JPS63139335A - Recording medium - Google Patents
Recording mediumInfo
- Publication number
- JPS63139335A JPS63139335A JP61285863A JP28586386A JPS63139335A JP S63139335 A JPS63139335 A JP S63139335A JP 61285863 A JP61285863 A JP 61285863A JP 28586386 A JP28586386 A JP 28586386A JP S63139335 A JPS63139335 A JP S63139335A
- Authority
- JP
- Japan
- Prior art keywords
- transfer
- recording medium
- image
- energy
- temperature
- 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
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- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
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- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、プリンターや、複写機、ファクシミリ等の記
録装置に用いられる新規な記録媒体に関するものである
。特に、ワンショットカラー記録に適した記録方式に用
いられる記録媒体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel recording medium used in recording devices such as printers, copying machines, and facsimiles. In particular, the present invention relates to a recording medium used in a recording method suitable for one-shot color recording.
近年、情報産業の急速な発展に伴ない、種々の情報処理
システムが開発され、また、それぞれの情報処理システ
ムに通した記録方法および装置も開発、採用されている
。このような記録方法の１つとして、感熱転写ｇ己録方
法は、使用する装置が軽量かつコンパクトで騒音がなく
、操作性、保守性にも優れており、最近広く使用されて
いる。この方法によれば、普通紙を被転写媒体として使
用可能である。In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices for each information processing system have also been developed and adopted. As one such recording method, the thermal transfer recording method has recently been widely used because the apparatus used is lightweight, compact, noiseless, and has excellent operability and maintainability. According to this method, plain paper can be used as the transfer medium.
しかしながら、従来の感熱転写記録方法にも欠点がない
訳ではない。それは、従来の感熱転写記録方法は転写記
録性能、すなわち印字品質が表面平滑度により大きく影
響され、平滑性の高い被転写媒体には良好な印字が行な
われるが、平滑性の低い被転写媒体の場合には著しく印
字品質が低下することである。しかし、最も典型的な被
転写媒体である紙を使用する場合にも、平滑性の高い紙
はむしろ特殊であり、通常の紙はｗＡｌａの絡み合いに
より種々な程度の凹凸を存する。したがって、従来の感
熱転写記録方法によれば、印字された像のエツジ部がシ
ャープでなかったり、像の一部が欠けたりして、印字品
質を低下させることになる。However, conventional thermal transfer recording methods are not without drawbacks. This is because in the conventional thermal transfer recording method, the transfer recording performance, that is, the print quality, is greatly affected by the surface smoothness.Good printing is performed on highly smooth transfer media, but on less smooth transfer media. In some cases, the print quality deteriorates significantly. However, even when using paper, which is the most typical transfer medium, highly smooth paper is rather special, and ordinary paper has various degrees of unevenness due to entanglement of wAla. Therefore, according to the conventional thermal transfer recording method, the edges of the printed image may not be sharp or a portion of the image may be missing, resulting in a reduction in print quality.
また、従来の感熱転写記録方法ではインク層の被転写媒
体への転写は、熱ヘッドからの熱のみによって行われる
が、限られた短い時間内に熱ヘッドを所定温度まで冷却
しなければならないこと、また、熱ヘツド面を構成して
いる発熱セグメント間の熱的クロストークを防止しなけ
ればならないこと等のために、論理的にも熱ヘッドから
の供給熱量を大きくすることは困難である。そのため、
従来の感熱転写記録方法では高速記録は難しかったもの
である。In addition, in conventional thermal transfer recording methods, the ink layer is transferred to the transfer medium using only heat from the thermal head, but the thermal head must be cooled to a predetermined temperature within a limited short time. Furthermore, it is logically difficult to increase the amount of heat supplied from the thermal head because of the need to prevent thermal crosstalk between the heat generating segments that make up the thermal head surface. Therefore,
High-speed recording is difficult with conventional thermal transfer recording methods.
また、熱伝導は電気や光などに較べて応答レスポンスが
遅いため、従来の熱ヘッドによる記録において、中間調
の再現が可能にまで熱パルスを制御することは一般に困
難であり、また、従来の感熱転写インク層は、階調性の
ある転写機能を備えていないため、中間調君己録はでき
なかったものである。In addition, because thermal conduction has a slower response than electricity or light, it is generally difficult to control heat pulses to the extent that halftones can be reproduced when recording with conventional thermal heads. Since the heat-sensitive transfer ink layer does not have a gradation transfer function, half-tone recording was not possible.
また、従来の感熱転写記録方法では、１回の転写で１色
の画像しか得ることができないため、多色の画像を得る
には、複数回の転写を繰り返えして色を重ね合わせるこ
とが必要であった。しかし、色の異なる画像を正確に重
ね合わせることは非常に困難であり、色ずれのない画像
を得ることは難しかった。特に、１つの画素に注目した
場合、１つの画素では色の重ね合わせは、はとんどなさ
れておらず、結局従来の感熱転写記録方法では色のずれ
た画素の集合体により多色の画像を形成していた。この
ため、従来の感熱転写記録方法では鮮明な多色画像は得
られなかった。In addition, with conventional thermal transfer recording methods, only one color image can be obtained with one transfer, so to obtain a multicolor image, the colors must be overlapped by repeating the transfer multiple times. was necessary. However, it is very difficult to accurately superimpose images of different colors, and it is difficult to obtain images without color shift. In particular, when focusing on a single pixel, colors are rarely superimposed in a single pixel, and in the end, in conventional thermal transfer recording methods, multicolor images are created by aggregation of pixels with shifted colors. was forming. For this reason, clear multicolor images cannot be obtained using conventional thermal transfer recording methods.
また、従来の感熱転写記録方法で多色の画像を得ようと
した場合、複数のサーマルヘッドを設けたり、あるいは
被転写媒体に逆送、停止等複雑な動きをさせなければな
らず、装置全体が大きく複雑になったり、記録速度が低
下する等の欠点があった。In addition, when trying to obtain multicolor images using conventional thermal transfer recording methods, it is necessary to install multiple thermal heads or to make complicated movements such as reverse feeding and stopping of the transfer medium, which requires the entire device. This method has drawbacks such as large and complicated data and a decrease in recording speed.
また、発色剤と顕色剤とを用いて多色の可視像を形成す
るものとして米国特許４，３９９，２０９号明細書があ
る。米国特許４，３９９，２０９号明細書は感光性組成
物と発色剤とを含有したマイクロカプセルを基材上に配
列した記録媒体を用い、記録画像に応じて変換された主
に紫外光によりマイクロカプセル内の感光性組成物を硬
化させて転写像を形成し、更にこの転写像を顕色層を有
する被記録媒体に重ねて、一対の圧力ローラ間のニップ
に通過させてマイクロカプセルを破壊しかつ画像を顕色
する転写画像形成システムを開示している。画像は、発
色剤を画像形成シートに造像的に転写し、そこで発色剤
が反応して画像を形成することによって多色画像を得る
ものである。Further, US Pat. No. 4,399,209 discloses a system that uses a color forming agent and a color developer to form a multicolor visible image. U.S. Pat. No. 4,399,209 uses a recording medium in which microcapsules containing a photosensitive composition and a coloring agent are arranged on a substrate, and uses mainly ultraviolet light converted in accordance with a recorded image to The photosensitive composition inside the capsule is cured to form a transferred image, and this transferred image is further superimposed on a recording medium having a color developer layer, and the microcapsule is destroyed by passing it through a nip between a pair of pressure rollers. The present invention also discloses a transfer image forming system that develops an image. A multicolor image is obtained by image-formingly transferring a color former to an image forming sheet, where the color former reacts to form an image.
また、米国特許４，４１６，９６６号明細書は、顕色剤
が感光マイクロカプセルと同一の支持体表面上に存在す
るセルフコンテインド（ｓｅｌｆ−ｃｏｎｔａｉｎｅｄ
）画像形成システムを開示している。記録画像に応じて
変換された主に紫外光により、露光した後、画像形成シ
ートを圧力ロールに通過させるときに、マイクロカプセ
ルは破壊し、内相を造像的に放出する。その際、発色剤
は、通常別個の層内に設けられる顕色剤に移行し、そこ
で発色剤は反応しかつ色画像を形成する。Further, US Pat. No. 4,416,966 discloses a self-contained color developer in which the color developer is present on the same support surface as the photosensitive microcapsules.
) discloses an image forming system. After exposure, primarily by ultraviolet light converted in accordance with the recorded image, the microcapsules rupture and release the internal phase imagewise when the imaging sheet is passed through a pressure roll. The color former then migrates to a developer, usually provided in a separate layer, where it reacts and forms a color image.
上記２方式のうような記録方式はいずれもマイクロカプ
セル内に光開始剤を含有し、光開始剤の感光波長域を異
ならせしめ、それぞれの感光波長域に対応するように変
換された主に紫外光により、マイクロカプセル内の内容
物を硬化させるものである。しかしながらこれらの方式
の共通の問題点は、像形成に用いる手段が、いずれも主
に紫外光すなわち光エネルギーのみをマイクロカプセル
を配列した基材上に照射することで、記録媒体上転写転
写像を形成するために、鮮明な記録画像を高速で得るに
は、光に対して高感度の感光材料を用いるか、または、
高いエネルギーの光を照射する必要があった。Both of the above two recording methods contain a photoinitiator in a microcapsule, and the photoinitiator has different photosensitive wavelength ranges, and mainly ultraviolet light is converted to correspond to each photosensitive wavelength range. The contents inside the microcapsules are cured by light. However, the common problem with these methods is that the means used for image formation mainly irradiates only ultraviolet light, that is, optical energy, onto the substrate on which microcapsules are arranged, which makes it difficult to transfer the image onto the recording medium. To form a clear recorded image at high speed, a photosensitive material with high sensitivity to light is used, or
It was necessary to irradiate it with high-energy light.
しかしながら、光反応のみを利用した高感度の記録媒体
の場合、光来照射時の感度も高く、室温付近での保存安
定性が悪いという致命的な欠点があった。また、高エネ
ルギー光を得るには装置が大型化し、多色記録を得るた
めの装置としては大型化し、装置コストも大となり、実
用上望ましくない。また、上記方式は、光エネルギーの
みを用いて像形成するため、プリンターなどのように、
外部からの信号に応じて画像を出力する場合や、カラー
複写機のように、カラー原稿からの画像読み取りをカラ
ーイメージスキャナーでデジタル信号に変換後、画像情
報を記録媒体に付与する場合には、不適当である。すな
わち、高エネルギー光を照射する場合には短波長、主に
紫外光を用いる必要があり、紫外光のデジタル制御可能
な光源は、現在得られていない。例えば、デジタル光源
を得る方法としては、液晶シャッターアレイやＬＥＤア
レイなどの光ヘッドが考案されているが、これらは小型
化に適しているとしても、紫外領域の波長では液晶分子
の劣化が起り、紫外光は取り出せない。However, high-sensitivity recording media that utilize only photoreactions have the fatal drawback of high sensitivity when irradiated with light and poor storage stability near room temperature. Furthermore, in order to obtain high-energy light, the apparatus becomes large, and in order to obtain multicolor recording, the apparatus becomes large and the apparatus cost becomes large, which is not desirable in practice. In addition, since the above method uses only light energy to form an image, it
When outputting an image in response to an external signal, or when converting an image read from a color document into a digital signal using a color image scanner, such as in a color copying machine, and then adding image information to a recording medium, It's inappropriate. That is, when irradiating high-energy light, it is necessary to use short wavelength light, mainly ultraviolet light, and a digitally controllable light source for ultraviolet light is currently not available. For example, as a method for obtaining a digital light source, optical heads such as liquid crystal shutter arrays and LED arrays have been devised, but although these are suitable for miniaturization, liquid crystal molecules deteriorate at wavelengths in the ultraviolet region. UV light cannot be extracted.
さらに、顕色方法として、ロイコ染料の発色を利用して
いるために本質的に記録画像の安定性が劣るという欠点
も有している。Furthermore, since the color development method uses leuco dye, it has the drawback that the stability of recorded images is essentially poor.
さらに、露光後の加圧による現像を容易にせしめるため
に、マイクロカプセルの内包物は常温で液相を育する感
光組成物とする必要があり、保存安定性にとぼしく、さ
らに得られた画像も未反応物が破壊されるため存在モノ
マー臭があり、実用的に望ましくない特性を有する。Furthermore, in order to facilitate development by applying pressure after exposure, the contents of the microcapsules must be a photosensitive composition that grows a liquid phase at room temperature, resulting in poor storage stability and poor image quality. Due to the destruction of unreacted substances, there is an odor from the monomers present, which is a characteristic that is undesirable for practical purposes.
本発明は、上記従来の開運点を解決する画像形成方法、
即ち、高品位の転写像を形成でき、高速記録が可能で、
中間調記録が可能で、多色の転写画像を得る場合にも被
転写媒体に複雑な動きをさせることなく、鮮明な、色ず
れのない多色画像が得られる画像形成方法に有効に供し
うる記録媒体を提供することを主な目的とする。The present invention provides an image forming method that solves the above-mentioned conventional problems,
In other words, high-quality transfer images can be formed, high-speed recording is possible,
It is possible to record halftones, and it can be effectively applied to an image forming method that can obtain a clear multicolor image without color shift without making complicated movements on the transfer medium even when obtaining a multicolor transfer image. The main purpose is to provide recording media.
さらに、本発明の目的は、特別な顕色層を必要としない
表面平滑度の低い一般的に用いられる普通紙に鮮明な転
写画像を形成できる記録媒体を提供することにある。A further object of the present invention is to provide a recording medium that does not require a special color developing layer and can form a clear transferred image on commonly used plain paper with low surface smoothness.
さらに、本発明の目的は、特別な光エネルギーの高いデ
ジタル光源を必要とすることなく、低いパワーでデジタ
ル画像記録できる高感度な記録媒体を提供することにあ
る。A further object of the present invention is to provide a highly sensitive recording medium that can record digital images with low power without requiring a special digital light source with high optical energy.
ざらに、本発明の目的は、保存安定性が高くかつ高感度
な記録媒体を提供することにある。Broadly speaking, an object of the present invention is to provide a recording medium with high storage stability and high sensitivity.
さらに、本発明の目的は、耐光性に優れた記録画像を得
ることのできる記録媒体を提供することにある。A further object of the present invention is to provide a recording medium on which recorded images with excellent light resistance can be obtained.
