子材料に変更し、更ｌこ少量の離型性物
質を添加することによって前記本発明の目的が達成され
ることを見出し、本発明を完成した。[Means and effects for solving the problem] As a result of intensive studies, the present inventors found that the binder of the thermal ink material is substantially different from the conventional crystalline wax (711) as the main component. The present invention was completed based on the discovery that the object of the present invention can be achieved by changing to a crystalline transparent polymer material and adding a small amount of a releasing substance.
すなわち、本発明は熱溶融性感熱インク材料層を支持体
上５こ設けた記録材料において、前記感熱インク材料が
非晶質ポリマーと離型性物質と着色剤を主成分とし、前
記非晶質ポリマーが感熱インク材料の非揮発成分中に少
なくとも５０重量％含まれていることを特徴とする感熱
記録材料である。That is, the present invention provides a recording material in which five heat-melting heat-sensitive ink material layers are provided on a support, wherein the heat-sensitive ink material contains an amorphous polymer, a releasing substance, and a colorant as main components, and the amorphous A heat-sensitive recording material characterized in that a polymer is contained in the non-volatile components of the heat-sensitive ink material in an amount of at least 50% by weight.
本発明で用いる非晶質ポリマーとは、従来感熱転写材料
のベース材として用いられているような結晶性ポリマー
（ポリエチレンテレフタレート等）とは異なり基本的ｌ
こ明確な融点を示さない実質的に非晶質の透明ポリマー
である。The amorphous polymer used in the present invention is different from crystalline polymers (polyethylene terephthalate, etc.) conventionally used as base materials for thermal transfer materials.
This is a substantially amorphous transparent polymer that does not exhibit a distinct melting point.
従来、感熱インク材の結着材料として用いられているワ
ックス類は、パラフィンワックス、カルナバワックス、
モンタンワックス、ミツロウ、木ロウ、キャンデリラワ
ックスや低分子量ポリエチレン、α−オレフィンオリゴ
マー及びこれらの共重合体や変性物であり、必要に応じ
て、更にスピンドル油等の鉱物油やアマニ油、キリ油等
の植物油、ジオクチルフタレート、ジブチルフタレート
等の可塑剤、オレイン酸、ステアリン酸等の高級脂肪酸
やその金属塩、アミドその他線導体を染顔料等に哄、ｔ
：混合分散し、薄層のプラスチックフィルムやコンデン
サ紙上ｌこ塗布することによって感熱転写記録材とされ
ていた。Conventionally, waxes used as binding materials for thermal ink materials include paraffin wax, carnauba wax,
Montan wax, beeswax, wood wax, candelilla wax, low molecular weight polyethylene, α-olefin oligomers, and copolymers and modified products thereof, and if necessary, mineral oil such as spindle oil, linseed oil, tung oil. etc., plasticizers such as dioctyl phthalate and dibutyl phthalate, higher fatty acids such as oleic acid and stearic acid, their metal salts, amides, and other wire conductors in dyes and pigments, etc.
: A thermal transfer recording material was made by mixing and dispersing the mixture and coating it on a thin layer of plastic film or capacitor paper.
この様な従来の結着材料たるワックス類は、結晶性であ
るため約５０’０から約１５０−０程度の温度領域に比
較的明瞭な融点を有し、融点以上に加熱すると急激に固
相力）ら液相へと変化する。Waxes, which are conventional binding materials, have a relatively clear melting point in the temperature range of about 50'0 to about 150'0 because they are crystalline, and when heated above the melting point, they rapidly turn into a solid state. force) to the liquid phase.
そして融点より３０℃程度高い温度で約１０−２乃至約
１０ ｐｏｉｓｅの低粘度液体となる。これｌこ対して
非晶質ポリマーの場合は本質的に融点は存在せず、ガラ
ス転移温度（Ｔｇ）を境にして徐々に固相から液相へと
変化する。この間の粘度変化はＷＬＦ式もしくはアンド
レード式に基本的に従い、Ｔｇより約５０”０高い温度
でもせいぜい１０３〜１０’ ｐｏｉｓｅ程度までしか
通常粘度は低下しない。感熱転写記録の場合、その転写
、定着感度は基本的ζこ結着材料の溶融粘度や溶融粘弾
性によって支配されるため、非晶質高分子を感熱インク
の結着材として用いることは、感度的に明らかに不利で
ある。しかしながら、本発明者らは特定の分子量とＴｇ
を有する非晶質ポリマーを結着材料として用い、更ｌこ
離型性物質を添加すると感度を犠牲にすることなく、画
質と画像の安定性を大幅ｌこ改善しうることを見出した
Ｏ
すなわち、本発明の感熱記録材料では、感熱インク層の
結着材成分として特定の非晶質ポリマーを感熱インク材
料の非揮発成分中ｌこ少な（とも５０重量％用いること
によって、従来結晶性ポリマー結着層の結晶によって生
じていた透過光の散乱が全く消失し、カラーの再現、
Ｈｔこインク材料の重ね記録によるカラーの再現ｌこお
いて鮮明な画像を得るために不可欠な結着材層の透明性
を保つことができる。At a temperature about 30° C. higher than the melting point, it becomes a low viscosity liquid of about 10 −2 to about 10 poise. On the other hand, amorphous polymers essentially have no melting point and gradually change from a solid phase to a liquid phase after reaching the glass transition temperature (Tg). The viscosity change during this period basically follows the WLF formula or Andrade formula, and the viscosity normally decreases to about 103 to 10' poise at most even at a temperature about 50'0 higher than Tg.In the case of thermal transfer recording, the transfer and fixing Sensitivity is governed by the melt viscosity and melt viscoelasticity of the basic binder material, so using an amorphous polymer as a binder for thermal ink is obviously disadvantageous in terms of sensitivity. We have determined that the specific molecular weight and Tg
It has been found that by using an amorphous polymer having a 0 as a binder material and adding a releasable substance, image quality and image stability can be significantly improved without sacrificing sensitivity. In the heat-sensitive recording material of the present invention, by using a specific amorphous polymer as a binder component of the heat-sensitive ink layer in a small amount (50% by weight) of the non-volatile components of the heat-sensitive ink material, conventional crystalline polymer The scattering of transmitted light caused by the crystals in the deposited layer completely disappears, resulting in improved color reproduction,
The transparency of the binder layer, which is essential for obtaining clear images in color reproduction by overlapping recording of Ht ink materials, can be maintained.
一般ｌこ結着剤として高分子材料を用いることは、記録
感度的１こ不利であると考えられているが、本発明にお
いては非晶質ポリマーの重量平均分子量とガラス転移温
度の２つの因子を制御し、かつ離型性物質の支持体界面
ｆこおける低エネルギー効果を利用することｌこよって
、従来のワックス系感熱記録材料と同等の記録感度を保
ちながら、ワックス系でみられたような結着層における
熱拡散を防いで優れた解像力を得るとともに、ポリマー
独特の可とう性や耐摩擦性の性質を生かし、定着性をこ
すぐれた印字が可能となる。Generally speaking, using a polymeric material as a binder is considered to be disadvantageous in terms of recording sensitivity, but in the present invention, two factors, the weight average molecular weight of the amorphous polymer and the glass transition temperature, are considered to be disadvantageous. By controlling the temperature and utilizing the low energy effect of the release material at the support interface f, it is possible to maintain recording sensitivity equivalent to that of conventional wax-based heat-sensitive recording materials, while maintaining the same recording sensitivity as that seen with wax-based materials. In addition to obtaining excellent resolution by preventing heat diffusion in the binding layer, it also takes advantage of the polymer's unique flexibility and abrasion resistance, making it possible to print with superior fixation properties.