さらに本発明の目的は、鮮明な階調性の高い多色記録画
像を小型で、安価な装置で得ることのできる記録媒体を
提供することにある。A further object of the present invention is to provide a recording medium that can produce clear, multicolor recorded images with high gradation using a small and inexpensive device.
さらに本発明の目的は、転写像形成時の環境依存性が極
めて少ない画像形成方法に供しつる記録媒体を提供する
ことにある。A further object of the present invention is to provide a recording medium that can be used in an image forming method with extremely low environmental dependence during transfer image formation.
（問題点を解決するための手段）
本発明の上記目的は、光を含むａ数種のエネルギーをそ
れらのうち少くとも一種のエネルギーを画像記録情報に
対応させて同時に付与することにより、その転写特性を
支配する物性が変化する転写記録層を支持体上に有する
記録媒体であって、該転写記録層が、
ａ）着色剤と、
ｂ）光重合開始剤と、
Ｃ）不飽和二重結合を有する千ツマ−、オリゴマー及び
ポリマーからなる群より選択された１種以上とを含む、
光エネルギー及び熱または熱エネルギーに変換しつるエ
ネルギーの付与によって感応する感応成分
を含み、該転写記録層の流動開始温度が４０℃以上１２
０℃以下の温度範囲内にあり、かつその粘性流動化のた
めの活性化エネルギーが５〜８０Ｋｃａｌ／ｍｏｌの範
囲であることを特徴とする記録媒体によって達成される
。(Means for Solving the Problems) The above object of the present invention is to transfer a plurality of types of energy including light by simultaneously applying at least one type of energy corresponding to image recording information. A recording medium having a transfer recording layer on a support whose physical properties governing characteristics change, the transfer recording layer comprising: a) a colorant; b) a photopolymerization initiator; and C) an unsaturated double bond. and one or more selected from the group consisting of polymers, oligomers, and polymers having
Contains a sensitive component that is sensitive to the application of light energy and heat or energy that converts into thermal energy, and the flow start temperature of the transfer recording layer is 40°C or higher12
This is achieved by a recording medium characterized in that the temperature is within a temperature range of 0° C. or lower, and the activation energy for viscous fluidization is in the range of 5 to 80 Kcal/mol.
本発明の記録媒体の転写記録層に含まれる感応成分は、
光及び熱若しくは熱エネルギーに変換し得るエネルギー
の付与により、その転写特性が変化するものであり、該
転写記録層にこれらエネルギーを記録情報に対応させて
同時に付与することにより、転写特性の異なる部分から
なる転写像を形成し得るものである。The sensitive component contained in the transfer recording layer of the recording medium of the present invention is
The transfer characteristics change by applying light and heat or energy that can be converted into thermal energy, and by simultaneously applying these energies to the transfer recording layer in correspondence with recorded information, parts with different transfer characteristics can be changed. It is possible to form a transfer image consisting of
従って、例えば本発明の記録媒体を用いた記録は、まず
転写層に光及び熱若しくは熱エネルギーに変換し得る２
種のエネルギーの少なくとも一方を、記録情報に対応さ
せて付与し、転写特性を支配する物性の異なる部分を形
成させて該物性の差からなる転写像を形成させ、この物
性差を利用して、該転写像を被記録材に転写して行なわ
れる。Therefore, for example, in recording using the recording medium of the present invention, light and heat or two that can be converted into thermal energy are first transferred to the transfer layer.
At least one of the energies of the seeds is applied in correspondence with the recorded information to form parts with different physical properties that govern the transfer characteristics to form a transferred image consisting of the difference in the physical properties, and by utilizing this physical property difference, This is done by transferring the transferred image onto a recording material.
この転写特性を支配する物性とは、使用する記録媒体の
種類により任意に定められるものであり、例えば、転写
像を熱溶融状態にして転写する転写記録媒体の場合には
、溶融温度、軟化温度又は、ガラス転移点などであり、
また、転写像を粘着状態又は、被転写媒体への浸透性状
態にして転写する転写記録媒体の場合には、同一温度に
おける粘度である。また、転写像を形成するに用いる複
数種のエネルギーも、使用する記録媒体の種類により任
意に定められ、例えば、光電子ビーム、熱、圧力、など
が適宜組合わされて用いられる。The physical properties that govern this transfer characteristic are arbitrarily determined depending on the type of recording medium used. For example, in the case of a transfer recording medium that transfers the transferred image in a thermally molten state, the physical properties that govern the transfer characteristics are the melting temperature and softening temperature. Or the glass transition point, etc.
In addition, in the case of a transfer recording medium in which the transferred image is transferred in an adhesive state or in a permeable state to the transfer medium, the viscosity is the same at the same temperature. Further, the plurality of types of energy used to form a transferred image are also arbitrarily determined depending on the type of recording medium used, and for example, a photoelectron beam, heat, pressure, etc. are used in an appropriate combination.
本発明の記録媒体を画像形成に供するに好ましい画像形
成方法を記す。その理解のために、光と熱エネルギーに
より転写像が形成される記録媒体を用いた例を挙げて第
１ａ図〜第１ｄ図により説明する。A preferred image forming method for forming an image on the recording medium of the present invention will be described. In order to understand this, an example using a recording medium on which a transferred image is formed by light and thermal energy will be explained with reference to FIGS. 1a to 1d.
第１ａ図〜第１ｄ図の各グラフの時間軸（横軸）はそれ
ぞれ対応している。また、転写記録層には、後述する少
なくとも光重合開始剤および不飽和二重結合を有する千
ツマ−、オリゴマーまたはポリマーの一種以上を含む感
応成分が含存されている。第１ａ図はサーマルヘッド等
の加熱手段を時間０〜ｔ３の開発熱駆動させた場合の加
熱手段の表面温度の上昇およびその後の温度降下の様子
を示すものである。この加熱手段に圧接されている転写
記録媒体は、加熱手段の温度変化に伴い、第１ｂ図に示
すような温度変化を示す。即ち、ｔｌの時間遅れをもワ
て温度上昇し、同様にｔ３より遅れてｔ４の時刻に最高
温度に達し以降温度が下降する。此の転写記録層はガラ
ス転移点Ｔｇｏを有し、Ｔｇｏ以上の温度領域で急激に
軟化し粘度か減少する。此の様子を第１Ｃ図の曲線Ａで
示した。時刻ｔ２でＴｇｏに達した以降最大温度に達す
る時刻ｔ、迄粘度降下が続き、温度低下と共に再び粘度
は増加してＴｇｏに降下する時刻ｔ６迄急激な粘度増加
を示す。此の場合転写記録層は加熱前と基本的に物性の
変化を受けておらず、次の転写工程で温度Ｔｇｏ以上に
加熱すれば上記したと同じ様に粘度の減少を示す。従っ
て、被転写媒体と圧接して転写に必要な加熱、例えばＴ
ｇｏ以上に加熱をすれば従来の熱転写記録の転写メカニ
ズムと同様な理由で転写記録層は転写されることになる
が、本発明の場合には、第１ｄ図に示すように、時刻ｔ
２より加熱と同時に光照射した場合、転写記録層に含ま
れている例えば光重合開始剤が活性化され温度が反応速
度を大きくするように充分なだけ上昇していると、感応
成分に含まれる不飽和二重結合を有するモノマー、オリ
ゴマーまたはポリマーの一種以上からなる組成物の重合
の確率が飛躍的に犬きくなる為、硬化が急激に進むよう
になる。The time axes (horizontal axes) of the graphs in FIGS. 1a to 1d correspond to each other. Further, the transfer recording layer contains a sensitive component containing at least a photopolymerization initiator and one or more of polymers, oligomers, or polymers having an unsaturated double bond, which will be described later. FIG. 1a shows the rise in the surface temperature of the heating means and the subsequent temperature drop when the heating means such as a thermal head is driven to develop heat from time 0 to t3. The transfer recording medium that is in pressure contact with the heating means exhibits a temperature change as shown in FIG. 1b as the temperature of the heating means changes. That is, the temperature rises after a time delay of tl, and similarly reaches the maximum temperature at time t4, which is delayed from t3, and thereafter the temperature decreases. This transfer recording layer has a glass transition point Tgo, and rapidly softens and decreases in viscosity in a temperature range above Tgo. This situation is shown by curve A in FIG. 1C. After reaching Tgo at time t2, the viscosity continues to decrease until time t, when the maximum temperature is reached, and as the temperature decreases, the viscosity increases again and shows a rapid increase until time t6, when it drops to Tgo. In this case, the physical properties of the transfer recording layer are basically unchanged from those before heating, and when heated to a temperature above Tgo in the next transfer step, the viscosity decreases in the same manner as described above. Therefore, the heating required for transfer by pressure contact with the transfer medium, for example, T
If heating is performed above go, the transfer recording layer will be transferred for the same reason as the transfer mechanism of conventional thermal transfer recording, but in the case of the present invention, as shown in FIG.
According to 2, when light is irradiated at the same time as heating, for example, a photopolymerization initiator contained in the transfer recording layer is activated, and if the temperature rises enough to increase the reaction rate, it is included in the sensitive component. Since the probability of polymerization of a composition comprising one or more monomers, oligomers, or polymers having unsaturated double bonds increases dramatically, curing proceeds rapidly.
こうして加熱と光照射とが同時に行なわれると、転写記
録層は第１ｃ図の曲線Ｂに示す様な挙動を示す。そして
反応が進むと共にガラス転移点が上昇し反応が終了する
時刻ｔ５ではＴｇｏからＴｇ’ に変化する。この様子
を第１ｄ図に示した。When heating and light irradiation are performed simultaneously in this manner, the transfer recording layer exhibits a behavior as shown by curve B in FIG. 1c. As the reaction progresses, the glass transition point rises and changes from Tgo to Tg' at time t5 when the reaction ends. This situation is shown in Figure 1d.
従って、次の転写工程で加熱するとＴｇ’ に変化した
部分と変化しない部分とでの性質の相異が生じる。これ
に伴なって、転写記録層が転写を開始する温度である転
写開始温度である転写開始温度Ｔａも変化し、Ｔａ’
となる。そこで例えばＴａ＜ Ｔｒ（Ｔａ’を満たすＴ
ｒに加熱すれば粘度が低下した部分とそうでない部分と
の差異が生じ被転写媒体に粘度低下した部分のみの転写
がされる。転写工程の温度安定精度に依るが、このとき
Ｔｇ’ Ｔｇｏは約２０℃以上が好ましい。特に、４
０℃以上が好ましい。この値はＴｇｏ ＞Ｔｇ’の場合
も同様である。このようにして画信号に応じて加熱又は
非加熱を制御し、同時に光照射する事で転写像を形成す
る事ができる。Therefore, when heated in the next transfer step, there will be a difference in properties between the part that has changed to Tg' and the part that has not changed. Along with this, the transfer start temperature Ta, which is the temperature at which the transfer recording layer starts transferring, also changes, and Ta'
becomes. So, for example, Ta < Tr (T that satisfies Ta'
When heated to r, a difference is created between a portion where the viscosity has decreased and a portion where the viscosity has not decreased, and only the portion where the viscosity has decreased is transferred to the transfer medium. Although it depends on the temperature stability accuracy of the transfer process, Tg' Tgo is preferably about 20° C. or higher at this time. In particular, 4
The temperature is preferably 0°C or higher. This value is also the same when Tgo>Tg'. In this way, a transfer image can be formed by controlling heating or non-heating according to the image signal and simultaneously irradiating light.
また、転写像形成工程に於ける加熱温度は、転写特性を
支配する物性が変化する反応速度を速くする為及びその
反応を安定に行なう為にも、７０℃以ト好ましくは８０
℃以上に設定する事が良好な結果を与える。In addition, the heating temperature in the transfer image forming step is preferably 70° C. or lower, preferably 80° C., in order to speed up the reaction rate at which the physical properties that govern the transfer characteristics change and to perform the reaction stably.
Setting the temperature above ℃ gives good results.
転写記録層の転写特性を支配する物性としては、以上説
明したガラス転移点以外にも溶融温度、軟化温度等が考
えられるがＪいずれの場合も複数種の千ネルギーの付与
前後での、溶融温度、軟化温度等の不可逆変化を利用し
て転写記録層中に転写像を形成するものである。また、
軟化温度、溶融温度、ガラス転移点はほぼ同様の傾向で
変動し、従ってガラス転移点を用いた前述の説明はその
まま溶融温度、軟化温度を用いた説明でもある。In addition to the glass transition point explained above, melting temperature, softening temperature, etc. can be considered as the physical properties that govern the transfer characteristics of the transfer recording layer. , a transferred image is formed in the transfer recording layer using irreversible changes such as softening temperature. Also,
The softening temperature, melting temperature, and glass transition point vary in almost the same manner, so the above explanation using the glass transition point is also an explanation using the melting temperature and softening temperature.
次に、軟化温度を用いて本発明の詳細な説明する。Next, the present invention will be explained in detail using the softening temperature.
転写記録層の軟化温度をＴｓとする。転写記録層の粘度
は、Ｔｓ以上の温度領域で急激に減少する。Let Ts be the softening temperature of the transfer recording layer. The viscosity of the transfer recording layer decreases rapidly in a temperature range of Ts or higher.
この様子は第１Ｃ図の曲線Ａで示されている。時刻ｔ２
でＴｓに達した以降最大温度に達する時刻ｔ４迄粘度降
下が続き、温度低下と共に再び粘度は増加しＴｓに降下
する時刻ｔ６迄急激な粘度増加を示す。この場合転写記
録層は加熱前と基本的に物性の変化を受けておらず、次
の転写工程で温度Ｔｓ以上に加熱すれば上記したと同じ
様に粘度の減少を示す。This situation is illustrated by curve A in FIG. 1C. Time t2
After reaching Ts, the viscosity continues to decrease until time t4 when the maximum temperature is reached, and as the temperature decreases, the viscosity increases again and shows a rapid increase until time t6 when it drops to Ts. In this case, the physical properties of the transfer recording layer are basically unchanged from those before heating, and when heated to a temperature Ts or higher in the next transfer step, the viscosity decreases in the same manner as described above.