以下本発明の感熱記録材料を詳細をこ説明する。The heat-sensitive recording material of the present invention will be explained in detail below.
本発明の感熱記録材料では、ゲルパーミェーションクロ
マトグラフィー（ＧＰＣ）法で測定したポリスチレン換
算の数平均分子量が約１０，０００以下、示差走査熱量
（ＤＳＣ）法で測定したガラス転移温度（Ｔｇ）が約４
０℃以上、より好ましくは数平均分子量が約５．０００
以下％ Ｔｇが約５０”Ｃから８０’Ｏの範囲１こある
非晶質ポリマーもしくはオリゴマーを結着材料として感
熱インク材料非揮発性成分中少な（とも５０重量％含む
よう壷こ使用する。The heat-sensitive recording material of the present invention has a polystyrene-equivalent number average molecular weight of about 10,000 or less as measured by gel permeation chromatography (GPC), and a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC). ) is about 4
0°C or higher, more preferably a number average molecular weight of about 5.000
An amorphous polymer or oligomer having a Tg in the range of about 50''C to 80'O is used as a binder material in a proportion (50% by weight) of the non-volatile components of the heat-sensitive ink material.
すなわち、感熱インク材料の非揮発性成分中前記非晶性
ポリマー含量が５０重量％より少ない場合には、感熱イ
ンク材料の透明性は著しく悪化し、良好なカラー再現性
を得られないのに対し、非品性ポリマー含量が５０重量
−以上、特に７０重量％以上となると非常に良好な透明
性を示し、特にインク材料の重ね合せによるカラー再現
にすぐれた効果を得ることができる。That is, when the content of the amorphous polymer in the non-volatile components of the thermal ink material is less than 50% by weight, the transparency of the thermal ink material deteriorates significantly and good color reproducibility cannot be obtained. When the content of the non-quality polymer is 50% by weight or more, especially 70% by weight or more, it exhibits very good transparency, and particularly excellent color reproduction can be obtained by superimposing ink materials.
＝８−
これは、全感熱インク材料成分中に占める結晶性成分の
増減に起因するものであり、感熱インク材料成分中に占
める非晶質成分が増加することζこよって、結晶による
光の散乱の程度が多（なり、透明性が悪化することによ
るものと考えられる。また非晶質ポリマーのＴｇが５０
℃未満、特に４０°Ｃ未満の場合は、感熱インク材料の
プロツキンダが起こりやすく、保存時や使用時の安定性
に欠ける。又Ｔｇが８０′Ｏを越える場合は、熱安定性
は良好であるが、感度が低下するため実用性に欠は特殊
な用途の外は利用できない。=8- This is due to the increase or decrease of the crystalline component in the total heat-sensitive ink material component, and the amorphous component in the heat-sensitive ink material component increases.Thus, the scattering of light by the crystals increases. This is thought to be due to the fact that the Tg of the amorphous polymer is 50.
If the temperature is below .degree. C., especially below 40.degree. C., the thermal ink material tends to undergo blockage and lacks stability during storage or use. If Tg exceeds 80'O, the thermal stability is good, but the sensitivity is lowered, so it is impractical and cannot be used except for special purposes.
Ｔｇが前記範囲内であっても、非晶質ポリマーの分子量
が高い場合にも感度が低下する事が実験的に確認された
。これは分子鎖の７１）らみ合い等に基づ（分子間の凝
集力ｔこ起因すると推測され、数平均分子量が約１万以
下、特に５ 、０００以下の場合に良好な転写、定着性
が得られた。重量平均分子量の設定は、感熱転写記録材
料の用途によって変わりつる。従来のワックス系インク
と同様に２値的転写画像を得たい時ｌこは、重量平均分
子量も約４万以下、より好ましくは約１万以下とし、分
子量分布を狭（することによって非晶質ポリマーの軟化
特性をより鋭敏にすることが望ましい。一方、濃度階調
性や多値転写画像を得たり、又多数回繰返し使用を行い
たい場合にはゆるやかな軟化特性を示す非晶質ポリマー
ヲ印加エネルギーζこ応じて溶融転写するのが望ましく
、そのため（こは重量平均分子量を必ずしも小さくする
必要はな（、約４万以上に設定しても良い。もちろんこ
の場合でも２値転写画像も良好に得ることができる。更
ｌこ又、分子量分布の形状は必ずしも単一分子量ピーク
を有する形状である必要はなく、複数の分子量ピークを
有する分布形状であってもよいし、架橋、分岐ポリマー
成分を併用してもよい。It has been experimentally confirmed that even if the Tg is within the above range, the sensitivity decreases when the molecular weight of the amorphous polymer is high. This is presumed to be due to the cohesive force between molecules (71) entanglement of molecular chains, etc., and good transfer and fixing properties are obtained when the number average molecular weight is about 10,000 or less, especially 5,000 or less. was obtained.The setting of the weight average molecular weight varies depending on the use of the thermal transfer recording material.When it is desired to obtain a binary transfer image similar to conventional wax-based inks, the weight average molecular weight is also approximately 40,000. Hereinafter, it is more preferable to make the softening characteristics of the amorphous polymer more sensitive by narrowing the molecular weight distribution by setting it to about 10,000 or less. In addition, when repeated use is desired, it is desirable to melt-transfer an amorphous polymer that exhibits gradual softening characteristics according to the applied energy; therefore, it is not necessary to reduce the weight average molecular weight. It may be set to about 40,000 or more.Of course, even in this case, a binary transfer image can be obtained well.Furthermore, the shape of the molecular weight distribution does not necessarily have to have a single molecular weight peak. , a distribution shape having a plurality of molecular weight peaks may be used, or a crosslinked or branched polymer component may be used in combination.
但し、重量平均分子量を約１万以上、特に４万以上Ｉこ
設定した場合は、感度的には不利である。However, if the weight average molecular weight is set to about 10,000 or more, particularly 40,000 or more, it is disadvantageous in terms of sensitivity.
非晶質ポリマーの化学組成及び構造は、勿論感熱インク
材料の特性に影響を与えるが、その効果は前述の分子は
やＴｇ程大きくない。分子量とＴｇの値が前記規定範囲
ｌこあれば、基本的に本発明の感熱インク材料ヒして適
用する事がＦｉＪ能である。The chemical composition and structure of the amorphous polymer will of course influence the properties of the thermal ink material, but the effect is not as great as that of Tg for the aforementioned molecules. If the molecular weight and Tg values are within the specified ranges, it is basically possible to apply the thermal ink material of the present invention.