従って、被転写媒体と圧接して転写に必要な加熱１例え
ばＴｓ以上に加熱をすれば従来の熱転写記録の転写メカ
ニズムと同様な理由で転写記録層は転写されることにな
るが、本発明の場合には、第１ｄ図に示すように、時刻
ｔ２より加熱と同時に光照射した場合、転写記録層が軟
化し転写記録層に含まれている例えば反応開始剤が活性
化され温度が反応速度を大きくするに充分なだけ上昇し
ていると、不飽和二重結合を有するモノマー、オリゴマ
ーまたはポリマーの一種以上からなる組成物が重合する
確率が飛躍的に大きくなる為、硬化が急激に進む。Therefore, if the transfer recording layer is brought into pressure contact with the transfer medium and heated above the heating required for transfer (for example, Ts), the transfer recording layer will be transferred for the same reason as the transfer mechanism of conventional thermal transfer recording. In this case, as shown in Fig. 1d, if light is irradiated at the same time as heating from time t2, the transfer recording layer will soften and, for example, a reaction initiator contained in the transfer recording layer will be activated, and the temperature will reduce the reaction rate. If the increase is sufficiently large, the probability that a composition consisting of one or more monomers, oligomers, or polymers having unsaturated double bonds will polymerize will dramatically increase, so that curing will proceed rapidly.
こうして加熱と光照射とが同時に行なわれると、転写記
録層は第１Ｃ図の曲線Ｂに示す様な挙動を示す。そして
反応が進むと共に軟化温度が上昇し架橋が終了する時刻
ｔ５ではＴｓからＴｓ’ に変化する。この様ｆを第１
ｄ図に示した。但し、第１ｂ図及び第１ｄ図に示したＴ
ｇ、 Ｔｇ’をＴｓ、 Ｔｓ’とする。従って次の転写
工程で加熱するとＴｓ’ に変化した部分と変化しない
部分とでの性質の相異が生じる。これに伴７て、転写記
録層が転写を開始する温度である転写開始温度Ｔａも変
化し、Ｔａ’となる。そこで例えばＴａ＜ Ｔｒ＜ Ｔ
ａ’ を満たすＴ「に加熱すれば被転写媒体に軟化温度
の上昇しない部分のみの転写がされる。転写工程の温度
安定精度に依るがこのときのＴｓ’ −Ｔｓは約２０℃
以上が好ましい。特に、４０℃以上が好ましい。この値
はＴｓ＞Ｔｓ’の場合も同様である。このようにして、
画信号に応じて加熱又は非加熱を制御し、同時に光照射
する事で転写像を形成する事がてきる。When heating and light irradiation are performed simultaneously in this manner, the transfer recording layer exhibits a behavior as shown by curve B in FIG. 1C. As the reaction progresses, the softening temperature rises and changes from Ts to Ts' at time t5 when crosslinking ends. This way f is the first
It is shown in figure d. However, T shown in Figures 1b and 1d
Let g, Tg' be Ts, Ts'. Therefore, when heated in the next transfer step, there will be a difference in properties between the part that has changed to Ts' and the part that has not changed. Along with this, the transfer start temperature Ta, which is the temperature at which the transfer recording layer starts transferring, also changes and becomes Ta'. So, for example, Ta<Tr<T
If heated to T' that satisfies a', only the portion where the softening temperature does not rise will be transferred to the transfer medium.Ts' - Ts at this time depends on the temperature stability accuracy of the transfer process, but at this time Ts' - Ts is approximately 20°C.
The above is preferable. In particular, the temperature is preferably 40°C or higher. This value is also the same when Ts>Ts'. In this way,
A transfer image can be formed by controlling heating or non-heating according to the image signal and simultaneously irradiating light.
尚、本発明における転写開始温度は、次の様にして測定
する。Incidentally, the transfer start temperature in the present invention is measured as follows.
ポリエチレンテレフタレート（ＰＥＴ）フィルム上に塗
布された６μ厚の転写記録層と被転写媒体として用いる
表面平滑度（ベック平滑度）が５０〜２００秒、厚さ０
．２ａ＋ｍの上質紙とを対向させて転写記録媒体と上質
紙とを次に示す２つのロールで挟持して２．５ｍｍ／ｓ
ｅｃ、の速度で搬送する。２つのロールのうち第１のロ
ールは転写記録媒体側に配され、 ３００Ｗのハロゲン
ヒータ内蔵の鉄ロールであり直径は４０ｍｏ＋である。A 6 μ thick transfer recording layer coated on a polyethylene terephthalate (PET) film and a surface smoothness (Beck smoothness) used as a transfer medium of 50 to 200 seconds and a thickness of 0.
．． The transfer recording medium and the high-quality paper are sandwiched between the following two rolls, with the high-quality paper of 2a+m facing each other, and the speed is 2.5 mm/s.
It is transported at a speed of ec. The first roll of the two rolls is placed on the transfer recording medium side, is an iron roll with a built-in 300W halogen heater, and has a diameter of 40mo+.
又、上質紙側の第２のロールは直径４０Ｉｌａｌの鉄ロ
ールの表面が０．５ｍｍ厚のフッ素ゴムで被覆されてお
り、２つのロールは線圧４にｇ ／ ｃ ｍの圧力で対
向している。第１のロールの表面をサーミスタで検出し
、所定の温度に維持する様にハロゲンヒーターを制御す
る。２つのロールの間を通過した後４秒後に上質紙を平
面に保ちながら、転写記録媒体を略９０°の角度で、ロ
ールの搬送速度と等速で引張り転写記録媒体と上質紙と
を剥離し、転写記録層の上質紙への転写の有無を観察す
る。こうして除々にヒートロール（第１のロール）の表
面温度、を上昇させながら（昇温速度１０℃／Ｍ Ｉ
Ｎ以下）転写画像の光学濃度が飽和したときの温度を測
定し、転写開始温度を知ることができる。The second roll on the high-quality paper side is an iron roll with a diameter of 40Il and the surface is coated with 0.5mm thick fluororubber, and the two rolls face each other with a linear pressure of 4 g/cm. There is. The surface of the first roll is detected by a thermistor, and the halogen heater is controlled to maintain it at a predetermined temperature. Four seconds after passing between the two rolls, while keeping the high-quality paper flat, the transfer recording medium was pulled at an angle of approximately 90° at a speed equal to the transport speed of the rolls, and the high-quality paper was separated from the transfer recording medium. , Observe whether or not the transfer recording layer has been transferred to the high-quality paper. In this way, while gradually increasing the surface temperature of the heat roll (first roll) (heating rate 10℃/M I
N or less) The transfer start temperature can be determined by measuring the temperature when the optical density of the transferred image is saturated.
ここで、転写を支配する物性変化とは、記録媒体のガラ
ス転移温度Ｔｇの変化、または、軟化温度Ｔｓの変化、
または溶融温度Ｔｍであることを記したが１本発明の記
録媒体は後の転写工程で記録画像を得るため、被記録体
への粘着状態又は、浸透性状聾が変化すれば良く、明確
な上記Ｔｇ、 ＴｓまたはＴｍの変化がなくても適応可
能である。Here, physical property changes governing transfer include changes in the glass transition temperature Tg or softening temperature Ts of the recording medium;
However, since the recording medium of the present invention obtains a recorded image in the subsequent transfer process, it is sufficient that the adhesion state to the recording medium or the penetrating property changes, and the clear above-mentioned It is adaptable even without changes in Tg, Ts or Tm.
また、転写像を形成する−に用いられる複数種のエネル
ギーとしては、光および熱または熱に変換しつる電気、
超音波、圧力から選ばれるエネルギーの組み合せがエネ
ルギー効率的に好ましい。In addition, the multiple types of energy used to form a transferred image include light and heat, or electricity that converts into heat;
A combination of energy selected from ultrasonic waves and pressure is preferable in terms of energy efficiency.
次に、本発明の効果を最も発現できる多色画像形成法に
ついて説明する。第２ａ図〜第２ｅ図は本発明の転写記
録媒体とサーマルヘッドとの関係を示した部分図で、記
録信号に従って変調された熱エネルギーを、転写特性を
支配する物性を変化させたい画像形成素体の色調により
選択された波長の光エネルギーと共に付与するものであ
る。「変調」とは画信号に応じてエネルギーの付与する
位置を変更することをいい、「共に」とは光エネルギー
と熱エネルギーを同時に付与する場合でもよいし、光エ
ネルギーと熱エネルギーを別々に付与する場合でもよい
。Next, a multicolor image forming method that can bring out the effects of the present invention most will be described. Figures 2a to 2e are partial diagrams showing the relationship between the transfer recording medium of the present invention and the thermal head, in which the thermal energy modulated according to the recording signal is used to change the physical properties governing the transfer characteristics of the image forming element. It is applied along with light energy of a wavelength selected according to the color tone of the body. "Modulation" refers to changing the position where energy is applied according to the image signal, and "together" can mean applying light energy and thermal energy at the same time, or applying light energy and thermal energy separately. It is okay if you do.
本発明の記録媒体１は、ベースフィルム１ｂ上に転写記
録層１ａを設けて構成されている。転写記録層１ａは、
微小な画像形成素体３１の分布層となっていて、各画像
形成素体３１は異なる色調を呈する。例えば、第２ａ図
〜第２ｄ図に示した実施例では、各画像形成素体３１に
はシアン（Ｃ）、マゼンタ（Ｍ）、イエロー（Ｙ）およ
びブラック（に）のいずれかの着色剤が含有されている
。しかし、各画像形成素体３１に含有される着色剤は、
シアン、マゼンタ、イエロー、ブラックに限るものでは
なく、用途に応じてどのような色の着色剤を用いてもか
まわない。各画像形成素体３１には、着色剤の他に光及
び熱のエネルギーが付与されたときに、転写特性を支配
する物性が急激に変化する感応成分を含有する。画像形
成素体３１は、基材１ｂ上にバインダーにより設けても
よいし、また、加熱により溶融して設けてもかまわない
。The recording medium 1 of the present invention is constructed by providing a transfer recording layer 1a on a base film 1b. The transfer recording layer 1a is
It is a distributed layer of minute image forming elements 31, and each image forming element 31 exhibits a different color tone. For example, in the embodiment shown in FIGS. 2a to 2d, each image forming element 31 has a colorant of cyan (C), magenta (M), yellow (Y), or black. Contains. However, the colorant contained in each image forming element 31 is
The coloring agent is not limited to cyan, magenta, yellow, and black, and any coloring agent may be used depending on the purpose. In addition to the colorant, each image forming element 31 contains a sensitive component whose physical properties governing transfer characteristics change rapidly when light and heat energy is applied. The image forming element 31 may be provided on the base material 1b using a binder, or may be provided by being melted by heating.
各画像形成素体３１の感応成分は、含有する着色剤によ
って波長依存性を有する。すなわち、イエローの着色剤
を含有した画像形成素体３１は、熱と波長λ（Ｙ）の光
が加えられたとき、架橋が急激に進み硬化する。同様に
、マゼンタの着色剤の含有する画像形成素体３１は、熱
と波長λ（Ｍ）の光、シアンの着色剤を含有する画像形
成素体３１は熱と波長λ（Ｃ）の光、ブラックの着色剤
を含有する画像形成素体３１は熱と波長λ（Ｋ）の光が
それぞれ加えられたとき、架橋が進み硬化する。硬化し
た画像形成素体３１は、次の転写工程で加熱されても粘
度が低下しないか、粘着性を存さない等のために、被転
写媒体に転写しない。熱と光は記録情報に応じて付与す
る。The sensitive component of each image forming element 31 has wavelength dependence depending on the colorant contained therein. That is, when the image forming element 31 containing the yellow colorant is exposed to heat and light of wavelength λ(Y), crosslinking rapidly progresses and the image forming element 31 is cured. Similarly, the image forming element 31 containing the magenta colorant receives heat and light of wavelength λ(M), and the image forming element 31 containing the cyan colorant receives heat and light of wavelength λ(C). The image forming element 31 containing a black colorant undergoes crosslinking and hardening when heat and light of wavelength λ(K) are respectively applied. The cured image forming element 31 is not transferred to the transfer medium because the viscosity does not decrease or the image forming element 31 does not exhibit adhesiveness even when heated in the next transfer step. Heat and light are applied depending on the recorded information.
次に本発明の記録媒体を用いた画像形成方法の具体例を
第２ａ図〜第２ｅ図を用いて示す。まず、記録媒体１を
サーマルヘッド２０に重ね、サーマルヘッド２０の全熱
部全域をカバーするように光を照射する。照射する光は
画像形成素体３１が反応する波長のものを順次照射する
。例えば、画像形成素体３１がシアン、マゼンタ、イエ
ロー、ブラックのいずれかに着色されている場合、波長
λ（Ｃ）、λ（Ｍ）、え（Ｙ）及びん（Ｋ）に光を順次
照射する。Next, a specific example of an image forming method using the recording medium of the present invention will be shown using FIGS. 2a to 2e. First, the recording medium 1 is stacked on the thermal head 20, and light is irradiated so as to cover the entire heated portion of the thermal head 20. The irradiated light has a wavelength that the image forming element body 31 reacts to, and is sequentially irradiated. For example, when the image forming element 31 is colored cyan, magenta, yellow, or black, light is sequentially irradiated with wavelengths λ(C), λ(M), E(Y), and N(K). do.
つまり、まず記録媒体１の転写記録層１ａ側から波長λ
（Ｙ）の光を照射するとともに、例えばサーマルヘッド
２０の発熱抵抗体２０ｂ、２０ｄ、２０ｅおよび２０ｆ
を発熱させる。すると、イエローの着色剤の含有する画
像形成素体３１のうち、熱と波長λ（Ｙ）の光の両方が
加えられた画像形成素体３１（第２ａ図でハツチングの
施された部分。以下、硬化した画像形成素体をハツチン
グで示す。That is, first, from the transfer recording layer 1a side of the recording medium 1, the wavelength λ is
(Y) and, for example, the heating resistors 20b, 20d, 20e, and 20f of the thermal head 20.
generates heat. Then, of the image forming element 31 containing the yellow colorant, the image forming element 31 to which both heat and light of wavelength λ(Y) are applied (the hatched part in FIG. 2a, below) , the cured image forming element is indicated by hatching.
）が硬化する。) hardens.