例えば、スチレン、ビニルトルエン、α−メチルスチレ
ン、２−メチルスチレン、クロルスチレン、ビニル安息
１２、ビニルベンゼンスルホン酸ソーダ、アミノスチレ
ン等のスチレン及び゛その誘導体、置換体の単独重合体
や共重合体、メチルメタクリレート、エチルメタクリレ
ート、ブチルメタクリレート、ヒドロキシエチルメタク
リレート等のメタクリル酸エステル類及びメタクリル酸
、メチルアクリレート、エチルアクリレート、ブチルア
クリレート、α−エチルへキシルアクリレート等のアク
リル酸エステル及びアクリル酸、ブタジェン、インプレ
ン等のジエン類、アクリロニトリル、ビニルエーテル類
、マレイン酸及びマレイン酸エステル類、無水マレイン
【獄、ケイ皮酸、塩化ビニル、酢酸ビニル等のビニル系
単量体の単独あるいは１ｍの単量体との共重合体を用い
ることが出来る。For example, homopolymers and copolymers of styrene and its derivatives and substituted products, such as styrene, vinyltoluene, α-methylstyrene, 2-methylstyrene, chlorostyrene, vinylbenzene-12, sodium vinylbenzenesulfonate, and aminostyrene. , methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, and acrylic acid esters such as methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, α-ethylhexyl acrylate, and acrylic acid, butadiene, imprene Dienes such as acrylonitrile, vinyl ethers, maleic acid and maleic esters, maleic anhydride, vinyl monomers such as cinnamic acid, vinyl chloride, vinyl acetate, etc. alone or in combination with 1m monomer. Polymers can be used.
又、縮合系樹脂としては、フタル酸、無水フタル酸、イ
ソフタル酸、テレフタル酸、ヘキサヒドロ無水フタル酸
、マロン酸、コハク酸、グルタル酸、アジピン酸、セバ
シン酸等の飽和二塩基酸や無水マレイン酸、フマール酸
、イタコン酸、テトラヒドロ無水フタル酸等の不飽和二
塩基酸とエチレングリコール、１．２−プロピレンクリ
コール、１，６−ヘキサンジオール、ヒスフェノールＡ
１ ビスフェノールＡプロピレンオキサイド付加物、ビ
スフェノールＡエチレンオキサイド付加物等のジオール
類との重縮合で得られるポリエステル樹脂を用いてもよ
い。この場合更にトリメリット酸、グリセリン、トリメ
チロールプロパン等の三官能化合物を用いて、分岐もし
くは架橋ポリエステルとしても良い。In addition, condensation resins include saturated dibasic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic anhydride, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, and maleic anhydride. , unsaturated dibasic acids such as fumaric acid, itaconic acid, and tetrahydrophthalic anhydride, and ethylene glycol, 1,2-propylene glycol, 1,6-hexanediol, hisphenol A
1. Polyester resins obtained by polycondensation with diols such as bisphenol A propylene oxide adducts and bisphenol A ethylene oxide adducts may also be used. In this case, a trifunctional compound such as trimellitic acid, glycerin, or trimethylolpropane may be further used to form a branched or crosslinked polyester.
勿論、前記ビニル系樹脂の場合もジビニルベンゼン等の
多官能単量体を用いて架橋ポリマーとして使用してよい
。Of course, the vinyl resin may also be used as a crosslinked polymer using a polyfunctional monomer such as divinylbenzene.
更Ｉこ又、ポリカーボネート、ポリアミド、エポキシ樹
脂、ポリウレタン、シリコーン系樹脂、フッ素系樹脂、
フェノール樹脂、テルペン樹脂、石油樹脂、水添石油樹
脂、アルキド樹脂、ケトン樹脂、セルロース誘導体等を
用いてもよい。Furthermore, polycarbonate, polyamide, epoxy resin, polyurethane, silicone resin, fluorine resin,
Phenol resins, terpene resins, petroleum resins, hydrogenated petroleum resins, alkyd resins, ketone resins, cellulose derivatives, etc. may be used.
これらの非晶質ポリマーもしくはオリゴマーを共重合体
の形で使用する場合、その共重合体はランダム共重合体
の外、要求用途に合わせて、交互共重合体、グラフト共
重合体、ブロック共重合体、相互貫入型共重合体等の共
重合様式を適宜選択して用いることが出来る。又、２種
以上のポリマー、オリゴマーを混合して用いる場合には
、溶融混合％溶液混合、エマルジョン混合等の機械的混
合の外、ポリマー、オリゴマー成分重合時に共存重合、
多段重合法等で混合してもよい。When these amorphous polymers or oligomers are used in the form of copolymers, the copolymers may be not only random copolymers, but also alternating copolymers, graft copolymers, and block copolymers depending on the required use. Copolymerization modes such as coalescence and interpenetrating copolymers can be appropriately selected and used. In addition, when using a mixture of two or more types of polymers or oligomers, in addition to mechanical mixing such as melt mixing% solution mixing or emulsion mixing, copolymerization during polymerization of the polymer or oligomer components,
They may be mixed by a multi-stage polymerization method or the like.
非晶質ポリマー、オリゴマーと共に結着材料成分として
添加される離型性物質は、示差走査熱量法（ＤＳＣ）で
測定した融点もしくは環球法で測定した軟化点が５０″
Ｃ以上、２００”０以下、より好ましくは６０υ以上、
１５０’Ｏ以下の常温で固体の有機物質、もしくは有機
／無機低分子量ポリマーであり、融点もしくは軟化点を
越えて急激に低粘性液体となる比較的表面エネルギーの
低い物質を指す。融点／軟化点が５０℃以下の場合ｔこ
は保存及び使用時の安定性に欠け、又融点が２００’０
以上の場合には、通常の感熱記録方式で印加される熱エ
ネルギーｆこ対してはほとんど添加効果がない。The releasing substance added as a binding material component along with the amorphous polymer and oligomer has a melting point measured by differential scanning calorimetry (DSC) or a softening point measured by the ring and ball method of 50''.
C or more, 200”0 or less, more preferably 60υ or more,
It refers to an organic substance or an organic/inorganic low molecular weight polymer that is solid at room temperature below 150'O, and has a relatively low surface energy that rapidly becomes a low viscosity liquid when it exceeds its melting point or softening point. If the melting point/softening point is below 50°C, it will lack stability during storage and use, and if the melting point is 200°C or lower, it will lack stability during storage and use.
In the above case, the addition has almost no effect compared to the thermal energy f applied in a normal thermosensitive recording method.
１００〜１８０℃程度の温度領域で、浴融粘度が約１０
ｐｏｉｓｅ以下に、より好ましくは約１ ｐｏｉｓｅ以
下に急激に低下する様な低粘性及び／もしくは臨界表面
張力が約４０ｄｙｎ／ｍ以下、より好ましくは約３０ｄ
ｙｎ／ｃｍ以下の低表面エネルギーを有する物質が離型
性物質として有効に作用する。In the temperature range of about 100 to 180℃, the bath melt viscosity is about 10
poise or less, more preferably about 1 poise or less, and/or the critical surface tension is about 40 dyn/m or less, more preferably about 30 dyn/m or less.