次に、第２ｂ図に示すように転写記録層１ａに波長λ（
Ｍ）の光を照射するとともに、発熱抵抗体２０ａ、２（
ｌｅ及び２Ｏｆを発熱させると２マゼンタの着色剤の含
有する画像形成素体３１のうち、熱と波長入（Ｍ）の光
が加えられた画像形成素体３■が硬化する６更に、第２
ｃ図、第２ｄ図に示すように、波長λ（Ｃ）の光、波長
λ（Ｋ）の光を照射するとともに、所望の発熱抵抗体を
加熱させると、光と熱の加えられた画像形成素体３１が
硬化し、最終的に硬化しなかった画像形成素体３１によ
り転写記録層１に転写像が形成される。この転写像は次
の転写工程で第２ｅ図に示すように被転写媒体１０に転
写される。Next, as shown in FIG. 2b, the transfer recording layer 1a is coated with a wavelength λ(
At the same time, the heating resistors 20a, 2(
When le and 2Of are made to generate heat, the image forming element 31 to which heat and wavelength (M) light have been applied is cured, of the image forming element 31 containing the magenta colorant.
As shown in Figures c and 2d, when a desired heating resistor is heated while being irradiated with light of wavelength λ(C) and light of wavelength λ(K), an image is formed by adding light and heat. The element body 31 is cured, and a transfer image is finally formed on the transfer recording layer 1 by the image forming element body 31 that has not been cured. This transferred image is transferred to the transfer medium 10 in the next transfer step as shown in FIG. 2e.
転写像が形成された記録媒体を転写工程で、被転写媒体
と接面させて、記録媒体又は被転写媒体側から加熱し転
写可能な部分からなる転写像を被転写媒体に選択的に転
写して画像を形成する。In the transfer process, the recording medium on which the transferred image has been formed is brought into contact with the transfer medium, and the transfer image consisting of the transferable portion is selectively transferred to the transfer medium by heating from the recording medium or the transfer medium side. to form an image.
従ってこのときの加熱温度は、転写工程において転写像
のみが選択的に転写するように定められる。また、転写
を効率的に行なうために、同時に加圧することも有効で
ある。加圧は、特に表面平滑度の低い被転写媒体を用い
る場合有効である。Therefore, the heating temperature at this time is determined so that only the transferred image is selectively transferred in the transfer process. Further, in order to perform the transfer efficiently, it is also effective to apply pressure at the same time. Pressure is particularly effective when using a transfer medium with low surface smoothness.
また、転写特性を支配する物性が室温における粘度であ
る場合には、加圧だけで転写が可能である。Furthermore, if the physical property that governs the transfer characteristics is the viscosity at room temperature, transfer is possible only by applying pressure.
又転写工程で加熱する事は安定的で保存性に優れた堅牢
な多色画像を得るのに適している。Furthermore, heating during the transfer process is suitable for obtaining stable, durable, and durable multicolor images.
以上第２ａ図〜第２ｄ図で説明した例では、光をサーマ
ルヘッド２０の全域に照射し、サーマルヘッド２０の発
熱抵抗体を選択的に発熱させて画像を形成する方法を示
したが、記録媒体のある部分を一様に加熱して（第２ａ
図で示すサーマルヘッド２０でいうならば、全発熱抵抗
体を発熱させる場合）、光照射を選択的に行なう事によ
っても同様に多色の画像を形成する事ができる。即ち、
記録信号に従って変調され、且つ転写特性を支配する物
性を変化させたい画像形成素体の色調により選択された
波長の光エネルギーを熱エネルギーと共に付与する。In the example explained above with reference to FIGS. 2a to 2d, a method is shown in which an image is formed by irradiating the entire area of the thermal head 20 with light and selectively causing the heating resistor of the thermal head 20 to generate heat. Heating a certain part of the medium uniformly (2nd a)
In the case of the thermal head 20 shown in the figure, in which all the heating resistors generate heat), a multicolor image can be similarly formed by selectively irradiating light. That is,
Light energy of a wavelength that is modulated according to the recording signal and that is selected depending on the color tone of the image forming element whose physical properties governing the transfer characteristics are desired to be changed is applied together with thermal energy.
以上説明したように、本発明の記録媒体は、特にベース
フィルム上に転写記録層を設けて構成し、かつ、転写記
録層には該記録媒体が微小な画像形成素体の分布層とな
しているものが画像濃度の高い記録媒体として好ましい
。As explained above, the recording medium of the present invention is constructed by providing a transfer recording layer on a base film, and the recording medium is formed as a distribution layer of minute image forming elements in the transfer recording layer. A recording medium with high image density is preferable.
このような本発明の記録媒体の有する転写記録層の構成
に必要な感応成分は、先に述べたように、少なくとも、
不飽和二重結合を有するモノマー、オリゴマー及びポリ
マーからなる群より選択した１種以上からなる組成物と
、光重合開始剤と、着色剤とを含むものである。As mentioned above, the sensitive components necessary for the structure of the transfer recording layer of the recording medium of the present invention include at least the following:
It contains a composition consisting of one or more selected from the group consisting of monomers, oligomers, and polymers having unsaturated double bonds, a photopolymerization initiator, and a colorant.
該光重合開始剤としては、アゾ化合物、有機イオウ化合
物、カルボニル化合物、ハロゲン化合物などのラジカル
開始剤が好ましい。例えば、ベンゾフェノン、ベンジル
、ベンゾインエチルエーテル、４−Ｎ、Ｎ−ジメチルア
ミノ−４°−メトキシ−ベンゾフェノン等のカルボニル
化合物、ジブチルスルフィド、ベンジル・ジスフィルド
、デシルフェニルスルフィド等の有機硫黄化合物、ジー
ｔｅｒｔ−ブチルバーオキシド、ベンゾイルパーオキシ
ド等の過酸化物四塩化炭素、臭化銀、２−ナフタリンス
ルホニルクロライド等のハロゲン化合物、アゾビスイソ
ブチロニトリル、ベンゼンジアゾニウムクロライド等の
窒素化合物等があげられる。As the photopolymerization initiator, radical initiators such as azo compounds, organic sulfur compounds, carbonyl compounds, and halogen compounds are preferable. For example, carbonyl compounds such as benzophenone, benzyl, benzoin ethyl ether, 4-N,N-dimethylamino-4°-methoxy-benzophenone, organic sulfur compounds such as dibutyl sulfide, benzyl disulfide, decylphenyl sulfide, di-tert-butyl Examples include peroxides such as peroxide and benzoyl peroxide, halogen compounds such as carbon tetrachloride, silver bromide, and 2-naphthalenesulfonyl chloride, and nitrogen compounds such as azobisisobutyronitrile and benzenediazonium chloride.
また、本発明の感応成分に用いられる不飽和二重結合を
存する千ツマ−、オリゴマー及びポリマーとしては、ポ
リイソシアネートと（必要に応じてポリオール類と反応
させておいてもよい）不飽和二重結合を含むアルコール
、アミン類の重付加反応により合成されるウレタン結合
を有するウレタンアクリレート、ウレタンメタクリレー
ト類、およびエポキシ樹脂とアクリル酸またはメタクリ
ル酸との付加反応により合成されるエポキシアクリレー
ト類、またはポリエステルアクリレート類、スピンアク
リラート類、ポリエーテルアクリレート類などがあげら
れるが、本発明はこれに限定されるものではない。In addition, the polymers, oligomers and polymers containing unsaturated double bonds used in the sensitive component of the present invention include polyisocyanates and unsaturated double bonds (which may be reacted with polyols if necessary). Urethane acrylates and urethane methacrylates with urethane bonds synthesized by polyaddition reactions of alcohols and amines containing bonds, and epoxy acrylates or polyester acrylates synthesized by addition reactions of epoxy resins with acrylic acid or methacrylic acid. Examples include spin acrylates, polyether acrylates, etc., but the present invention is not limited thereto.
またポリマーとしては主鎖にポリアルキル、ポリエーテ
ル、ポリエステル、ポリウレタンなどの骨格を存し側鎖
にアクリル基、メタクリル基、シンナモイル基、シンナ
ミリデンアセチル基、フリルアクリロイル基ケイ皮酸エ
ステルなどに代表される重合性、架橋性の反応基を導入
したものがあげられるが本発明はこれに限定されるもの
ではない。In addition, polymers have skeletons such as polyalkyl, polyether, polyester, and polyurethane in the main chain, and acrylic, methacrylic, cinnamoyl, cinnamylidene acetyl, and furyl acryloyl groups in the side chains, such as cinnamate esters. Examples include those into which polymerizable and crosslinkable reactive groups have been introduced, but the present invention is not limited thereto.
また以上に挙げたモノマー、オリゴマー、ポリマーの１
種以上からなる組成物は、光重合開始剤と混合された最
に、常温で半固体もしくは固体状であることが望ましい
が、液状のものでも以下に述べる結着性組成体と混合す
ることで半固体もしくは固体状を維持するものであれば
構わない。Also, one of the monomers, oligomers, and polymers listed above.
It is desirable that the composition consisting of at least one species be in a semi-solid or solid state at room temperature after being mixed with a photopolymerization initiator, but even if it is in a liquid state, it can be mixed with the binding composition described below. Any material may be used as long as it maintains a semi-solid or solid state.
この結着性組成体としては、従来公知の有機高分子重合
体を用いることができる。例えば、側鎖にカルボキシル
基を有する付加重合体、例えばメタクリ酸共重合体、ア
クリル酸共重合体、イタコン酸共重合体、部分エステル
化マレイン酸共重合体、マレイン酸共重合体等がある。As this binding composition, conventionally known organic polymers can be used. Examples include addition polymers having carboxyl groups in side chains, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, partially esterified maleic acid copolymers, and maleic acid copolymers.
また、塩素化ポリエチレン、塩素化ポリプロピレンなと
の塩素化ポリオレフィン、ポリメチルメタクリレート、
ポリアクリル酸、ポリメタクリル酸、ポリアクリル酸、
アルキルエステル、アクリル酸アルキルエステルとアク
リロニトリル、塩化ビニル、塩化ビニリデン、スチレン
、ブタジェン等の共重合物、ポリ塩化ビニル、塩化ビニ
ルとアクリロニトリルの共重合物、ポリ酢酸ビニル、酢
酸ビニルと塩化ビニルの共重合物、ポリビニルアルコー
ル、ポリビニルピロリドン、ポリアクリルニトリル、ア
クリルニトリルとスチレンの共重合物、アクリルニトリ
ルとブタジェン及びスチレンとの共重合物、ポリビニル
アルキルエーテル、ポリメチルビニルケトン、ポリエチ
ルビニルケトン、ポリエチレン、ポリプロピレン、ポリ
スチレン、ポリアミド、ポリブタジェン、ポリイソプレ
ン、ポリウレタン、ポリエチレンテレフタレート、塩化
ゴム、ポリクロロプレン、ポリスチレン−ブタジェン共
重合体などがある。上記ポリマーのうち、好適に用いら
れるものとして塩化ポリエチレン、ポリメチルメタクリ
レート、ポリ塩化ビニル、塩化ビニリデン−アクリロニ
トリル共重合物、ポリスチレン、スチレン−アクリル共
重合体、ポリビニルブチラール、ポリビニルアセテート
、塩化ビニル−酢酸ビニル共重合物、塩化ゴムなどがあ
る。これらは単独もしくは２種以上の混合物であっても
良い。In addition, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polymethyl methacrylate,
polyacrylic acid, polymethacrylic acid, polyacrylic acid,
Alkyl ester, copolymer of acrylic acid alkyl ester and acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc., polyvinyl chloride, copolymer of vinyl chloride and acrylonitrile, polyvinyl acetate, copolymer of vinyl acetate and vinyl chloride polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile with butadiene and styrene, polyvinyl alkyl ether, polymethyl vinyl ketone, polyethyl vinyl ketone, polyethylene, polypropylene , polystyrene, polyamide, polybutadiene, polyisoprene, polyurethane, polyethylene terephthalate, chlorinated rubber, polychloroprene, polystyrene-butadiene copolymer, and the like. Among the above polymers, polyethylene chloride, polymethyl methacrylate, polyvinyl chloride, vinylidene chloride-acrylonitrile copolymer, polystyrene, styrene-acrylic copolymer, polyvinyl butyral, polyvinyl acetate, vinyl chloride-vinyl acetate There are copolymers, chlorinated rubber, etc. These may be used alone or in a mixture of two or more.
また、ワックス類も用いることができ、キャンデリラワ
ックス、カルナウバワックス、ライスワックスなどの植
物系ワックス、みつろう、鯨ろうなどの動物性ワックス
、セレシン、モンタンワックスなどの鉱物系ワックス、
パラフィンワックスなどの石油ワックス、ポリエチレン
ワックス、サゾールワックス、モンタンワックス誘導体
、パラフィンワックス誘導体、硬化ひまし油、硬化ひま
し油誘導体、ステアリン酸などの脂肪酸や脂肪酸アミド
エステルからなる合成ワックスがある。本発明において
はこれらワックス類を１種類あるいは２種類以上混合し
て用いてもよい。Waxes can also be used, including vegetable waxes such as candelilla wax, carnauba wax and rice wax, animal waxes such as beeswax and spermaceti, mineral waxes such as ceresin and montan wax,
There are petroleum waxes such as paraffin wax, polyethylene wax, Sasol wax, montan wax derivatives, paraffin wax derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, and synthetic waxes made of fatty acids and fatty acid amide esters such as stearic acid. In the present invention, one type or a mixture of two or more types of these waxes may be used.
なお、これら結着性組成体の配合量は、これを含む場合
の感応成分の所望とする特性を損なわない範囲内に選択
すれば良いが、例えば１〜９０重量部、好ましくは１〜
６０重量部重量上程ると良い。The blending amount of these binding compositions may be selected within a range that does not impair the desired properties of the sensitive component when it is included, but for example, 1 to 90 parts by weight, preferably 1 to 90 parts by weight.
It is preferable to increase the amount by 60 parts by weight.
また、特に、光及び熱エネルギーの両方を受けて転写像
を形成する場合の転写記録層の構成には、上記した光エ
ネルギーを受けて作用する光重合開始剤と不飽和二重結
合を存する千ツマ−、オリボマーまたはポリマーの一種
以上からなる組成物との反応における反応速度の温度依
存性が大きくなるように、光重合開始剤と該組成物の種
類を選らんで組合せて用いれば良い。In particular, in the case where a transfer image is formed by receiving both light and thermal energy, the structure of the transfer recording layer includes a photopolymerization initiator that acts in response to the above-mentioned light energy, and unsaturated double bonds. The type of the photopolymerization initiator and the composition may be selected and used in combination so that the temperature dependence of the reaction rate in the reaction with the composition consisting of one or more of polymers, oligomers, oligomers, and polymers is increased.