A substance having a low surface energy of yn/cm or less acts effectively as a releasing substance.
具体的ｆこは、例えばパルミチン酸、ステアリン酸等の
高級脂肪酸、ステアリン酸亜鉛の如き脂肪酸金属塩類、
脂肪酸エステル類もしくはその部分ケン化物、脂肪酸ア
ミド類等の脂肪酸誘導体、高級アルコール類、多価アル
コール類のエステル等誘導体、パラフィンワックス、カ
ルナバワックス、モンタンワックス、ミツロウ、木ロウ
、キャンデリラワックス等のワックス類、粘度平均分子
量が約１，０００から約１０，０００程度の低分子量ポ
リエチレン、ポリプロピレン、ポリブチレン等のポリオ
レフィン類、或いはオレフィン、α−オレフィン類と無
水マレイン酸、アクリル酸、メタクリル酸等の有機酸、
酢酸ビニル等との低分子量共重合体、低分子量酸化ポリ
オレフィン、ノ１０ゲン化ポリオレフィン類、ラウリル
メタクリレート、ステアリルメタクリレート等長鎖アル
キル側鎖を有するメタクリル酸エステル、アクリル酸エ
ステル又はパーフロロ基ヲ有するアクリル酸エステル、
メタクリル酸エステル類の単独もしくはスチレン類等の
ビニル系単鎗体との共重合体、ポリジメチルシロキサン
、ポリジフェニルシロキサン等の低分子ｉｆ シＩＪコ
ーンレジン及びシリコーン変性有機物質等、更には長鎖
脂肪族基を有するアンモニウム塩、ピリジニウム塩等の
カチオン性界面活性剤、或いは同様に長鎖脂肪族基を有
するアニオン、ノニオン界面活性剤、パーフロロ系界面
活性剤等、から１種以上選択して用いることが出来る。Specific examples include higher fatty acids such as palmitic acid and stearic acid, fatty acid metal salts such as zinc stearate,
Fatty acid esters or partially saponified products thereof, fatty acid derivatives such as fatty acid amides, derivatives such as esters of higher alcohols and polyhydric alcohols, waxes such as paraffin wax, carnauba wax, montan wax, beeswax, wood wax, candelilla wax, etc. polyolefins such as low molecular weight polyethylene, polypropylene, and polybutylene with a viscosity average molecular weight of about 1,000 to about 10,000, or olefins, α-olefins, and organic acids such as maleic anhydride, acrylic acid, and methacrylic acid. ,
Low molecular weight copolymers with vinyl acetate etc., low molecular weight oxidized polyolefins, 10-genated polyolefins, methacrylic acid esters having long alkyl side chains such as lauryl methacrylate, stearyl methacrylate, acrylic esters or acrylic acids having perfluoro groups ester,
Methacrylic acid esters alone or copolymers with vinyl monomers such as styrenes, low molecular weight resins such as polydimethylsiloxane, polydiphenylsiloxane, IJ cone resins, silicone-modified organic substances, and long-chain fats. Select and use one or more of cationic surfactants such as ammonium salts and pyridinium salts having group groups, or anionic surfactants, nonionic surfactants, and perfluorinated surfactants that similarly have long-chain aliphatic groups. I can do it.
これらの離型性物質は加熱時溶融し、感熱インク材料と
支持体界面ｌこおいて、その低凝集力及び／もしくは低
表面エネルギー効果に基いて主結着材料である非晶質ポ
リマー分子間及び／もしくは非晶質ポリマーと支持体界
面の過度の凝集力や接着力を低減するため、より低エネ
ルギーで印加が可能ｌこなり、記録感度、画質、特に解
像度等が向上する。These releasable substances melt when heated, and at the interface between the thermal ink material and the support, due to their low cohesive force and/or low surface energy effect, they form bonds between the amorphous polymer molecules that are the main binding material. And/or because the excessive cohesive force or adhesive force at the interface between the amorphous polymer and the support is reduced, it is possible to apply energy with lower energy, thereby improving recording sensitivity, image quality, and especially resolution.
離型性物質の多（は結晶性材料であるため過度ｌこ添加
すると結晶により光散乱が生じ透明性が悪化して特ｔこ
カラー再現性を劣化させるので必要以上Ｅこ添加すべき
ではない。Since the mold releasing substance is a crystalline material, if excessively added, the crystals cause light scattering, deteriorating transparency and especially color reproducibility, so it should not be added more than necessary. .
又、低粘性及び／もしくは低表面エネルギーであるため
、紙等の被記録体に対するインクの定着性悪化を招いた
り、画像が広がって解像度が低下したりする。Furthermore, since the ink has low viscosity and/or low surface energy, it may cause deterioration in the fixability of the ink to a recording medium such as paper, or the image may spread and the resolution may be reduced.
逆ｔこ添加量が少ないと有効ｌこその機能を発揮−１６
＝
しえない。従って、感熱インク結清材料中の非晶質ポリ
マーと離型性物質の重量比は約７０＝３０乃至約９９＝
１、特に好ましくは約８０：２０乃至約９５：５の範囲
で用いる時、本発明の感熱インク材料は最も有効ｌこ特
ｔこカラー再現性を劣化させることな（その目的を達成
しつる。勿論、非晶質ポリマーの量を結着材料中７０重
量係以下に落としても、感熱インクとしては実用化しつ
るが前述の如（画質が劣化する傾向が犬となる。When the amount of inverse T added is small, it exhibits its effective function-16
= I can't do it. Therefore, the weight ratio of the amorphous polymer and the release material in the thermal ink clearing material is about 70=30 to about 99=
1, particularly preferably in the range of about 80:20 to about 95:5, the thermal ink materials of the present invention are most effective without degrading color reproducibility. Of course, even if the amount of amorphous polymer in the binder material is reduced to less than 70% by weight, it may be put to practical use as a thermal ink, but as mentioned above, the image quality tends to deteriorate.
なお、離型性物質と非晶質ポリマー等地のインク材料と
は、混合時に化学結合を生じてもよい。特ｌこ離型性物
質の分散を改善するためには非晶質ポリマー中の活性基
と離型性物質の活性基の反応、相互作用を利用して、分
散の安定化をはかることができる。又、離型性物質存在
下で非晶質ポリマー単量体を重合、縮合重合することで
非晶質ポリマーと離型性物質をグラフト化したり、均一
分散させることも有効である。Note that the releasing substance and the ink material, such as an amorphous polymer, may form a chemical bond when mixed. In order to improve the dispersion of the release material, it is possible to stabilize the dispersion by utilizing the reaction and interaction between the active groups in the amorphous polymer and the active groups of the release material. . It is also effective to graft or uniformly disperse the amorphous polymer and the release material by polymerizing or condensation polymerizing the amorphous polymer monomer in the presence of the release material.