例えば、熱溶融性のウレタンアクリレート系の重合性モ
ノマーと、２−クロロチオキサントンあるいはエチル−
Ｐ−ジメチルアミノベンゾエート（反応開始剤）の組合
せが挙げられる。For example, heat-melting urethane acrylate polymerizable monomer and 2-chlorothioxanthone or ethyl-
A combination of P-dimethylaminobenzoate (reaction initiator) may be mentioned.
また、転写性の調整剤として、アクリル系樹脂を更に上
記感応成分に加えることができる。Moreover, an acrylic resin can be further added to the above-mentioned sensitive component as a transferability adjusting agent.
本発明の記録媒体の転写記録層の有する感応成分に含有
させる着色剤は、光学的に認識できる画像を形成するた
めに含有させる成分であり、各種顔料、染料が適宜用い
られ、例えば上述の感応成分と混合されて転写記録層を
構成し得る。The coloring agent contained in the sensitive component of the transfer recording layer of the recording medium of the present invention is a component contained in order to form an optically recognizable image, and various pigments and dyes may be used as appropriate. components may be mixed to form a transfer recording layer.
該着色剤として用いる顔料、染料の例としては、カーボ
ンブラックや黄鉛、モリブデン赤、ベンガラ等の無機顔
料、バンザイエロー、ベンジジンイエロー、ブリリアン
トカーミン６Ｂ、レークレッドＣ、パーマネントレッド
Ｆ５Ｒ、フタロシアニンブルー、ビクトリアブルーレー
ク、ファストスカイブルー等の有機顔料、ロイコ染料、
フタロシアニン染料等の着色剤などがあげられる。着色
剤の量としては、必要に応じて結着性組成体を含む感応
成分に対し、０．１から３０重量部が好ましい。Examples of pigments and dyes used as the coloring agent include carbon black, yellow lead, molybdenum red, inorganic pigments such as red red, Banza yellow, benzidine yellow, brilliant carmine 6B, lake red C, permanent red F5R, phthalocyanine blue, and Victoria. Organic pigments such as Blue Lake and Fast Sky Blue, leuco dyes,
Examples include coloring agents such as phthalocyanine dyes. The amount of the colorant is preferably 0.1 to 30 parts by weight based on the sensitive component including the binding composition if necessary.
本発明の転写記録媒体は、例えば、支持体上に上述した
転写記録層を構成できる各種成分から所望に応じて選択
した材料を、必要に応じて溶媒中に混合または分散し、
それを支持体上に塗工するなどの方法により転写記録層
を形成して得ることがでる。The transfer recording medium of the present invention can be prepared, for example, by mixing or dispersing in a solvent, if necessary, a material selected from various components capable of forming the above-mentioned transfer recording layer on a support;
It can be obtained by forming a transfer recording layer by coating it on a support.
なお、支持体としては、ポリエステル、ポリカーボネー
ト、トリアセチルセルロース、ナイロン、ポリイミド、
ポリエチレンテレフタレート、アルミニウムなどの金属
等を用いることができ、これらはフィルム状、板状、ド
ラム状、球状であっても良い。In addition, as a support, polyester, polycarbonate, triacetyl cellulose, nylon, polyimide,
Metals such as polyethylene terephthalate and aluminum can be used, and these may be in the shape of a film, plate, drum, or sphere.
なお、一層に塗工して使用する場合には、感応成分の大
気中の酸素阻害による感度低下を防止する為、ポリエチ
レン、ポリプロピレン等のフィルムを転写記録層上に圧
着せしめ、転写記録転写像形成後に剥離する手段も有効
である。また、感応成分を造粒し、酸素透過性の小さい
高分子化合物にて被覆すれば、感度低下の防止更には画
像の解像性も向上でき得る。更には、呈する色の異なる
着色材料及び吸収波長領域の異なる光重合開始剤より成
る複数種の組成体をマイクロカプセル化し、画像形成組
体とし、ランダムに支持体上に担持させて転写記録層を
形成することによりカラー記録に対応する転写記録媒体
となる。When coating in one layer, in order to prevent a decrease in sensitivity due to atmospheric oxygen inhibition of the sensitive component, a film of polyethylene, polypropylene, etc. is pressed onto the transfer recording layer to form a transfer recording image. It is also effective to peel it off afterwards. Further, by granulating the sensitive component and coating it with a polymer compound having low oxygen permeability, it is possible to prevent a decrease in sensitivity and improve image resolution. Furthermore, a plurality of compositions consisting of coloring materials exhibiting different colors and photopolymerization initiators having different absorption wavelength regions are microencapsulated to form an image forming assembly, which is randomly supported on a support to form a transfer recording layer. By forming this, it becomes a transfer recording medium compatible with color recording.
転写記録層を構成する画像形成素体にマイクロカプセル
を使用する場合には、コア部に上記説明した材料を含有
させる。マイクロカプセルの壁材に用いられる材料とし
ては、ゼラチンとアラビアゴム、エチルセルロース、ニ
トロセルロース等のセルロース系尿素ホルマリン、ナイ
ロン、テトロン、ポリウレタン、ポリカーボネイト、無
水マレイン酸系共重合体、塩化ビニルデン、ポリ塩化ビ
ニル、ポリエチレン、ポリスチレン、ＰＥＴ等のポリマ
ー系等が挙げられる。When microcapsules are used in the image forming element constituting the transfer recording layer, the above-described material is contained in the core portion. Materials used for the walls of microcapsules include gelatin and gum arabic, cellulose-based urea-formalin such as ethyl cellulose and nitrocellulose, nylon, tetron, polyurethane, polycarbonate, maleic anhydride copolymers, vinyldene chloride, and polyvinyl chloride. , polyethylene, polystyrene, PET, and other polymer systems.
本発明の転写記録媒体の転写記録層の厚みは１〜２０μ
が好ましく、特に３〜１０μが好ましい。転写記録層が
マイクロカプセルの画像形成素体で構成されている場合
には、マイクロカプセルの粒径は１〜２０μが好ましく
、特に３〜１０μの粒径が好ましい。また、マイクロカ
プセルの粒径分布は、数平均径に対して±５０％以下が
好ましく、特に±２０％以下が好ましい。マイクロカプ
セルの壁材の厚さは、 ０．１〜２．０μが好ましく、
特に０．１〜０．５μが好ましい。The thickness of the transfer recording layer of the transfer recording medium of the present invention is 1 to 20 μm.
is preferable, and particularly preferably 3 to 10μ. When the transfer recording layer is composed of image forming elements of microcapsules, the particle size of the microcapsules is preferably 1 to 20 μm, particularly preferably 3 to 10 μm. Further, the particle size distribution of the microcapsules is preferably ±50% or less, particularly preferably ±20% or less with respect to the number average diameter. The thickness of the wall material of the microcapsule is preferably 0.1 to 2.0μ,
Particularly preferred is 0.1 to 0.5μ.
マイクロカプセル化の方法としては従来公知の方法がい
ずれも適用でき、例えば、単純コアセルベーション法、
コンプレックスコアセルベーション法、界面重合法、１
ｎ−ｓｉｔｕ重合法、界面沈殿法、相分離法、スプレー
ドライング法、気中懸濁被覆法、メカノケミカル法など
が用いられる。Any conventionally known method can be applied as the microencapsulation method, such as simple coacervation method,
Complex coacervation method, interfacial polymerization method, 1
The n-situ polymerization method, interfacial precipitation method, phase separation method, spray drying method, air suspension coating method, mechanochemical method, etc. are used.
マイクロカプセルの画像形成素体を支持体に結着させる
には、例えばポリビニルアルコール（ＰＶＡ）やエポキ
シ系接着剤などの塗布用パイングーにより行う。塗布用
バインダーの厚みは、０．１〜１μが好ましい。The microcapsule image forming element is bound to the support using a coating agent such as polyvinyl alcohol (PVA) or epoxy adhesive. The thickness of the coating binder is preferably 0.1 to 1 μm.
本発明の多色画像形成方法に使用する多色転写記録媒体
は、転写記録層を構成する画像形成素体が、色材の種類
によって波長依存性を有する必要がカラー画像を再現す
る場合にある。前にも述べた様に、転写記録層がｎ種類
の色の画像形成素体により構成されている場合には、着
色された色ごとに異なる波長の光、即ちｎ種類の異なる
波長で急激に反応速度が変化する様な感応成分の組合せ
で画像形成素体の分布層を構成する。この様な感応成分
の組合せとして、例えば、増感剤としての様におよそ４
００〜５００ｒ＋ｍで感光するものと、また
様におよそ４８０〜６００ｎｍで感光するものを用いる
事によって２色記録を可能にする。この場合両者の感光
域は、 ４８０〜５００ｎｍの波長域が重なってはいる
が感度の低い領域でもあり、また光源を適当に選択する
事で、殆ど完全に両者を分離できる。In the multicolor transfer recording medium used in the multicolor image forming method of the present invention, in order to reproduce a color image, the image forming element constituting the transfer recording layer needs to have wavelength dependence depending on the type of coloring material. . As mentioned earlier, when the transfer recording layer is composed of image forming elements of n types of colors, light of different wavelengths for each colored color, that is, n types of different wavelengths are suddenly emitted. The distribution layer of the image forming element is composed of a combination of sensitive components whose reaction rates change. As a combination of such sensitizing ingredients, for example, as a sensitizer, about 4
Two-color recording is made possible by using one that is sensitive to 00 to 500 r+m and another that is sensitive to about 480 to 600 nm. In this case, although the wavelength range of 480 to 500 nm overlaps, the photosensitive range of both is a low sensitivity range, and by appropriately selecting a light source, it is possible to almost completely separate the two.
また、これらに３４０〜４００ｎｍで感光するアゾ化合
物や３００〜４００ｎｍで感光するハロゲン化合物を組
合せる事によって３色の画像形成素体を用いる事ができ
る為、フルカラー記録へと展開が可能となる。Further, by combining these with an azo compound sensitive to 340 to 400 nm or a halogen compound sensitive to 300 to 400 nm, it is possible to use a three-color image forming element, making it possible to develop full-color recording.
更に、反応開始剤の組合せとして、■２−クロロチオキ
サントン／エチルｐ−ジメチルアミノベンゾエイトと、
■ジクロロベンゾフェノン／エチルｐ−ジメチルアミノ
ベンゾエイトの組合せを用いることもできる。この組合
せに対して使用する光源としては、αピーク波長が３９
０ｎｍの蛍光灯とβビーク波長３１３ｎｍの蛍光灯が使
用できる。同一反応量を得る（転写濃度が等しい）ため
に必要な照射エネルギーは■−αの組合せを１とすると
、■−βは４、■−βの組合せは１．ｌ、■−αは５で
ある。Furthermore, as a reaction initiator combination, (1) 2-chlorothioxanthone/ethyl p-dimethylaminobenzoate;
(2) A combination of dichlorobenzophenone/ethyl p-dimethylaminobenzoate can also be used. The light source used for this combination has an α peak wavelength of 39
A fluorescent lamp with a wavelength of 0 nm and a fluorescent lamp with a β peak wavelength of 313 nm can be used. The irradiation energy required to obtain the same reaction amount (equal transfer concentration) is 1 for the combination of ■-α, 4 for the combination of ■-β, and 1 for the combination of ■-β. l, -α is 5.
従って、αの照射エネルギーを１、βの照射エネルギー
を１．１ とすることで、■、■の反応を区別すること
ができる。Therefore, by setting the irradiation energy of α to 1 and the irradiation energy of β to 1.1, it is possible to distinguish the reactions ■ and ■.
また異なる色調を呈する画像形成素体に含まれる感応成
分の波長依存性がほぼ等しい場合も、着色剤のフィルタ
効果によって、波長依存性を持たせる事が可能である。Furthermore, even if the wavelength dependencies of the sensitive components contained in image forming elements exhibiting different color tones are approximately equal, it is possible to impart wavelength dependence through the filter effect of the colorant.
例えば着色剤が青の場合、この青の着色剤は青い光の波
長約４００〜５００ｎｍを反射及び透過し、緑〜赤の５
００〜７００ｎｍの波長の光を吸収する。従って、青い
着色剤を含有する画像形成素体は青い光に感応する。同
様な理由で赤い着色剤を有する場合赤い光に感応する事
ができる。そこで青から赤までの光に感応ずつる感応成
分を有してもその着色剤によって波長依存性を持たせる
事が出来る。For example, if the colorant is blue, this blue colorant reflects and transmits blue light wavelengths of approximately 400 to 500 nm, and green to red wavelengths of approximately 400 to 500 nm.
Absorbs light with a wavelength of 00 to 700 nm. Therefore, an imaging element containing a blue colorant is sensitive to blue light. For the same reason, if it has a red colorant, it can be sensitive to red light. Therefore, even if it has a sensitive component that is sensitive to light from blue to red, it can be made wavelength dependent by using the colorant.
本発明で使用する転写記録媒体は、空気中の酸素のため
に転写記録層のラジカル反応が抑圧されることがある。In the transfer recording medium used in the present invention, radical reactions in the transfer recording layer may be suppressed due to oxygen in the air.
これを防止するために、例えばポリビニルアルコール水
溶液に界面活性剤を少量加えたものを酸素防止層として
転写記録層上に塗布するのが好ましい。この酸素防止層
は転写像形成後水洗いして除去する。又、マイクロカプ
セル化された素体の場合は壁材に酸素防止層としての機
能を持たせる事ができる。In order to prevent this, it is preferable to apply, for example, an aqueous polyvinyl alcohol solution to which a small amount of a surfactant is added as an oxygen-preventing layer on the transfer recording layer. This oxygen prevention layer is removed by washing with water after the transfer image is formed. In addition, in the case of a microencapsulated element, the wall material can have a function as an oxygen prevention layer.
本発明で使用する転写記録媒体は、代表的には、例えば
、次のようにして製造することができる。The transfer recording medium used in the present invention can typically be manufactured, for example, as follows.
光重合開始剤、不飽和二重結合を存するモノマー、オリ
ゴマー及びポリマーの一種以上からなる成分、光重合開
始剤、増感剤、安定剤、着色剤等の感応成分を構成でき
る各材料や、その他所型の応じて用いられる各材料を、
溶融混合してアプリケーター等により支持体上に塗布し
て本発明の転写記録媒体を作成する。また、転写記録層
が画像形成素体により構成されている場合には、前記成
分を各色毎に噴霧乾燥法等によって、微小な画像形成素
体とし、更にポリエステル樹脂等のバインダーと共に各
色画像形成素体をメチルエチルケトン、エチレングリコ
ールジアセタート等の溶剤中で充分混合した後、ポリイ
ミド等のフィルム上ヘソルベントコートを行い、更に８
０℃で３分間乾燥させて溶剤を除去する事によって所望
の記録媒体を得る事ができる。Photopolymerization initiators, monomers containing unsaturated double bonds, components consisting of one or more of oligomers and polymers, materials that can constitute sensitive components such as photopolymerization initiators, sensitizers, stabilizers, colorants, etc. Each material used depending on the type of work,
The transfer recording medium of the present invention is prepared by melting and mixing and applying the mixture onto a support using an applicator or the like. In addition, when the transfer recording layer is constituted by an image forming element, the above-mentioned components are made into minute image forming elements by spray drying method etc. for each color, and then each color image forming element is formed with a binder such as a polyester resin. After thoroughly mixing the body in a solvent such as methyl ethyl ketone or ethylene glycol diacetate, solvent vent coating is performed on a film such as polyimide, and further 8
A desired recording medium can be obtained by drying at 0° C. for 3 minutes to remove the solvent.
画像形成素体が、マイクロカプセルにより構成されてる
場合には、例えば後述の実施例に詳述されているような
方法によりマイクロカプセルの画像形成素体を製造し、
粒子上の画像形成素体の場合と同様にして、支持体上の
ソルベントコート法により塗布する。When the image-forming element is composed of microcapsules, the image-forming element of microcapsules is manufactured, for example, by a method detailed in the Examples below,
In the same manner as in the case of image forming elements on particles, coating is performed on a support by a solvent coating method.
また、該粒子状素体を支持体上に静電気的に付着させて
も良く、その場合には該粒子状素体または支持体または
両方をコロナ帯電させるか摩擦帯電させ付着させる。Further, the particulate element may be electrostatically attached to a support, and in that case, the particulate element or the support or both are corona-charged or tribo-electrified and attached.
なお、本発明でいう感応成分の支持体への担持は、上記
のようなツルベンコートや静電気的に感応成分を支持体
に付着させる方法等の物理的方法によって、また例えば
画像形成素体と支持体とが接する表面のそれぞれに官能
基を持たせ化学的に結着する方法等の化学的方法により
行ない得るものである。Note that the supporting of the sensitive component on the support in the present invention may be carried out by a physical method such as the above-mentioned turben coating or a method of electrostatically attaching the sensitive component to the support, or by a physical method such as a method of attaching the sensitive component to the support by attaching the image forming element to the support. This can be achieved by a chemical method such as a method in which functional groups are provided on each of the surfaces in contact with the surface and chemically bonded.
以上のようにして形成される本発明の記録媒体の転写記
録層は、その流動開始温度が４０℃以上１２０℃以下で
粘性流動化のための活性エネルギーが５から８０ Ｋｃ
ａｌ／＋ｏｌの範囲であるものが好ましい。より好まし
くは５から３０ Ｋｃａｌ／ｍｏｌである。The transfer recording layer of the recording medium of the present invention formed as described above has a flow initiation temperature of 40° C. or higher and 120° C. or lower, and an active energy for viscous fluidization of 5 to 80 Kc.
A range of al/+ol is preferred. More preferably 5 to 30 Kcal/mol.
ここで流動開始温度とは通常の軟化温度とは異なるもの
で、加熱加圧下における流動現象の数値である。具体的
には、高化式フローテスター（島津制作所）を用いオリ
フィス径１ｍｍのオリフィス内より、荷重２０ Ｋ ｇ
／ ｃ ｒｎ”を印加しながら一定昇温速度で加熱し
、流出させ、その流出開始温度を測定する。また、粘性
流動化とは、感応成分が液体ではないが加圧時に粘性を
有し、しかも流動するのを防げる程には粘性でない状態
にすることを意味し、そのための活性エネルギーは、上
記したフローテスターを用い、粘性流動化状態における
溶融粘度を測定し、次の（１）式で示されるアンドレー
ドの式（＾ｎｄｒａｄｅ ’ｓ ｆｏｒｍｕｌａ ）に
従って算出される。Here, the flow start temperature is different from the normal softening temperature, and is a numerical value of the flow phenomenon under heating and pressurization. Specifically, a load of 20 Kg was applied from inside an orifice with an orifice diameter of 1 mm using a Koka type flow tester (Shimadzu Corporation).
/ crn'' is applied at a constant temperature increase rate, the material is allowed to flow out, and the temperature at which the material begins to flow is measured. Also, viscous fluidization means that the sensitive component is not a liquid but has viscosity when pressurized. Moreover, it means to make the state not viscous enough to prevent it from flowing, and the activation energy for this is determined by measuring the melt viscosity in the viscous fluidized state using the above-mentioned flow tester, and using the following equation (1). It is calculated according to Andrade's formula shown.
η＝Ａ８Ｅ−／Ｒ” （１）但し、 η
：溶融粘度（ｃｐｓ）
Ａ：定数
Ｅａ：粘性流動化のための活性化エネルギー（Ｋｃａｌ
／ｍｏｌ）
Ｒ：気体定数 （１，９８７ｃａｌ／ｄｅｇ、ｍｏｌ）
Ｔ：絶対温度（°Ｋ）
すなわち、（１）式から、活性化エネルギーはとして求
められる。したがって、温度Ｔを変化させ、溶融粘度η
を測定し、１／Ｔに対してｌｏｇηをプロットするこで
得られた直線の傾きに気体定数Ｒを乗ずれば、活性化エ
ネルギー（Ｅａ）が求められる。η=A8E-/R” (1) However, η
: Melt viscosity (cps) A: Constant Ea: Activation energy for viscous fluidization (Kcal
/mol) R: gas constant (1,987cal/deg, mol)
T: Absolute temperature (°K) That is, from equation (1), the activation energy is determined as: Therefore, by changing the temperature T, the melt viscosity η
Activation energy (Ea) can be obtained by multiplying the slope of the straight line obtained by measuring and plotting log η against 1/T by the gas constant R.
すなわち、本発明の記録媒体を画像形成に供するに好ま
しい画像形成方法は前述したように、光および熱エネル
ギーを付与することで画像情報に応じた転写像を形成し
た後、例えば加熱等の処理によって該転写像を被転写体
に転写可能な状態にして転写する方法であるため、該転
写体の流動開始温度と、粘性流動化のための活性化エネ
ルギーは最終的に得られる転写画像の画質に大きく影響
する。すなわち、流動開始温度が４０℃より低い場合に
は、前述した転写像形成のプロセスにおいて、非転写像
部、すなわち、光エネルギーを付与するが熱エネルギー
は付与されない場合、具体的な例としてのサーマルヘッ
ドを加熱しない場合にも、記録媒体の物性が変化してし
まい、実質的に転写プロセスにおける転写部、非転写部
に差異がなくなり、画像が得られないか、コントラスト
の悪い画像となる。That is, as described above, a preferable image forming method for subjecting the recording medium of the present invention to image formation is to form a transfer image according to image information by applying light and thermal energy, and then to perform a treatment such as heating. Since this is a method of transferring the transferred image in a transferable state to the transfer target, the flow start temperature of the transfer body and the activation energy for viscous fluidization affect the quality of the final transferred image. It has a big impact. That is, when the flow start temperature is lower than 40°C, in the above-mentioned transfer image formation process, there is a non-transfer image area, that is, when light energy is applied but no thermal energy is applied, thermal energy as a specific example. Even when the head is not heated, the physical properties of the recording medium change, and there is virtually no difference between transferred and non-transferred areas in the transfer process, resulting in no image being obtained or an image with poor contrast.
さらに流動開始温度が１２０℃を越えるものは、転写像
形成のための熱エネルギーが極めて高くなって、転写像
形成のためのスピードが遅くなり、結果的に実用的な記
録スピードでは転写部と非転写部に差異がなくなり、こ
れまた画像が得られないかコントラストの悪い画像とな
る。Furthermore, if the flow start temperature exceeds 120°C, the thermal energy for forming a transferred image becomes extremely high, and the speed for forming a transferred image becomes slow. As a result, at a practical recording speed, the transfer part and the There will be no difference in the transfer area, and either no image will be obtained or an image with poor contrast will result.
すなわち、光および熱エネルギーまたは熱に変換するエ
ネルギーの同時付与によって記録媒体の転写特性を支配
する物性が変化す、ることで転写像が形成され得る記録
媒体の実用的な転写像コントラストを大にするためには
、該転写記録媒体の流動開始温度が少なくとも４０℃以
上１２０℃以下であることか必要である。In other words, the physical properties governing the transfer characteristics of the recording medium are changed by the simultaneous application of light and thermal energy or energy converted into heat, thereby greatly increasing the practical transferred image contrast of the recording medium on which the transferred image can be formed. In order to achieve this, it is necessary that the flow start temperature of the transfer recording medium is at least 40°C or more and 120°C or less.
さらに、このようにして得られた転写像を、被転写記録
媒体に転写する際に得られる転写画像に明確なコントラ
ストと、解像度を広い転写条件で得るためには、すなわ
ち実際には圧力、または熱または圧力および熱を印加す
る際の条件の広いラチチュードを得るためには、流動開
始温度以上での加圧時の粘度が被転写記録媒体に転写さ
れ得るのに充分な粘度を存し、かつ、粘度変化の温度依
存性、すなわち、前述した粘性流動化のための活性化エ
ネルギーが５から８０にｃａｌ／ｍｏｌの範囲であるの
が好ましい。Furthermore, in order to obtain clear contrast and resolution in the transferred image obtained in this way to a recording medium under a wide range of transfer conditions, pressure or In order to obtain a wide latitude in the conditions when applying heat or pressure and heat, the viscosity at the time of application of pressure above the flow initiation temperature is sufficient to enable transfer to the recording medium to be transferred, and The temperature dependence of the viscosity change, that is, the activation energy for the above-mentioned viscous fluidization is preferably in the range of 5 to 80 cal/mol.
該活性化エネルギーが５より小さい場合には、転写画像
部の記録媒体が、被転写記録媒体に転写される際に充分
な付着力が発生せず転写効率が低下し、実用に充分な画
像濃度が得られないか、付着のための多大な熱エネルギ
ーまたは圧力を必要とし、望ましくない。また、該活性
化エネルギーが８０ Ｋｃａｌ／＋ｏｌより大きい場合
には、付着力は充分であるが、転写の際の温度が高い場
合には記録媒体が低粘度すぎて、被膜性が不良となり部
分転写してしまい、これまた転写効率が低下し、コント
ラストの低下や解像度の低下が発生しやすい。If the activation energy is less than 5, sufficient adhesive force will not be generated when the recording medium in the transferred image area is transferred to the recording medium to be transferred, resulting in a decrease in transfer efficiency, and the image density will not be sufficient for practical use. or require significant thermal energy or pressure for adhesion, which is undesirable. If the activation energy is greater than 80 Kcal/+ol, the adhesion is sufficient; however, if the temperature during transfer is high, the viscosity of the recording medium is too low, resulting in poor coating properties and partial transfer. This also reduces the transfer efficiency and tends to cause a decrease in contrast and resolution.
なお、上述のような特定された物性を有する転写記録層
は、例えば後述の実施例に示されているような代表的方
法によって形成可能である。Note that the transfer recording layer having the specified physical properties as described above can be formed, for example, by a typical method as shown in Examples below.
以上説明したように、光を含む複数種のエネルギーをそ
れらのうち少くとも一種のエネルギーを画像記録情報に
対応させて同時に付与することにより、その転写特性を
支配する物性が変化する転写記録層を支持体上に有する
記録媒体であって、該転写記録層が、
ａ）着色剤と、
ｂ）光重合開始剤と、
Ｃ）不飽和二重結合を有するモノマー、オリゴマー及び
ポリマーからなる群より選択された１種以上とを含む、
光エネルギー及び熱または熱エネルギーに変換しつるエ
ネルギーの付与によって感応する感応成分
を含み、該転写記録層の流動開始温度が４０℃以上１２
０℃以下の温度範囲内にあり、かつその粘性流動化のた
めの活性化エネルギーが５〜８０にｃａｌ／ｍｏｌの範
囲であることを特徴とする本発明の記録媒体により、高
品位の画像を形成で中間調記録が可能でさらに多色記録
画像が容易に安価に形成できるようになった。As explained above, by simultaneously applying multiple types of energy, including light, at least one type of energy corresponding to image recording information, a transfer recording layer whose physical properties governing its transfer characteristics change can be created. A recording medium on a support, the transfer recording layer comprising: a) a colorant; b) a photopolymerization initiator; and C) a monomer, oligomer, and polymer having an unsaturated double bond. including one or more types of
Contains a sensitive component that is sensitive to the application of light energy and heat or energy that converts into thermal energy, and the flow start temperature of the transfer recording layer is 40°C or higher12
High-quality images can be produced using the recording medium of the present invention, which is within a temperature range of 0°C or lower and has an activation energy for viscous fluidization in the range of 5 to 80 cal/mol. It is now possible to record halftones during formation, and furthermore, it has become possible to easily and inexpensively form multicolor recorded images.
さらに、表面平滑度の低い一般的に用いられる曽通紙に
も鮮明なかぶりのない記録画像が得られる記録媒体が提
供できるようになった。Furthermore, it has become possible to provide a recording medium that can produce clear, fog-free recorded images even on commonly used paper sheets with low surface smoothness.
さらに、光および熱または夏に変換しつるエネルギーを
転写像形成手段として用いることができるため、デジタ
ル画像の記録が容易に形成できるようになった。Additionally, digital image records can now be easily formed because light and heat or solar energy converted to summer can be used as a transfer image forming means.
さらに、本発明の記録場他意は、光および熱または熱に
変換しうるエネルギーを同時に付与して初めて転写像が
形成されるものであるため、高感度記録と保存安定性の
両方を同時に満足させることが可能となった。Furthermore, the recording field of the present invention is unique in that a transferred image is formed only when light and heat or energy that can be converted into heat is applied simultaneously, so that both high-sensitivity recording and storage stability are satisfied at the same time. It became possible.
（実施例）
以下本発明を実施例に従い説明するが、これに限定され
るものではない。(Example) The present invention will be described below with reference to Examples, but is not limited thereto.