本発明の感熱記録材料では、この外史Ｉこ、帯電制御及
び／又は防止剤、導電化剤、酸化防止剤、熱伝導率向上
剤、磁性体、強誘電体、防腐剤、香料、プロツキンダ防
止剤、補強充填剤、離型剤、発泡剤、昇華性物質、赤外
線吸収剤等を感熱インク材の内部もしくは外部（こ添加
して用いてもよい。In the heat-sensitive recording material of the present invention, these materials include a charge control and/or preventive agent, a conductive agent, an antioxidant, a thermal conductivity improver, a magnetic material, a ferroelectric material, a preservative, a fragrance, and a protskinder inhibitor. , a reinforcing filler, a mold release agent, a foaming agent, a sublimable substance, an infrared absorber, etc. may be added inside or outside the heat-sensitive ink material.
但し前述のように、全感熱インク材料の非揮発性成分中
、前記非晶質ポリマー成分が型針濃度で５０％以上、特
ｌこ好ましくは７０％以上占めることが必要である。However, as mentioned above, it is necessary that the amorphous polymer component accounts for 50% or more, particularly preferably 70% or more, of the non-volatile components of the total heat-sensitive ink material in terms of mold needle concentration.
着色剤としては、カーボンブラック、オイルブラック、
黒鉛等の黒色系染顔料：Ｃ，１，ＰｉμｎｔＹｅ１１ｏ
ｗｌ、同３、同７４、同９７、同９８等のアセト酢酸ア
リールアミド系モノアゾ黄顔料（ファストエロー系）
”、 Ｃ，Ｉ、Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１２、同
１３、同１４等のアセト酢酸アリールアミド系ジスアゾ
黄顔料； Ｃ，１，５ｏｌｖｅｎｔ Ｙｅｌｌｏｗ １
９、同７７、同７９、Ｃ，１，Ｄｉｓｐｅｒｇｅ Ｙｅ
ｌｌｏｗ １６４等の黄染料；Ｃ，１，Ｐｉｇｍｅｎｔ
Ｒｅｄ ４８、同４９：１、同５３：１、同５７：１
、同８１、同１２２、同５等の赤もしくは紅顔料：Ｃ，
１，５ｏｌｖｅｎｔ Ｒｅｄ ５２、同５８、同８等の
赤系染料；Ｃ，１，Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：
３等銅フタロシアニン及びその誘導体、変性体等のＷ系
染顔料など、又有色もしくは無色の昇華性染料等従来、
印刷インクその他の着色用途で周知の染顔料が使用でき
る。Colorants include carbon black, oil black,
Black dye and pigment such as graphite: C, 1, PiμntYe11o
Acetoacetate arylamide monoazo yellow pigments (fast yellow type) such as wl, 3, 74, 97, 98, etc.
", C,I, Pigment Yellow 12, 13, 14 and other acetoacetate arylamide disazo yellow pigments; C, 1,5olvent Yellow 1
9, 77, 79, C, 1, Disperge Ye
Yellow dye such as low 164; C, 1, Pigment
Red 48, 49:1, 53:1, 57:1
, 81, 122, 5 grade red or red pigments: C,
Red dyes such as 1,5olvent Red 52, 58, and 8; C,1, Pigment Blue 15:
W-based dyes and pigments such as tertiary copper phthalocyanine and its derivatives and modified products, as well as colored or colorless sublimable dyes, etc.
Well-known dyes and pigments can be used for printing inks and other coloring applications.
これら染顔料は単独でも２４以上混合して用いてもよい
。勿論、体質顔料や白色顔料と混合し、色調を調整して
もよい。更に又、結着材成分に対する分散性を改善する
ため、着色剤表面を界面活性剤、シランカップリング剤
等のカップリング剤、高分子材料で処理したり、高分子
染料や高分子ダラフト顔料を用いてもよい。These dyes and pigments may be used alone or in combination of 24 or more. Of course, the color tone may be adjusted by mixing with an extender pigment or a white pigment. Furthermore, in order to improve the dispersibility of the binder component, the surface of the colorant may be treated with a surfactant, a coupling agent such as a silane coupling agent, or a polymeric material, or a polymeric dye or a polymeric duraft pigment may be added to the surface of the colorant. May be used.
本発明の感熱転写記録側材は、非晶質ポリマーもしくは
オリゴマーと離型性物質、着色剤、更に必要に応して前
述の各種添加剤を混合した感熱インク材料を支持体上に
設置することで形成される。The heat-sensitive transfer recording side material of the present invention includes a heat-sensitive ink material mixed with an amorphous polymer or oligomer, a releasing substance, a colorant, and, if necessary, the various additives mentioned above, on a support. is formed.
感熱インク材料の混合は、結着材料を溶解及び／もしく
は安定に分散しうる浴媒および／もしくは分散媒中で浴
液及び／もしくは分散エマルションとし、ボールミル、
サンドミル、アトライター、３本ロール等の混合分散機
で調製することができる。The heat-sensitive ink materials are mixed into a bath liquid and/or a dispersion emulsion in a bath medium and/or dispersion medium that can dissolve and/or stably disperse the binder material, and then mixed with a ball mill,
It can be prepared using a mixing and dispersing machine such as a sand mill, attritor, or three-roll mill.
父、浴媒等を特ζこ用いることな（、加熱型３本ロール
、加熱加圧ニーダ−、バンバリーミキサ−等で浴融混合
してもよい。The mixture may be melt-mixed using a heated three-roll roller, heated pressure kneader, Banbury mixer, etc., without using a specific bath medium or the like.
更に父、着色剤、添加剤、離型性物質等存在下で主結着
材料である非晶質ポリマー、オリゴマーを重合により調
製し感熱インク材料としてもよい。Furthermore, a heat-sensitive ink material may be prepared by polymerizing an amorphous polymer or oligomer, which is the main binding material, in the presence of a parent material, a colorant, an additive, a releasing substance, etc.
この様ｌこして調製された感熱インク材料は支持体上ｌ
こグラビアコーター、ワイヤーバー 等’）用いて浴液
及び／もしくは浴融コート法で塗布、印刷される。The heat-sensitive ink material prepared in this manner can be applied onto a support.
It is coated and printed using a bath liquid and/or bath melt coating method using a gravure coater, wire bar, etc.
又、感熱インク材料をスプレィドライ法、粉砕法等で粉
体化し、その後静電コート法等ｌこよって支持体上に粉
体コートしてもよい。この場合、粉体コート後、更に必
要に応じて加熱、加圧、浴媒処理等を行い、感熱粉体イ
ンクを支持−２０＝
体上に定着して用いてもよい。更に又、この様な感熱粉
体インクを調製する場合（こは着色剤、添加剤、離型性
物質等の存在下で主結着材料である非晶質ポリマーを懸
濁重合法、分散重合法等、直接重合法で重合し、粉体イ
ンクを調製してもよい。Alternatively, the thermal ink material may be pulverized by a spray drying method, a pulverization method, etc., and then powder coated onto a support by an electrostatic coating method or the like. In this case, after powder coating, heating, pressurization, bath medium treatment, etc. may be further performed as necessary, and the heat-sensitive powder ink may be fixed on the support and used. Furthermore, when preparing such a heat-sensitive powder ink (in this case, an amorphous polymer, which is the main binder material, is processed by suspension polymerization or dispersion polymerization in the presence of colorants, additives, release substances, etc.). A powder ink may be prepared by polymerizing by a direct polymerization method such as a legal method.