実施例１
第１表に示す成分をジクロルメタン溶剤に溶解せしめ、
厚さ６μのポリエチレンテレフタレートフィルム上にラ
ンベントコート法により乾燥時に厚さ４戸となるように
塗布した。該塗布膜上にポリビニルアルコール（Ｍｗ＝
１２００）水溶液をランベントコート法にて塗布し酸
素防止膜（膜厚１〇−）を形成し本発明の記録媒体を得
た。Example 1 The components shown in Table 1 were dissolved in dichloromethane solvent,
It was coated onto a polyethylene terephthalate film with a thickness of 6 μm by the lambent coating method so that the film had a thickness of 4 coats when dried. Polyvinyl alcohol (Mw=
1200) Aqueous solution was coated by the lambent coating method to form an oxygen-preventing film (thickness: 10 -) to obtain a recording medium of the present invention.
次に上記手法により作製した試料をロール状に巻き回し
て第３図に示す装置に組み込んだ。Next, the sample prepared by the above method was wound into a roll and incorporated into the apparatus shown in FIG. 3.
サーマルヘッド４としては８ドツト／ｍｒｎのＡ−４サ
イズのライン・タイプで発熱素子列がエツジ部に配列さ
れているものを用い、記録媒体１の支持体側が発熱素子
に接する様に配し、記録媒体１のテンションにより発熱
素子に押圧される様にした。そして対向した部所にケミ
カルランプ（発光ピーク３９０ｍｍ、東芝（株）製ＦＬ
１０Ａ７０Ｅ３９） ３を配置した。The thermal head 4 is an A-4 size line type with 8 dots/mrn and heat generating element rows are arranged at the edge portion, and is arranged so that the support side of the recording medium 1 is in contact with the heat generating elements. The tension of the recording medium 1 was made to press against the heating element. A chemical lamp (emission peak: 390 mm, FL manufactured by Toshiba Corporation) was installed in the opposite area.
10A70E39) 3 was placed.
次に画信号に応じてサーマルヘッドの発熱を制御する。Next, the heat generation of the thermal head is controlled according to the image signal.
本実施例においては光と熱が与えられてガラス転移点が
上昇すると共に転写開始温度が上昇する転写記録層を扱
う為、ネガ記録となる。即ちサーマルヘッドの制御はマ
ーク信号（黒）の場合は通電せずマーク信号でない（白
）の時に通電して発熱させる。In this embodiment, since the transfer recording layer is treated with light and heat applied to raise the glass transition point and the transfer start temperature, negative recording is performed. That is, the thermal head is controlled such that it does not conduct electricity when a mark signal (black) is present, but conducts current when it is not a mark signal (white) to generate heat.
此の発熱時の通電エネルギーは０．８ｗ／ｄｏｔ ｘ２
０ｍｓｅｃであった。こうしてケミカルランプで光照射
を一様にしながら上記した様な要領で画信号に応じてサ
ーマルヘッドを制御、駆動し５０ｍ５ｅｃ／Ｉｉ、ｎｅ
の繰り返し周期で同期して記録媒体をスッテピングモー
タとドライブゴムロールで搬送した。The energizing energy during this heat generation is 0.8w/dot x2
It was 0 msec. In this way, the thermal head is controlled and driven in accordance with the image signal in the manner described above while uniformly irradiating light with the chemical lamp.
The recording medium was conveyed synchronously with a stepping motor and a drive rubber roll at a repeating period of .
次いでポリビニルアルコール膜を除去し、第４図に示す
様に転写工程において表面平滑度１０〜３０秒の範囲に
ある普通紙１０を転写記録層に重ねて、ビートロール８
とピンチロール９とで挟んで搬送した。ヒートロール８
は３００Ｗのヒータ７を内部に持ち、表面を２ｍｍ厚さ
のシリコンゴムで被覆したアルミロールで表面を５０〜
１５０℃の範囲の任意の温度に保つ様ヒータを制御した
。ピンチロール９はＪＩＳゴム硬度計の硬度５０°のシ
リコンゴムロールで膜厚を１〜１．５Ｋｇ／ｃｒｎ’と
した。Next, the polyvinyl alcohol film is removed, and as shown in FIG.
and pinch rolls 9 and transported. heat roll 8
has a 300W heater 7 inside, and the surface is covered with an aluminum roll coated with 2mm thick silicone rubber.
The heater was controlled to maintain a desired temperature within the range of 150°C. The pinch roll 9 was a silicone rubber roll having a hardness of 50° as measured by a JIS rubber hardness meter, and had a film thickness of 1 to 1.5 kg/crn'.
ビートロール８の５０℃〜１５０℃の温度範囲内で、普
通紙は転写記録層に重ねて搬送した後、これらを剥離し
たところ普通紙上に定着性の良好なかぶりのない高品位
画像を形成できた。When the plain paper was conveyed over the transfer recording layer within the temperature range of 50°C to 150°C of the beat roll 8 and then peeled off, a high-quality image with good fixability and no fogging could be formed on the plain paper. Ta.
その際、非画像部すなわち光と熱が同時に印加された部
分は、 １５０℃の温度でも普通紙に転写せず、画像部
は６０℃の温度で転写し、転写温度のコントラストが９
０℃と高く、転写条件のラチチュードの広い結果であっ
た。また、前記記録媒体を室温で６ケ月間保存した後で
も、同様の結果であった。 なお、第１表に示した組成
体を高化式フローテスター（島津製作所）を用いオリフ
ィス径１ｍｍのオリフィス内より荷重２０Ｋｇ／ｃ♂を
印加しなから一定昇温速度で加熱し、流出させ、その流
動開始温度を前述した方法に従って測定したとこと４５
℃であった。さらに４５℃以上１５０℃までの粘度（η
）を測定し、得られた結果について１／Ｔに対し、ｌｏ
ｇηをプロットし、得られら直線の傾きから粘性流動化
のための活性化エネルギーを求めたところ２３Ｋｃａｌ
／ｍｏｌであった。At that time, the non-image area, that is, the area where light and heat were applied at the same time, was not transferred to plain paper even at a temperature of 150°C, and the image area was transferred at a temperature of 60°C, with a transfer temperature contrast of 9.
The temperature was as high as 0°C, and the latitude of the transfer conditions was wide. Furthermore, similar results were obtained even after the recording medium was stored at room temperature for 6 months. In addition, the composition shown in Table 1 was heated at a constant temperature increase rate while applying a load of 20 kg/c♂ from the inside of an orifice with an orifice diameter of 1 mm using a Koka type flow tester (Shimadzu Corporation), and allowed to flow out. The flow initiation temperature was measured according to the method described above45.
It was ℃. Furthermore, the viscosity (η
), and for the obtained results, lo
The activation energy for viscous fluidization was determined from the slope of the obtained straight line by plotting gη and found to be 23 Kcal.
/mol.
実施例２
第２表に示す成分を用い実施例１と同様の方法で記録媒
体を作成し、同様の方法で画像を得たところ普通紙−ヒ
に定着性の良好なかぶりのない高品位画像を形成できた
。その際、非画像部は１５０℃の温度でも転写せず、画
像部は７０℃の温度で転写し、転写温度のコントラスト
が８０℃と高かった。Example 2 A recording medium was prepared using the components shown in Table 2 in the same manner as in Example 1, and an image was obtained in the same manner. A high-quality image with good fixability and no fog was obtained on plain paper. was able to form. At that time, the non-image area was not transferred even at a temperature of 150°C, and the image area was transferred at a temperature of 70°C, and the transfer temperature contrast was as high as 80°C.
また、該記録媒体を室温で６ケ月間保存した後でも、同
様の結果が得られた。なお、第２表の組成体の流動開始
温度と、粘性流動化のための活性化エネルギーを実施例
１と同様にして求めたところ、それぞれ８０℃、７にｃ
ａｌ／ｍｏ＋であった。Further, similar results were obtained even after storing the recording medium at room temperature for 6 months. The flow initiation temperature and activation energy for viscous fluidization of the compositions shown in Table 2 were determined in the same manner as in Example 1, and were found to be 80°C and 7°C, respectively.
al/mo+.
実施例３
第３表に示す成分を用い実施例１と同様の方法で記録媒
体を作成し、同様の方法で画像を得たところ、同様に普
通紙上に定着性の良好なかぶりのない高品位画像を形成
できた。その際、非画像部は１５０℃の温度でも転写せ
ず、画像部は５０℃の温度で転写し、転写温度のコント
ラストは １００℃と高かった。また、該記録媒体を室
温で６ケ月間保存した後でも、同様の結果が得られた。Example 3 A recording medium was prepared in the same manner as in Example 1 using the components shown in Table 3, and an image was obtained in the same manner.As a result, a high quality image with good fixability and no fogging was obtained on plain paper. I was able to form an image. At that time, the non-image area was not transferred even at a temperature of 150°C, the image area was transferred at a temperature of 50°C, and the contrast in transfer temperature was as high as 100°C. Further, similar results were obtained even after storing the recording medium at room temperature for 6 months.
なお、第３表の組成体の流動開始温度と、粘性流動化の
ための活性化エネルギーを実施例１と同様にして求めた
ところ、それぞれ４２℃、５３Ｋｃａｌ／ｍｏｌであっ
た。The flow start temperature and activation energy for viscous fluidization of the compositions shown in Table 3 were determined in the same manner as in Example 1, and were found to be 42° C. and 53 Kcal/mol, respectively.
実施例４
第４表に示す成分を用い実施例１と同様の方法で記録媒
体を作成した。光源３を東芝（株）類ケミカルランプＦ
Ｌ１０Ａ７０Ｅ３５ （発光ビーク３３５ｎｍ）を用い
た他は、実施例１と同様に行ない画像を得たところ普通
紙上に定着性の良好なかぶりのない高品位画像を得た。Example 4 A recording medium was prepared in the same manner as in Example 1 using the components shown in Table 4. Light source 3 is Toshiba Corporation type chemical lamp F
An image was obtained in the same manner as in Example 1 except that L10A70E35 (emission peak: 335 nm) was used, and a high quality image with good fixability and no fog was obtained on plain paper.
その際、非画像部は１５０℃の温度でも転写せず、画像
部は５０℃の温度で転写し、転写温度のコントラストは
１００℃と高かった。また、また保存安定性も同様に良
好であった。なお、実施例１と同様にして測定した第４
表の組成体の流動開始温度と、粘性流動化のための活性
化エネルギーはそれぞれ４０℃、７５にｃａｌ／ｍｏｌ
であった。At that time, the non-image area was not transferred even at a temperature of 150°C, and the image area was transferred at a temperature of 50°C, and the transfer temperature contrast was as high as 100°C. Moreover, the storage stability was similarly good. In addition, the fourth
The flow initiation temperature and activation energy for viscous fluidization of the compositions in the table are 40°C and 75 cal/mol, respectively.
Met.
比較例１
結着性組成体として飽和共重合ポリエステル（ＳＰ−１
３１、日本合成化学工業製）６５重量％、重合性千ツマ
−
（Ｃｔ１２＝ ＣＨＣＯＯＣＨ２Ｇ）１２０ Ｃ０ＮＨ
（Ｘ２ ＣＨ２を１８重量％とじた他は実施例１と同様
に記録媒体を作成し、同様の方法で転写像形成し、転写
温度を調べたところ、画像部が１４０℃で転写し、非画
像部は１５０℃で転写した。しかも、画像も １４０℃
で部分的に転写するだけで、はとんど、転写像を再現で
きなかった。実施例１と同様にして測定した記録媒体に
用いた組成体の流動開始温度は １３０℃であり、粘性
流動化のための活性化エネルギーは８にｃａｌ／ｍｏｌ
であった。Comparative Example 1 Saturated copolymer polyester (SP-1
31, manufactured by Nippon Gosei Chemical Industry Co., Ltd.) 65% by weight, polymerizable 100% polymer (Ct12=CHCOOCH2G) 120 C0NH
(X2 A recording medium was prepared in the same manner as in Example 1 except that 18% by weight of CH2 was added, a transfer image was formed in the same manner, and the transfer temperature was examined. The part was transferred at 150℃.The image was also transferred at 140℃.
The transfer image could only be partially transferred, and the transferred image could not be reproduced. The flow initiation temperature of the composition used in the recording medium measured in the same manner as in Example 1 was 130°C, and the activation energy for viscous fluidization was 8 cal/mol.
Met.
比較例２
結着性組成体として酸化ワックスＮＦＳ−９０３５（日
本精蝋社製）を６０重量％、重合性モノマー（ＣＨ２＝
ＯＨ（：００ＣＨ２（：）１２０ Ｃ０ＮＨ＋２ Ｃ
Ｈ２を２３重量％とし、溶剤としてキシレンを用いた他
は実施例１と同様に記録媒体を作成し、同様の方法で転
写像を形成し、転写温度を調べたところ、画像部が４０
℃で転写し、非画像部は６０℃で転写し、転写温度のコ
ントラストは２０℃と小さかった。しかも、非画像部に
まだら状のカブリが生じた。記録媒体に用いた組成体の
流動開始温度は４０℃であり、粘性流動化のための活性
化エネルギーは４５にｃａｌ／ｌｌ１ｏｌであった。Comparative Example 2 60% by weight of oxidized wax NFS-9035 (manufactured by Nippon Seiro Co., Ltd.) as a binding composition and a polymerizable monomer (CH2=
OH(:00CH2(:)120 C0NH+2C
A recording medium was prepared in the same manner as in Example 1 except that H2 was 23% by weight and xylene was used as the solvent, a transfer image was formed in the same manner, and the transfer temperature was checked.
The transfer was carried out at 60°C, and the non-image area was transferred at 60°C, and the transfer temperature contrast was as small as 20°C. Moreover, mottled fogging occurred in non-image areas. The fluidization start temperature of the composition used for the recording medium was 40° C., and the activation energy for viscous fluidization was 45 cal/llol.
実施例５
第２表、及び′：ｌｃＪ表に示す成分を個々に、下記の
方法に従ってマイクロカプセル化した。Example 5 The components shown in Table 2 and ':lcJ Table were individually microencapsulated according to the following method.
すなわち、まず各々の組成体１０ｇを個々に塩化メチレ
ン２０重量部に混合したもを、カチオン又はノニオン等
ＨＬＢ値の少なくとも１０以上の界面活性剤とゼラチン
１ｇを溶解した水２００ｍ１に混合し、６０℃加温下ホ
モミキサーによって、８，０００〜１０，０００ｒ ｐ
ｍで撹拌して乳化し、平均粒径２６μの油滴を得る。That is, first, 10 g of each composition was individually mixed with 20 parts by weight of methylene chloride, mixed with 200 ml of water in which 1 g of gelatin and a surfactant such as a cationic or nonionic surfactant with an HLB value of at least 10 was dissolved, and the mixture was heated at 60°C. 8,000-10,000 rpm using a homomixer under heating
Stir at m to emulsify and obtain oil droplets with an average particle size of 26 μm.
更に６０℃下で撹拌を３０分間続は塩化メチレンを留去
することにより平均粒径をｌＯｕ＋とした。これにアラ
ビアゴム１ｇを溶かした水２０ｍ ｌを加え、ゆっくり
冷却しながらＮ１１４叶（アンモニア）水を添加しｐＨ
１１以上にすることによってマイクロカプセルスラリー
を得、こわにグルタルアルデヒド２０％水溶液１．０ｍ
ｌをゆっくり加えてカプセル壁を硬化させた。Stirring was further continued at 60° C. for 30 minutes, and methylene chloride was distilled off to give an average particle size of lOu+. Add 20ml of water in which 1g of gum arabic was dissolved, and add N114 ammonia water while cooling slowly to adjust the pH.
11 or more to obtain a microcapsule slurry, and then add 1.0 m of a 20% glutaraldehyde aqueous solution.
1 was added slowly to harden the capsule walls.
次に、ヌッチェ濾過器で個液分離し、真空乾燥器で３５
℃、１０時間乾燥してマイクロカプセル状の計２種の画
像形成素体を得た。Next, separate the individual liquids using a Nutsche filter, and use a vacuum dryer to
C. for 10 hours to obtain a total of two types of image forming elements in the form of microcapsules.
前記の如くして形成された平均粒径１０μの２種の画像
形成素体を等全混合し、ＰＶＡ５％水溶液に界面活性剤
を１００ｃｃ当たり数滴垂らしてなる付着剤１ｆを用い
て厚さ６鱗のポリエチレンテレフタレートフィルムより
なる支持体１ａ上に付着して転写記録層１ｂを形成しこ
れによって転写記録媒体ｌを構成した。これを第５図に
示す。The two types of image forming elements having an average particle size of 10 μm formed as described above were thoroughly mixed, and the adhesive 1f made by dropping a few drops of a surfactant per 100 cc in a 5% PVA aqueous solution was used to form a film with a thickness of 6 μm. A transfer recording layer 1b was formed by adhering to a support 1a made of a scaled polyethylene terephthalate film, thereby constituting a transfer recording medium 1. This is shown in FIG.
上記転写記録媒体をロール状に巻き回して第３ａ図に示
す装置に組み込んだ。ここで３で示される光源の代りに
、両組成体の吸収特性に対応させた第３ｂ図に示すよう
な２種の、すなわち発光ピーク波長３３５ｎｍ （東芝
製ｆｌｌＯＡ７０Ｅ３９）及び発光ピーク波長３９０ｒ
＋ｍ （東芝製ＦＬＩＯ＾７０Ｅ３９）の蛍光灯を並列
に配置し、記録媒体面との間に１＋ｎｍ幅のスリットを
介して照射できるものとした。The transfer recording medium was wound into a roll and incorporated into the apparatus shown in FIG. 3a. Here, instead of the light source shown in 3, two kinds of light sources as shown in FIG.
+m (FLIO^70E39 manufactured by Toshiba) fluorescent lamps were arranged in parallel and could be irradiated through a slit with a width of 1+ nm between them and the surface of the recording medium.
転写記録層１ｂは所定波長の光と熱とが付与されると転
写特性が変化し、記録紙１０に転写されなくなる性質を
有している為に第６図のタイミングチャートに示すよう
に、赤色記録に際しては発熱素子列のうち画信号の赤に
相当する発熱素子に通電せず、画信号の白（記録媒体１
０は白色とする）に相当する部分に２５ＩＩｌｓの通電
を行ない、５ｆｆＩＳの遅れをもって蛍光灯３ｂを一様
に照射した。When the transfer recording layer 1b is exposed to light and heat of a predetermined wavelength, its transfer characteristics change and it no longer transfers to the recording paper 10, so as shown in the timing chart of FIG. During recording, power is not applied to the heating elements of the heating element array that correspond to the red color of the image signal, and the white color of the image signal (recording medium 1
A current of 25 IIls was applied to the portion corresponding to the color (0 is white), and the fluorescent lamp 3b was uniformly irradiated with a delay of 5ffIS.
このときの照射時間は４５ＩＩＳとした。The irradiation time at this time was 45 IIS.
次に黒色記録に際しては、前記照射終了（ｆｉ５０ＩＩ
ＩＳ経過してから、即ち前記通電時間より １００ｏｓ
後に今度は発熱素子列のうち画信号の黒に相当する発熱
素子には通電せずに画信号の白に相当する部分に２５ｍ
５の通電を行い、Ｓｍｓ後に蛍光灯３Ｃを一様に照射す
る。このときの照射時間も前記と同様に４５ｍ５である
。Next, when recording black, the irradiation is completed (fi50II
100 os after IS elapsed, that is, from the above-mentioned energization time
Later, in the heating element row, the heating element corresponding to the black of the image signal was not energized, and the part corresponding to the white of the image signal was heated for 25 m.
5, and after SMS, the fluorescent lamp 3C is uniformly irradiated. The irradiation time at this time was also 45 m5 as described above.
以上のような要領で赤、黒、白の画信号に応じて、サー
マルヘッド４を制御して転写記録層１ｂにネガ像（転写
像）を形成し、 ２００ａ＋ｓ／ ｌ１ｎｃの繰り返し
周期で同期して転写記録媒体１を更に搬送した。第４図
に示した転写部に置いて、前記転写像が形成された転写
記録層１ｂを記録紙１０に圧接して加熱することによっ
て赤、黒２色の転写像を記録紙１０に転写することが出
来た。その後、剥離ローラ５によってこれらを剥離し、
所望の色の画像記録を記録紙１０上に得た。In the manner described above, a negative image (transfer image) is formed on the transfer recording layer 1b by controlling the thermal head 4 according to the red, black, and white image signals, and is synchronized with a repeating cycle of 200a+s/l1nc. The transfer recording medium 1 was further conveyed. Placed in the transfer section shown in FIG. 4, the transfer recording layer 1b on which the transferred image has been formed is pressed against the recording paper 10 and heated, thereby transferring the red and black two-color transfer images onto the recording paper 10. I was able to do it. After that, these are peeled off by a peeling roller 5,
An image record of the desired color was obtained on recording paper 10.
上記の如くして２色記録がワンショットで行われ、画像
信号に忠実な高品位画像が得られた。Two-color recording was performed in one shot as described above, and a high-quality image faithful to the image signal was obtained.
尚、第７図に第２表に示す成分の開始剤の吸収スペクト
ルＡ、第４表に示す成分の開始剤の吸収スペクトルＢ及
び第８図に使用した二種の蛍光灯の発光スペクトルを示
す。Furthermore, Figure 7 shows the absorption spectrum A of the initiator having the components shown in Table 2, the absorption spectrum B of the initiator having the components shown in Table 4, and the emission spectrum of the two types of fluorescent lamps used in Figure 8. .
第１表 第２表 第３表 第４表Table 1 Table 2 Table 3 Table 4
第１ａ図、第１ｂ図、第１ｃ図および第１ｄ図は光と熱
エネルギーにより転写像を形成する場合の転写像形成の
原理を説明する図、第２図は本発明の記録媒体を用いた
記録方法の一例の工程図、第３ａ図、第３ｂ図及び第４
図は本発明の記録媒体を用いた記録方法に用いることの
できる記録装置の主要構成部の該略図、第５図は本発明
に於てカラー記録を実施する為、転写記録材料をマイク
ロカプセル化し、基材フィルム像に担持した形態を示す
図、第６図は熱および光を付与するタイミングチャート
、第７図は実施例５において、２種の組成体中に含有さ
れた光重合開始剤の吸収スペクトル、第８図は実施例５
に於いて、用いた蛍光灯の発光スペクトルである。
１は転写記録媒体、１ｂは転写記録層、２は供給ロール
３はランプ（３ｂ、３ｃは二色作画に用いる光源である
。）、４はサーマルヘッド、５は制御回路、７はヒータ
ー、８はビートローラ、９はピンチローラ、１０は普通
紙、１１は巻取りロール、１２は記録画像である。Figures 1a, 1b, 1c, and 1d are diagrams explaining the principle of forming a transferred image using light and thermal energy, and Figure 2 is a diagram illustrating the principle of forming a transferred image using the recording medium of the present invention. Process diagram of an example of the recording method, Figures 3a, 3b, and 4
The figure is a schematic diagram of the main components of a recording device that can be used in the recording method using the recording medium of the present invention, and FIG. FIG. 6 is a timing chart for applying heat and light, and FIG. 7 is a diagram showing the form of the photopolymerization initiator contained in the two types of compositions in Example 5. Absorption spectrum, Figure 8 is Example 5
This is the emission spectrum of the fluorescent lamp used. 1 is a transfer recording medium, 1b is a transfer recording layer, 2 is a supply roll 3 is a lamp (3b and 3c are light sources used for two-color printing), 4 is a thermal head, 5 is a control circuit, 7 is a heater, 8 1 is a beat roller, 9 is a pinch roller, 10 is plain paper, 11 is a winding roll, and 12 is a recorded image.
Claims (5)
とも一種のエネルギーを画像記録情報に対応させて同時
に付与することにより、その転写特性を支配する物性が
変化する転写記録層を支持体上に有する記録媒体であっ
て、 該転写記録層が、 ａ）着色剤と、 ｂ）光重合開始剤と、 ｃ）不飽和二重結合を有するモノマー、オリゴマー及び
ポリマーからなる群より選択された１種以上とを含み、
光エネルギー及び熱または熱エネルギーに変換しうるエ
ネルギーの付与によって感応する感応成分 を含み、該転写記録層の流動開始温度が４０℃以上１２
０℃以下の温度範囲内にあり、かつその粘性流動化のた
めの活性化エネルギーが５〜８０Ｋｃａｌ／ｍｏｌの範
囲であることを特徴とする記録媒体。(1) By simultaneously applying multiple types of energy, including light, at least one type of energy corresponding to image recording information, a transfer recording layer whose physical properties governing its transfer characteristics change can be formed on a support. A recording medium comprising: a) a colorant; b) a photopolymerization initiator; and c) a monomer, oligomer, or polymer having an unsaturated double bond. including more than one species;
Contains a sensitive component that is sensitive to the application of light energy and heat or energy that can be converted into heat energy, and the flow start temperature of the transfer recording layer is 40°C or higher12
1. A recording medium having a temperature range of 0° C. or lower and an activation energy for viscous fluidization in a range of 5 to 80 Kcal/mol.
層状に担持されていることを特徴とする特許請求の範囲
第１項記載の記録媒体。(2) The recording medium according to claim 1, wherein the sensitive component is physically or chemically supported in a layered manner on a support.
る特許請求の範囲第１項および第２項記載の記録媒体。(3) The recording medium according to claims 1 and 2, wherein the sensitive component is a particulate element.
がそれぞれ異なる複数種の素体を支持体上に混合状態で
担持したことを特徴とする特許請求の範囲第１項から第
３項記載の記録媒体。(4) Claims 1 to 3 are characterized in that a plurality of types of elements having different sensitivity wavelength ranges of sensitive components contained in the particulate element are supported in a mixed state on a support. Recording medium described in section.
されていることを特徴とする特許請求の範囲第１項から
第４項記載の記録媒体。(5) The recording medium according to any one of claims 1 to 4, wherein the particulate element containing the sensitive component is encapsulated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61285863A JPH07111578B2 (en) | 1986-12-02 | 1986-12-02 | recoding media |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61285863A JPH07111578B2 (en) | 1986-12-02 | 1986-12-02 | recoding media |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63139335A true JPS63139335A (en) | 1988-06-11 |
| JPH07111578B2 JPH07111578B2 (en) | 1995-11-29 |
Family
ID=17697020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61285863A Expired - Fee Related JPH07111578B2 (en) | 1986-12-02 | 1986-12-02 | recoding media |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07111578B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0229651A (en) * | 1988-07-19 | 1990-01-31 | Canon Inc | Recording medium |
| JPH0387827A (en) * | 1989-08-31 | 1991-04-12 | Fuji Photo Film Co Ltd | Photosensitive and thermosensitive recording material |
| US8951153B2 (en) | 2009-06-19 | 2015-02-10 | Mitsuboshi Belting Ltd. | Power transmission mechanism |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6159448A (en) * | 1984-08-23 | 1986-03-26 | ザ、ミード、コーポレーシヨン | Photosensitive image forming material using capsulization radio-sensitive composition having improved tone quality |
| JPS6161150A (en) * | 1984-08-23 | 1986-03-28 | ザ、ミード、コーポレーシヨン | Photosensitive image formation system using oil-filled microcapsule |
| JPS61114234A (en) * | 1984-10-09 | 1986-05-31 | ザ・ミ−ド・コ−ポレ−シヨン | Image system employing photosensitive microcapsule containing 3-substituted coumalin and other photo bleachablesensitizer |
| JPS61200535A (en) * | 1985-02-28 | 1986-09-05 | Fuji Photo Film Co Ltd | Image receiving sheet |
-
1986
- 1986-12-02 JP JP61285863A patent/JPH07111578B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6159448A (en) * | 1984-08-23 | 1986-03-26 | ザ、ミード、コーポレーシヨン | Photosensitive image forming material using capsulization radio-sensitive composition having improved tone quality |
| JPS6161150A (en) * | 1984-08-23 | 1986-03-28 | ザ、ミード、コーポレーシヨン | Photosensitive image formation system using oil-filled microcapsule |
| JPS61114234A (en) * | 1984-10-09 | 1986-05-31 | ザ・ミ−ド・コ−ポレ−シヨン | Image system employing photosensitive microcapsule containing 3-substituted coumalin and other photo bleachablesensitizer |
| JPS61200535A (en) * | 1985-02-28 | 1986-09-05 | Fuji Photo Film Co Ltd | Image receiving sheet |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0229651A (en) * | 1988-07-19 | 1990-01-31 | Canon Inc | Recording medium |
| JPH0387827A (en) * | 1989-08-31 | 1991-04-12 | Fuji Photo Film Co Ltd | Photosensitive and thermosensitive recording material |
| US8951153B2 (en) | 2009-06-19 | 2015-02-10 | Mitsuboshi Belting Ltd. | Power transmission mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07111578B2 (en) | 1995-11-29 |
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