支持体としては、ポリエチレンテレフタレート等のポリ
エステル、ポリイミド及びイミド系共重合体、フッ素系
ポリマー、ポリプロピレン等のプラスチックスフィルム
、コンデンサ祇等の薄層シート、フィルム類が都合よく
用いられる。これらのシート、フィルム、或いはロール
類はその内部ｌこ熱伝導性、熱安定性等を改善するため
の熱特性改質材や離型剤、帯電防止剤、導電剤、補強剤
を添加して用いても良い。父、熱ヘッド等を用いて記録
を行う場合には支持体の熱ヘッドと接する側ζこ、耐熱
性、走行性等を改善するため、シリコーン系、フッ素系
の化合物、樹脂層や架橋ポリマ一層、金属層、セラミッ
クス層等を設けてもよい。As the support, polyesters such as polyethylene terephthalate, polyimides and imide copolymers, fluorine polymers, plastic films such as polypropylene, thin sheets and films such as capacitors are conveniently used. These sheets, films, or rolls have thermal property modifiers, mold release agents, antistatic agents, conductive agents, and reinforcing agents added to their interior to improve thermal conductivity, thermal stability, etc. May be used. When recording is performed using a thermal head, etc., silicone-based, fluorine-based compounds, resin layers, or cross-linked polymer layers are added to improve heat resistance, runnability, etc. on the side of the support that comes into contact with the thermal head. , a metal layer, a ceramic layer, etc. may be provided.
更ｊこ、前記フィルム内添剤を外層ｌこ添加してもよい
。これら支持体表面は、平滑であっても或いはまた凹凸
部、溝等を設けてもよく、又、多孔質性であってもよい
。又、支持体として熱ヘッドと類似の構造を有する電熱
変換素子や光熱変換素子を直接用い、その上ｔこ感熱イ
ンク層を設けてもよい。Furthermore, the above-mentioned film internal additives may be added to the outer layer. The surface of these supports may be smooth, or may have irregularities, grooves, etc., or may be porous. Alternatively, an electrothermal conversion element or a photothermal conversion element having a structure similar to that of a thermal head may be directly used as the support, and a heat-sensitive ink layer may be provided thereon.
支持体フィルム、シートの厚さ、感熱インク層の厚さは
用途に応じて適宜選択すれば良いが、一般（こ支持体厚
みは約１μｍから約２００μｍ程度のものが使用しやす
い。解像性をあげるには約１μｍから約１０μｍ程度が
好まれる。感熱インク層は０．５μｍ程度から、これも
用途により５０μｍ程度まで、通常は約１μｍから約２
０μｍ程度の範囲で設定すると使用しやすい。感熱イン
ク層と支持体間ｌこは接着性を制御する中間層を配Ｉｆ
Ｌ、たり、感熱インク層自体を物性の異なる複数種の
感熱インク材料の多層コート層としたり、平面内に物性
の異なる複数種のインク材を分割コートしてもよい。The thickness of the support film and sheet and the thickness of the heat-sensitive ink layer may be selected appropriately depending on the application, but in general (the thickness of the support is about 1 μm to about 200 μm is easy to use. The thickness of the heat-sensitive ink layer is preferably from about 1 μm to about 10 μm to increase the thickness.
It is easy to use if it is set in the range of about 0 μm. An intermediate layer is provided between the heat-sensitive ink layer and the support to control adhesion.
Alternatively, the thermal ink layer itself may be a multilayer coating layer of multiple types of thermal ink materials having different physical properties, or multiple types of ink materials having different physical properties may be dividedly coated within a plane.
この様にして形成された感熱記録材料は熱ヘッド、レー
ザー、フラッシュ光或いは電気信号を直接通電する等の
手段により印加信号に対応して加熱され、紙、フィルム
等の被記録体に対して接触状態で、或いは非接触状態で
飛翔させることにより、感熱インク材料が転写記録され
る。記録性を向上させるためには加圧、発泡等の機械力
の外、電場、磁場、超音波、浴剤等を併用する事も可能
である。The heat-sensitive recording material formed in this way is heated in accordance with the applied signal by means such as a thermal head, laser, flash light, or direct electrical signal, and is brought into contact with a recording medium such as paper or film. The heat-sensitive ink material is transferred and recorded by being ejected in a non-contact state or in a non-contact state. In order to improve recording properties, it is also possible to use electric fields, magnetic fields, ultrasonic waves, bath agents, etc. in addition to mechanical forces such as pressurization and foaming.
〔実施例］
以下、本発明を実施例により説明するが、勿論本発明は
これら例により限定されるものではない。なお、以下の
例中、部は特に指定のない限り重量部を表わす。[Examples] Hereinafter, the present invention will be explained with reference to Examples, but of course the present invention is not limited to these Examples. In addition, in the following examples, parts represent parts by weight unless otherwise specified.
実施例１
下記組成ｌこより７種類の感熱インク材料をボールミル
中で４０時間混練して作成した。Example 1 Seven kinds of heat-sensitive ink materials having the following composition were kneaded in a ball mill for 40 hours.
これにより得られた感熱インク材料（インクＡ１〜７）
を厚さ６μｍのポリエステルフィルム上に、ワイヤーバ
ーコーティング５こより塗布した後、乾燥し、感熱イン
クの厚さが３μｍの感熱記録材料を作成した。これらの
感熱記録材料の代表的な記録特性を富士ゼロックス（株
）製ＦＸＰ−６感熱転写プリンターにより評価した結果
を下表に示す。Thermal ink materials obtained thereby (inks A1 to 7)
Five wire bar coatings were applied onto a polyester film having a thickness of 6 μm and dried to prepare a heat-sensitive recording material having a heat-sensitive ink thickness of 3 μm. Typical recording properties of these heat-sensitive recording materials were evaluated using an FXP-6 heat-sensitive transfer printer manufactured by Fuji Xerox Co., Ltd. The results are shown in the table below.
表１こ示した通りワックスを結着剤さした従来型（イン
クＡＩ）では、記録感度において優れるが画数の多い漢
字等では文字のつぶれを生じ、又、転写像を指で強（こ
すると転写像の周囲にこすり取られたインクによる汚れ
を生じた。一方弁晶質ポリマーのみを結着剤とし離型性
物質を含有しない場合（Ａ２）記録感度ζこおいてワッ
クス型（ＡＩ ）の約１．６倍のサーマルヘッド印加エ
ネルギーを要し、比較的低感度であった。As shown in Table 1, the conventional type (Ink AI) that uses wax as a binder has excellent recording sensitivity, but when it comes to characters with a large number of strokes, such as kanji characters, the characters become blurred. On the other hand, when the crystalline polymer alone is used as a binder and no release material is contained (A2), the recording sensitivity ζ is approximately equal to that of the wax type (AI). It required 1.6 times more energy to be applied to the thermal head, and the sensitivity was relatively low.
本発明ζこよる感熱記録材料（扁３〜７）は記録感度で
ワックス型（Ａ１）とほぼ同等であり、更には、つぶれ
のない鮮明な印字が得られ、転写像をこすってもインク
の剥離はな（１優れた記録特性を示した。又、離型性物
質の含有率を単Ｅこ増加しても記録感度改善の効果が少
ないにも力）かわらず、解像性、定着Ｉｆを悪化させる
傾向が見受けられ（Ａ５，６）、最適範囲を有すること
が確認された。The heat-sensitive recording material (Flats 3 to 7) according to the present invention has a recording sensitivity that is almost equivalent to that of the wax type (A1), and furthermore, clear prints without crushing can be obtained, and even if the transferred image is rubbed, the ink can be removed. Although the release rate was low (1.Excellent recording characteristics were exhibited.Also, even if the content of the releasing substance was increased, the effect of improving the recording sensitivity was small), but the resolution and fixing If (A5, 6), and it was confirmed that there was an optimal range.
実施例２
下記組成により感熱インク材料をボールミル中で４０時
間混練して作成し、これを厚さ６μｍｎのポリエステル
フィルム上に塗布し、乾燥後の感熱インク層厚が２．５
μｍの感熱記録材料を作成した。Example 2 A thermal ink material with the following composition was kneaded in a ball mill for 40 hours, and this was applied onto a polyester film with a thickness of 6 μm, so that the thermal ink layer thickness after drying was 2.5 μm.
A micrometer thermosensitive recording material was prepared.
実施例１と同様富士ゼロックス（ｌｆｆｉ） ＨＦＸ
Ｐ−６感熱転写プリンターで印字を行ったところワック
ス型インクの約１．１倍のサーマルヘッド印加エネルギ
ーで、つぶれかな（、輪廓が明瞭でこすれ等で汚れを生
じない強固な印字が得られた。Same as Example 1 Fuji Xerox (lffi) HFX
When printing with a P-6 thermal transfer printer, the energy applied to the thermal head was about 1.1 times that of wax-type ink, and strong printing with clear edges and no stains due to rubbing was obtained. .
又、ＯＨＰ用ソートに転写したものは良好な透明性を有
し、これをスクリーンに投映したところ濁りのない鮮や
力）な青色の投映ｆ象が得られたＯ
実施例３
下記組成の感熱インク材料を実施例１と同様にして作成
し、厚さ６μｍのポリエステルフィルム上憂こ塗布し、
乾燥後の感熱インク層厚が３μｍの感熱記録材料を作成
した。In addition, the image transferred to the OHP sort had good transparency, and when it was projected onto a screen, a bright blue image with no turbidity was obtained. An ink material was prepared in the same manner as in Example 1, and applied onto a 6 μm thick polyester film.
A heat-sensitive recording material having a heat-sensitive ink layer thickness of 3 μm after drying was prepared.
＝２７−
この感熱記録材料を実施例１と同様ｉこ富士ゼロックス
（味）ｌ！ｉ！ｐｘｐ−６感熱転写プリンターで印字を
行なったところワックス型インクの約１．１倍のサーマ
ルヘッド印加エネルギーで、鮮明で十分な定着強度を有
する印字が得られた。=27- This heat-sensitive recording material was used in the same manner as in Example 1. i! When printing was performed using a PXP-6 thermal transfer printer, clear prints with sufficient fixing strength were obtained with approximately 1.1 times the energy applied to the thermal head compared to wax-type ink.
実施例４
下記組成を有する感熱インク材料をアトライターにて混
合分散を行って作成した。Example 4 A thermal ink material having the following composition was mixed and dispersed using an attritor.
上記で得た感熱インク材料を乾燥後の塗布重量が３．５
ｆ ／ｎ？となる様ｌこ厚さ６μｍのポリエステルフ
ィルム上ｌこグラビアコーティングｌこより塗布し、感
熱記録材料とした。The coating weight of the thermal ink material obtained above after drying is 3.5
f/n? A gravure coating was applied onto a polyester film having a thickness of 6 μm to obtain a heat-sensitive recording material.
これを実施例１と同様富士ゼロックス（（転）製ＦＸ
Ｐ−６°感熱転写プリンターで印字を行なったところ、
極めてシャープで解像性の高い、強固な印字が得られた
。As in Example 1, use the Fuji Xerox FX
When printed with a P-6° thermal transfer printer,
Extremely sharp, high resolution, and strong printing was obtained.
実施例５
実施例４と同様ζこして、下記組成を有する感熱インク
材料を調製し、感熱記録材料を作成し、評価した。Example 5 A heat-sensitive ink material having the following composition was prepared in the same manner as in Example 4, and a heat-sensitive recording material was prepared and evaluated.
これにより実施例４同様、極めてシャープで解像性の高
い、強固な印字を得た。As a result, as in Example 4, extremely sharp, high-resolution, and strong printing was obtained.
本発明の感熱記録材料は転写材上における、＊ｉこカラ
ー画像の再現性、記録感度、転写性、定着性、解像性に
おいて優れている。The heat-sensitive recording material of the present invention is excellent in the reproducibility, recording sensitivity, transferability, fixing performance, and resolution of color images on the transfer material.
本発明に用いられる非晶質ポリマーは従来感熱記録材料
に用いられていた結着剤である結晶性のワックスとは異
なり、結着剤として非晶質ポリマーを用いること（こよ
って結晶性ワックスを用いた場合に生じていた光散乱が
全くなくなる力）、もしくは実質的に問題のない程度ζ
こ制御できるので本発明の感熱記録材料の結着層ｌこ極
めて良好な透明性を示す。The amorphous polymer used in the present invention is different from the crystalline wax that is a binder conventionally used in heat-sensitive recording materials. power that completely eliminates light scattering that would occur when used), or to the extent that there is virtually no problem
Since this can be controlled, the binding layer of the heat-sensitive recording material of the present invention exhibits extremely good transparency.
特ｆこ、インク材料を数回（こわたり重ね記録して鮮明
なカラー画像、特にビクトリアルフルカラー再現像を得
る目的で、例えばマゼンタ、イエロー、シアン色のイン
ク材料を重ね合わせて、２次色あるいは３次色を得る場
合（こは、本発明の感熱インク材料を少な（とも上層部
のインク材料として重ねると、その透明性が良好である
ためＣと、下層部のインク層力）らの反射光も顔料自体
の特性による反射光に近いものとなり、目的とする２次
色あるいは３次色との色差のないカラーを得ることがで
きる。In particular, in order to obtain a clear color image, especially a Victorian full-color reproduction image by overlapping the ink materials several times, for example, magenta, yellow, and cyan ink materials are overlaid to record secondary colors. Alternatively, when obtaining a tertiary color (in this case, a small amount of the thermal ink material of the present invention (both C and the strength of the ink layer in the lower layer), since its transparency is good when layered as an ink material in the upper layer). The reflected light is also close to the reflected light due to the characteristics of the pigment itself, and it is possible to obtain a color with no color difference from the desired secondary or tertiary color.
また従来ワックス系のものｌこ代えて高分子材料を結着
剤として用いることは記録感度的ζこは不利と考えられ
ているが、本発明では特定の非晶質ポリマーを用いるこ
とｌこよってワックス系の結着剤を用いる場合と同等の
記録感度を得ることができ、また高分子材料の特性、す
なわちゆるや力）な浴融特性を生かすことｌこよってイ
ンク材料ｔこおける印加エネルギーの熱拡散をな（し優
れた解像力を得ることができる。更に結着剤としてポリ
マーを用いるためζこ町とう性があり摩擦等に対して耐
久性を有し、従来のワックス系感熱記録材料の欠点であ
った定着性の悪さをも改善することができる。Furthermore, using a polymeric material as a binder instead of a conventional wax-based binder is considered to be disadvantageous in terms of recording sensitivity, but in the present invention, it is possible to use a specific amorphous polymer. It is possible to obtain the same recording sensitivity as when using a wax-based binder, and also to take advantage of the properties of the polymer material, that is, the gentle bath melting properties, which reduces the amount of energy applied to the ink material. Excellent resolving power can be obtained through heat diffusion.Furthermore, since polymer is used as a binder, it has high elasticity and is resistant to friction, etc., and is superior to conventional wax-based thermosensitive recording materials. It is also possible to improve the poor fixability, which was a drawback.
Claims (1)
材料において、前記感熱インク材料が非晶質ポリマーと
離型性物質と着色剤を主成分とし、前記非晶質ポリマー
が感熱インク材料の非揮発成分中に少なくとも５０重量
％含まれていることを特徴とする感熱記録材料。 ２、非晶質ポリマーと離型性物質との重量比が７０：３
０〜９９：１である特許請求の範囲第１項に記載の感熱
記録材料。[Scope of Claims] 1. A recording material in which a heat-melting heat-sensitive ink material layer is provided on a support, wherein the heat-sensitive ink material contains an amorphous polymer, a releasing substance, and a colorant as main components, and 1. A heat-sensitive recording material, characterized in that the non-volatile component of the heat-sensitive ink material contains at least 50% by weight of a crystalline polymer. 2. Weight ratio of amorphous polymer and mold release material is 70:3
The heat-sensitive recording material according to claim 1, wherein the ratio is 0 to 99:1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60086539A JPS61244592A (en) | 1985-04-24 | 1985-04-24 | Thermal recording material |
| DE3613846A DE3613846C2 (en) | 1985-04-24 | 1986-04-24 | Heat-sensitive recording material and its use |
| GB8609991A GB2176903B (en) | 1985-04-24 | 1986-04-24 | Image recording material for heat sensitive hot-melt transfer recording. |
| US07/657,272 US5071502A (en) | 1985-04-24 | 1991-02-19 | Heat-sensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60086539A JPS61244592A (en) | 1985-04-24 | 1985-04-24 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61244592A true JPS61244592A (en) | 1986-10-30 |
| JPH0513072B2 JPH0513072B2 (en) | 1993-02-19 |
Family
ID=13889801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60086539A Granted JPS61244592A (en) | 1985-04-24 | 1985-04-24 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61244592A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162287A (en) * | 1986-12-26 | 1988-07-05 | Kao Corp | Thermal transfer recording medium |
| JPH01123789A (en) * | 1987-11-09 | 1989-05-16 | Fuji Xerox Co Ltd | Thermal recording material |
| JPH01123790A (en) * | 1987-11-09 | 1989-05-16 | Fuji Xerox Co Ltd | Thermal recording material |
| JPH02277690A (en) * | 1989-04-20 | 1990-11-14 | Ricoh Co Ltd | Thermal transfer recording medium |
| JPH03266681A (en) * | 1990-03-15 | 1991-11-27 | Oike Ind Co Ltd | Thermal transfer ribbon and decoration of character pattern formed by use of same |
| JPH09104175A (en) * | 1995-10-11 | 1997-04-22 | Fujicopian Co Ltd | Heat transfer recording material |
| EP1088678A1 (en) | 1999-09-30 | 2001-04-04 | Toppan Printing Co., Ltd. | Thermal transfer recording medium and image forming method |
| EP1088675A3 (en) * | 1999-09-30 | 2001-04-25 | Toppan Printing Co., Ltd. | Thermal transfer recording medium, image-forming method and image-bearing body |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57105395A (en) * | 1980-12-22 | 1982-06-30 | Fuji Kagakushi Kogyo Co Ltd | Thermal transfer recording medium |
| JPS58201693A (en) * | 1982-05-20 | 1983-11-24 | Ricoh Co Ltd | Heat sensitive transfer type recording material |
| JPS6040295A (en) * | 1984-03-30 | 1985-03-02 | Nippon Telegr & Teleph Corp <Ntt> | Repeatedly usable thermal transfer material |
-
1985
- 1985-04-24 JP JP60086539A patent/JPS61244592A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57105395A (en) * | 1980-12-22 | 1982-06-30 | Fuji Kagakushi Kogyo Co Ltd | Thermal transfer recording medium |
| JPS58201693A (en) * | 1982-05-20 | 1983-11-24 | Ricoh Co Ltd | Heat sensitive transfer type recording material |
| JPS6040295A (en) * | 1984-03-30 | 1985-03-02 | Nippon Telegr & Teleph Corp <Ntt> | Repeatedly usable thermal transfer material |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162287A (en) * | 1986-12-26 | 1988-07-05 | Kao Corp | Thermal transfer recording medium |
| JPH01123789A (en) * | 1987-11-09 | 1989-05-16 | Fuji Xerox Co Ltd | Thermal recording material |
| JPH01123790A (en) * | 1987-11-09 | 1989-05-16 | Fuji Xerox Co Ltd | Thermal recording material |
| JPH02277690A (en) * | 1989-04-20 | 1990-11-14 | Ricoh Co Ltd | Thermal transfer recording medium |
| JPH03266681A (en) * | 1990-03-15 | 1991-11-27 | Oike Ind Co Ltd | Thermal transfer ribbon and decoration of character pattern formed by use of same |
| JPH09104175A (en) * | 1995-10-11 | 1997-04-22 | Fujicopian Co Ltd | Heat transfer recording material |
| EP1088678A1 (en) | 1999-09-30 | 2001-04-04 | Toppan Printing Co., Ltd. | Thermal transfer recording medium and image forming method |
| EP1088675A3 (en) * | 1999-09-30 | 2001-04-25 | Toppan Printing Co., Ltd. | Thermal transfer recording medium, image-forming method and image-bearing body |
| US6468379B1 (en) | 1999-09-30 | 2002-10-22 | Toppan Printing Co., Ltd. | Thermal transfer recording medium and image forming method |
| US6709542B1 (en) | 1999-09-30 | 2004-03-23 | Toppan Printing Co., Ltd. | Thermal transfer recording medium, image-forming method and image-bearing body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0513072B2 (en) | 1993-02-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |