JP6845788B2 - Xerographic recording material - Google Patents
Xerographic recording material Download PDFInfo
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- JP6845788B2 JP6845788B2 JP2017221586A JP2017221586A JP6845788B2 JP 6845788 B2 JP6845788 B2 JP 6845788B2 JP 2017221586 A JP2017221586 A JP 2017221586A JP 2017221586 A JP2017221586 A JP 2017221586A JP 6845788 B2 JP6845788 B2 JP 6845788B2
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- toner
- recording material
- resin
- receiving layer
- electrophotographic
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- Paper (AREA)
Description
本発明は黄変耐性及び高いトナー定着性を有し、印刷後の記録材料の捌き性に優れた電子写真記録材料に関するものである。 The present invention relates to an electrophotographic recording material having yellowing resistance and high toner fixability, and excellent handling property of the recording material after printing.
電子写真方式による記録は、複写機をはじめ、端末のプリント出力、ファクシミリ、少部数印刷など様々な分野に適用されている。出力装置の進歩も著しく、印刷速度は向上し、フルカラーは言うに及ばず、トナーの改良により高精細化を達成し、色再現性も大きく向上し、文書出力から写真出力まで様々な用途に使用されるようになってきた。 Recording by the electrophotographic method is applied to various fields such as copiers, terminal print output, facsimile, and small number of copies printing. The progress of the output device is remarkable, the printing speed is improved, not to mention full color, high definition is achieved by improving the toner, the color reproducibility is greatly improved, and it is used for various purposes from document output to photographic output. It has come to be done.
このような電子写真方式のうち、乾式電子写真方式は、複写機などに代表される方式で、画像を形成するトナーは、顔料と合成樹脂からなる固体粉末トナーを使用する。画像形成方法は、コロナ帯電によって発生させた感光体ロール上の静電画像にトナーが吸着し、さらにトナーが記録材料に転写し、転写された記録材料を定着ロールで加熱することによりトナーが定着し画像形成する方式である。かかる方式では、トナーの微細化に限界があり、高解像度が得られ難い。また、画線部のトナー定着部分の光沢が高くなり、非画線部と光沢差が生じて、不自然な描写になる等の不具合がある。 Among such electrophotographic methods, the dry electrophotographic method is a method typified by a copying machine or the like, and a solid powder toner composed of a pigment and a synthetic resin is used as the toner for forming an image. In the image forming method, the toner is adsorbed on the electrostatic image on the photoconductor roll generated by corona charging, the toner is further transferred to the recording material, and the transferred recording material is heated by the fixing roll to fix the toner. This is a method of forming an image. With this method, there is a limit to the miniaturization of toner, and it is difficult to obtain high resolution. In addition, there is a problem that the gloss of the toner fixing portion of the image portion becomes high, a gloss difference occurs from the non-image portion, and the depiction becomes unnatural.
一方で、湿式電子写真方式では、液体中にトナーを分散させるため、固体粉末トナーの飛散などが問題とならず、乾式電子写真方式に比べてトナーの大きさを１／１０以下まで微細化できるとの利点がある。すなわち画線部を形成するドットを微細にできること、加えて色材として顔料を使用できるために耐候性の問題がないことを特徴とし、さらに画線部と非画線部との光沢差を生じることがなく、写真出力に好適な方式である。 On the other hand, in the wet electrophotographic method, since the toner is dispersed in the liquid, scattering of solid powder toner does not become a problem, and the toner size can be reduced to 1/10 or less as compared with the dry electrophotographic method. There is an advantage with. That is, the dots forming the image area can be made fine, and since the pigment can be used as the coloring material, there is no problem of weather resistance, and a gloss difference between the image area and the non-image area is generated. This method is suitable for photographic output.
湿式トナーは記録材料への転写に先立って、あるいは記録材料にトナーが転写された後に乾燥させることによって、湿式トナー中の溶媒を取り除き画像が形成される。記録材料への転写に先立って湿式トナー中の溶媒を取り除く場合には、おおよそ６０〜１２０℃に加熱されたブランケットロールが利用される。該ブランケットロールの熱により溶媒成分が取り除かれ、トナーが熱溶融して粘着性が生じ記録材料に画像が転写される。一方、トナーが転写された後に乾燥させる場合には、溶剤を含有する湿式トナーを転写させた記録材料を加熱して、記録材料上で溶媒を取り除き、かつトナーを熱溶融し定着する。 The wet toner is dried prior to transfer to the recording material or after the toner is transferred to the recording material to remove the solvent in the wet toner and form an image. When removing the solvent in the wet toner prior to transfer to the recording material, a blanket roll heated to approximately 60-120 ° C. is utilized. The solvent component is removed by the heat of the blanket roll, the toner is hot-melted to cause stickiness, and the image is transferred to the recording material. On the other hand, when the toner is transferred and then dried, the recording material to which the wet toner containing a solvent is transferred is heated to remove the solvent on the recording material, and the toner is hot-melted and fixed.
このように湿式電子写真においては、記録材料に画像を転写するときには電荷の作用を利用せず、例えば前者の方法、すなわち加熱されたブランケットロールから記録材料に画像を転写する方法においては、湿式トナーと記録材料との接着性が、湿式トナーとブランケットロールの接着性よりも高くなるようにして画像を転写させる。つまりブランケットロールから記録材料への湿式トナーの転写能力が重要である。記録材料とトナーの接着性を高める目的でトナー自身の接着能力を必要以上に高くすると、記録材料への定着は良くなる一方で、それと同時にブランケットロールとトナーの接着性も高まることとなりブランケットロールからトナーが剥がれにくくなるため、結局、トナーの接着能力を高くすることはできない。このため、加熱されたブランケットロールから記録材料に画像を転写する方式の場合、印刷をしてもトナー粒子が十分に転写しない、あるいは十分なトナー強度が得られないといった欠点があった。トナーの転写が十分でなく不完全であると、ブランケットロール表面にトナーの残留物が残り、後に印刷される画像に残像（ゴースト）として現れ画像品質が著しく低下する。また、十分なトナー強度が得られない場合には、印刷物の画像はその後の取り扱いで著しく劣化する。 Thus, in wet electrophotographic, the action of electric charge is not utilized when transferring an image to a recording material, for example, in the former method, that is, in the method of transferring an image from a heated blanket roll to a recording material, a wet toner is used. The image is transferred so that the adhesiveness between the image and the recording material is higher than the adhesiveness between the wet toner and the blanket roll. In other words, the ability to transfer wet toner from the blanket roll to the recording material is important. If the adhesive capacity of the toner itself is increased more than necessary for the purpose of improving the adhesiveness between the recording material and the toner, the adhesion to the recording material will be improved, and at the same time, the adhesiveness between the blanket roll and the toner will also be improved. Since the toner is hard to peel off, it is not possible to improve the adhesive ability of the toner after all. Therefore, in the case of the method of transferring an image from a heated blanket roll to a recording material, there are drawbacks that the toner particles are not sufficiently transferred even if printing is performed, or sufficient toner strength cannot be obtained. If the toner transfer is insufficient and incomplete, toner residue remains on the surface of the blanket roll and appears as an afterimage (ghost) in the image to be printed later, and the image quality is significantly deteriorated. Further, if sufficient toner strength is not obtained, the image of the printed matter is significantly deteriorated in the subsequent handling.
そこで、十分なトナー定着強度が得られるための手段として、定着剤を用紙に塗布する方法がある。例えばヒューレット・パッカード社のＨＰ Ｉｎｄｉｇｏ（登録商標）デジタル印刷機であれば、“サファイヤ処理”というポリエチレンイミンで被覆する処理があるが、記録材料の保存期間中に黄変が生じる、印刷後の取り扱いによりトナーが剥がれるなどの問題があった。 Therefore, as a means for obtaining sufficient toner fixing strength, there is a method of applying a fixing agent to paper. For example, in the case of Hewlett-Packard's HP Indigo (registered trademark) digital printing machine, there is a treatment called "sapphire treatment" in which it is coated with polyethyleneimine, but yellowing occurs during the storage period of the recording material, and handling after printing. There was a problem that the toner was peeled off.
他方、写真出力用途においては記録材料に高い平滑性が要求されるため、該記録材料としては、天然パルプを主成分とする紙基材をフィルム形成能のある樹脂で被覆した熱可塑性樹脂被覆紙またはポリマーフィルムが好適であり、該熱可塑性樹脂被覆紙やポリマーフィルムの表面にトナー受理層を設けた記録材料が知られている。例えば、特開２００７−６５５１７号公報には、紙基材に貼り合わされたポリマーフィルム上に特定のガラス転移温度を有する樹脂と低抵抗処理剤、有機ポリマー微粒子を含むトナー受理層を有する電子写真記録材料が提案されている。 On the other hand, since high smoothness is required for the recording material in photographic output applications, the recording material is a thermoplastic resin-coated paper in which a paper base material containing natural pulp as a main component is coated with a resin capable of forming a film. Alternatively, a polymer film is preferable, and a thermoplastic resin-coated paper or a recording material in which a toner receiving layer is provided on the surface of the polymer film is known. For example, Japanese Patent Application Laid-Open No. 2007-65517 describes an electrophotographic record having a toner receiving layer containing a resin having a specific glass transition temperature, a low resistance treatment agent, and organic polymer fine particles on a polymer film bonded to a paper substrate. The material has been proposed.
しかし、これらの樹脂被覆紙やポリマーフィルムは静電気が帯電しやすく、印刷時の記録材料の重送や、印刷後における記録材料の捌き性が問題となる場合がある。そこで、記録材料に帯電した静電気による上記問題を回避するため帯電防止剤の使用が検討されており、例えば、特開２００６−２４０１８６号公報には、支持体として用いる熱可塑性樹脂被覆紙の該被覆樹脂中に帯電防止剤を添加する電子写真記録材料が提案されている。しかしながら、帯電防止剤と熱可塑性樹脂との混合ムラがトナー記録面に影響を及ぼし、画像ムラやトナー定着強度の低下等の問題が生じる。 However, these resin-coated papers and polymer films are easily charged with static electricity, and there may be problems such as double feeding of the recording material at the time of printing and the handleability of the recording material after printing. Therefore, the use of an antistatic agent has been studied in order to avoid the above-mentioned problem due to static electricity charged on the recording material. For example, Japanese Patent Application Laid-Open No. 2006-240186 describes the coating of a thermoplastic resin-coated paper used as a support. An electrophotographic recording material in which an antistatic agent is added to a resin has been proposed. However, uneven mixing of the antistatic agent and the thermoplastic resin affects the toner recording surface, causing problems such as image unevenness and a decrease in toner fixing strength.
また、樹脂被覆紙やポリマーフィルム上に設けたトナー受理層に帯電防止剤を添加した電子写真記録材料も提案されている（例えば特許文献１〜３参照）。しかしながら、十分なトナー定着性と印刷後の記録材料の捌き性を両立することは困難であった。 Further, an electrophotographic recording material in which an antistatic agent is added to a toner receiving layer provided on a resin-coated paper or a polymer film has also been proposed (see, for example, Patent Documents 1 to 3). However, it has been difficult to achieve both sufficient toner fixability and handleability of the recording material after printing.
本発明は、黄変耐性及び高いトナー定着性を有し、印刷後の記録材料の捌き性に優れた電子写真記録材料を提供することを課題とする。 An object of the present invention is to provide an electrophotographic recording material which has yellowing resistance and high toner fixability and is excellent in handling of a recording material after printing.
本発明の上記課題は、以下の発明によって基本的に達成される。
１）熱可塑性樹脂被覆紙支持体上に、アイオノマー樹脂と下記一般式（Ｉ）で示される化合物を含むトナー受理層を有することを特徴とする電子写真記録材料。
The above object of the present invention is basically achieved by the following invention.
1) An electrophotographic recording material comprising a toner receiving layer containing an ionomer resin and a compound represented by the following general formula (I) on a thermoplastic resin-coated paper support.
（上記式中、Ｒ１はアルキル基を表し、Ｘ−は、アニオン性の対イオンを表す。） (In the above formula, R 1 represents an alkyl group and X − represents an anionic counterion.)
本発明により、黄変耐性及び高いトナー定着性を有し、印刷後の記録材料の捌き性に優れた電子写真記録材料を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an electrophotographic recording material which has yellowing resistance and high toner fixability and is excellent in handleability of the recording material after printing.
湿式電子写真方式では、湿式トナーとして、液体中にトナー粒子が分散されているトナー分散物を使用する。従来技術として湿式電子写真方式用記録材料に対して用いられてきたサファイヤ処理とは、前述の通りトナー定着強度を高めるために、カチオン性であるエチレンイミン等の有機成分を記録材料の表面に付与し、アニオン性のトナー分散物を定着させることを原理とする処理方法である。しかしながら、サファイヤ処理では、用いられるカチオン性の有機成分の反応性が高いため、共存する物質と反応し、画像を記録後に白紙黄変、印刷部分の変色が起こるとの問題が生じた。 In the wet electrophotographic method, a toner dispersion in which toner particles are dispersed in a liquid is used as the wet toner. The sapphire treatment, which has been used for recording materials for wet electrophotographic methods as a conventional technique, is to add a cationic organic component such as ethyleneimine to the surface of the recording material in order to increase the toner fixing strength as described above. However, it is a treatment method based on the principle of fixing an anionic toner dispersion. However, in the sapphire treatment, since the reactivity of the cationic organic component used is high, there is a problem that it reacts with a coexisting substance, causing yellowing of blank paper and discoloration of the printed portion after recording an image.
本発明においては、トナー受理層は、少なくとも、アイオノマー樹脂を含有する。これにより、高いトナー定着強度が得られるとともに、上記サファイヤ処理で生じるような白紙黄変等の問題が生じない。高いトナー定着強度が得られる理由としては、アイオノマー樹脂中の金属イオンによって、トナー分散物を定着させることができるためと考えられる。白紙黄変等の問題が生じない理由としては、使用するアイオノマー樹脂の反応性が低いためと考えられる。 In the present invention, the toner receiving layer contains at least an ionomer resin. As a result, high toner fixing strength can be obtained, and problems such as yellowing of blank paper that occur in the above sapphire treatment do not occur. It is considered that the reason why high toner fixing strength can be obtained is that the toner dispersion can be fixed by the metal ions in the ionomer resin. The reason why problems such as yellowing of blank paper do not occur is considered to be that the reactivity of the ionomer resin used is low.
本発明において、トナー受理層に用いるアイオノマー樹脂には、従来公知のアイオノマー樹脂を用いることができるが、エチレン系アイオノマー樹脂が好ましい。エチレン系アイオノマー樹脂とは、エチレンを含むα−オレフィンと、α，β−不飽和カルボン酸との共重合体に、原子価が１〜３の金属イオンを付加せしめたイオン性共重合体であり、金属イオンによる分子間架橋構造を有する。ここで、α，β−不飽和カルボン酸の代表例としては、アクリル酸、メタクリル酸、イタコン酸などが挙げられる。また、原子価が１〜３の金属イオンの代表例としては、Ｎａ＋、Ｋ＋、Ｃａ２＋、Ｚｎ２＋、Ａｌ３＋などが挙げられる。エチレン系アイオノマー樹脂は、例えば、エチレン−不飽和カルボン酸共重合体のアイオノマー樹脂またはエチレン−不飽和カルボン酸共重合体のアイオノマーと多価エポキシ化合物との架橋体を挙げることができる。中でも、エチレン−不飽和カルボン酸共重合体のアイオノマー樹脂が好ましい。かかるアイオノマー樹脂は、例えば住友精化（株）などからザイクセン（登録商標）として市販され、これらを入手し、利用することができる。 In the present invention, conventionally known ionomer resins can be used as the ionomer resin used for the toner receiving layer, but ethylene-based ionomer resins are preferable. The ethylene ionomer resin is an ionic copolymer obtained by adding metal ions having a valence of 1 to 3 to a copolymer of an α-olefin containing ethylene and an α, β-unsaturated carboxylic acid. , Has an intermolecular bridge structure by metal ions. Here, typical examples of α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid and the like. Typical examples of metal ions having a valence of 1 to 3 include Na + , K + , Ca 2+ , Zn 2+ , and Al 3+ . Examples of the ethylene-based ionomer resin include an ionomer resin of an ethylene-unsaturated carboxylic acid copolymer or a crosslinked product of an ionomer of an ethylene-unsaturated carboxylic acid copolymer and a polyvalent epoxy compound. Of these, an ionomer resin of an ethylene-unsaturated carboxylic acid copolymer is preferable. Such ionomer resins are commercially available as Zyxen (registered trademark) from Sumitomo Seika Chemical Co., Ltd., for example, and these can be obtained and used.
本発明において、トナー受理層は、アイオノマー樹脂に加えて、少なくとも、前記した一般式（Ｉ）で示される化合物を含有する。上記一般式（Ｉ）で示される化合物はアイオノマー樹脂との相溶性に優れるため、得られるトナー受理層も画像ムラやトナー定着強度の低下が発生することなく、効果的に記録材料の捌き性を改善することができる。 In the present invention, the toner receiving layer contains at least the compound represented by the above-mentioned general formula (I) in addition to the ionomer resin. Since the compound represented by the general formula (I) has excellent compatibility with the ionomer resin, the obtained toner receiving layer does not cause image unevenness or deterioration of the toner fixing strength, and effectively improves the handling property of the recording material. Can be improved.
前記一般式（Ｉ）中、Ｒ１はアルキル基を表し、炭素数８〜１２のアルキル基が好ましく、直鎖でも分岐していても良い。Ｘ−は、アニオン性の対イオンであり、具体的にはハロゲンイオン、スルホン酸イオン、アルキルスルホン酸イオン、アリールスルホン酸イオン、アルキルカルボン酸イオン、アリールカルボン酸イオン、等が挙げられる。これらは、第一工業製薬（株）などからカチオーゲン（登録商標）ＥＳタイプとして市販され、入手できる。 In the general formula (I), R 1 represents an alkyl group, and an alkyl group having 8 to 12 carbon atoms is preferable, and it may be linear or branched. X − is an anionic counterion, and specific examples thereof include halogen ion, sulfonic acid ion, alkyl sulfonic acid ion, aryl sulfonic acid ion, alkyl carboxylic acid ion, and aryl carboxylic acid ion. These are commercially available as Catiogen (registered trademark) ES type from Dai-ichi Kogyo Seiyaku Co., Ltd. and the like.
本発明において、トナー受理層中における一般式（Ｉ）で示される化合物の添加比率は、印刷後の記録材料の捌き性およびトナー定着強度の点から、アイオノマー樹脂の固形分量に対して、２〜１０質量％であることが好ましい。一般式（Ｉ）で示される化合物の添加比率が２質量％以上であれば、十分な帯電防止が達成でき、印刷後の記録材料の捌き性における問題を完全に防ぐことができる。一般式（Ｉ）で示される化合物の添加比率が１０質量％以下であれば、十分なトナー定着強度が得られる。 In the present invention, the addition ratio of the compound represented by the general formula (I) in the toner receiving layer is 2 to 2 with respect to the solid content of the ionomer resin from the viewpoint of the handleability of the recording material after printing and the toner fixing strength. It is preferably 10% by mass. When the addition ratio of the compound represented by the general formula (I) is 2% by mass or more, sufficient antistatic property can be achieved, and problems in the handleability of the recording material after printing can be completely prevented. When the addition ratio of the compound represented by the general formula (I) is 10% by mass or less, sufficient toner fixing strength can be obtained.
本発明において、トナー受理層は、更に公知の帯電防止剤を併用してもよい。一般式（Ｉ）で示される化合物と併用する場合の帯電防止剤としては、無機系の帯電防止剤が好ましく、例えば銅、金、銀、ニッケル、アルミニウム、スズなどの導電性金属又は導電性金属酸化物、あるいはカーボンブラックが好ましく用いられる。上記帯電防止剤の含有量は、一般式（Ｉ）で示される化合物の含有量に対し、等量以下とすることが好ましい。 In the present invention, a known antistatic agent may be further used in combination with the toner receiving layer. As the antistatic agent when used in combination with the compound represented by the general formula (I), an inorganic antistatic agent is preferable, and for example, a conductive metal such as copper, gold, silver, nickel, aluminum, tin, or a conductive metal. Oxide or carbon black is preferably used. The content of the antistatic agent is preferably equal to or less than the content of the compound represented by the general formula (I).
本発明において、トナー受理層は、更に無機顔料成分を含有してもよい。無機顔料成分としては、例えば、シリカ、アルミナおよびアルミナ水和物、酸化チタン、酸化亜鉛、硫酸バリウムなどが好ましく用いられる。 In the present invention, the toner receiving layer may further contain an inorganic pigment component. As the inorganic pigment component, for example, silica, alumina and alumina hydrate, titanium oxide, zinc oxide, barium sulfate and the like are preferably used.
本発明において、トナー受理層は、アイオノマー樹脂に加えて他の樹脂成分を含有してもよい。用いられる樹脂成分としては、公知の樹脂を使用することができ、例えば、スチレン−ブタジエン共重合体、アクリル酸またはメタクリル酸若しくはこれらのエステル等の誘導体を含む重合体若しくは共重合体、酢酸ビニル重合体、酢酸ビニル−マレイン酸エステル共重合体、エチレン−酢酸ビニル共重合体、酢酸ビニル−塩化ビニル共重合体等の酢酸ビニル系重合体、ポリビニルエーテル、アルキルビニルエーテル−無水マレイン酸共重合体、スチレン−無水マレイン酸共重合体およびそれらの塩、塩化ビニリデン系共重合体、あるいはこれらの各種重合体のカルボキシル基等の官能基含有単量体による官能基変性重合体、ポリビニルピロリドン、ポリビニルピリジニウムハライド、ポリエチレングリコール、ポリプロピレングリコール等の合成ポリマー、メラミン樹脂、尿素樹脂等の熱硬化合成樹脂系等の接着剤およびポリウレタン樹脂、ポリビニルブチラール、アルキッド樹脂等の合成樹脂系接着剤、ゼラチン、酸化澱粉、カチオン化澱粉、エーテル化澱粉等の澱粉類、カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、などである。これら樹脂成分のうち２種以上を併用してもよい。上記した他の樹脂成分の含有量は、アイオノマー樹脂の含有量に対し、等量以下とすることが好ましい。 In the present invention, the toner receiving layer may contain other resin components in addition to the ionomer resin. As the resin component used, a known resin can be used, for example, a polymer or copolymer containing a styrene-butadiene copolymer, acrylic acid or methacrylic acid or a derivative such as an ester thereof, a vinyl acetate weight. Combined, vinyl acetate-maleic acid ester copolymer, ethylene-vinyl acetate copolymer, vinyl acetate-based polymer such as vinyl acetate-vinyl chloride copolymer, polyvinyl ether, alkyl vinyl ether-maleic anhydride copolymer, styrene -Maleic anhydride copolymers and their salts, vinylidene chloride-based copolymers, or functional group-modified polymers with functional group-containing monomers such as carboxyl groups of these various polymers, polyvinylpyrrolidone, polyvinylpyridinium halide, Synthetic polymers such as polyethylene glycol and polypropylene glycol, heat-curable synthetic resin-based adhesives such as melamine resin and urea resin, and synthetic resin-based adhesives such as polyurethane resin, polyvinyl butyral and alkyd resin, gelatin, oxidized starch, cationization Stars such as starches and etherified starches, cellulose derivatives such as carboxymethyl celluloses and hydroxyethyl celluloses, and the like. Two or more of these resin components may be used in combination. The content of the other resin components described above is preferably equal to or less than the content of the ionomer resin.
トナー受理層には、他に各種無機酸、有機酸、ｐＨ調整剤、画像保存剤、着色剤、増粘剤、その他の界面活性剤等を適宜加えることができる。 In addition, various inorganic acids, organic acids, pH adjusters, image preservatives, colorants, thickeners, other surfactants and the like can be appropriately added to the toner receiving layer.
本発明におけるトナー受理層の厚みは、０．０５〜１０μｍであることが好ましい。 The thickness of the toner receiving layer in the present invention is preferably 0.05 to 10 μm.
本発明の電子写真記録材料は、熱可塑性樹脂被覆紙支持体を有する。かかる熱可塑性樹脂被覆紙は、天然パルプを主成分とする紙基材の両面に、フィルム形成能のある熱可塑性樹脂によって形成された樹脂被覆層を有する。被覆する熱可塑性樹脂としては、炭化水素系プラスチック、極性ビニル系プラスチック、線状構造プラスチック、セルロース系プラスチック等の樹脂が好ましい。炭化水素系プラスチックの例としては、ポリエチレン、ポリプロピレン、ポリメチルペンテン、ポリブテン、結晶性ポリブタジエン、ポリスチレン、ポリブタジエン、スチレン−ブタジエン共重合体などが挙げられる。極性ビニル系プラスチックの例としては、ポリ塩化ビニル、ポリ酢酸ビニル、ポリ塩化ビニリデン、エチレン−酢酸ビニル共重合体、アイオノマー、ポリメタクリル酸メチルなどが挙げられる。線状構造プラスチックの例としては、ポリアセタール、ポリアミド、ポリカーボネート、ポリフェニレンエーテル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリイミド、ポリアミドイミド、ポリフェニレンスルフィド、ポリオキシベンゾイル、ポリエーテルエーテルケトン、ポリエーテルイミドなどが挙げられる。セルロース系プラスチックの例としては、酢酸セルロース、酢酸酪酸セルロース、セロファン、セルロイドなどが挙げられる。樹脂被覆層の厚みは、片面あたり５〜６０μｍであることが好ましい。支持体の厚みとしては５０〜３００μｍであることが好ましい。 The electrophotographic recording material of the present invention has a thermoplastic resin-coated paper support. Such a thermoplastic resin-coated paper has resin-coated layers formed of a thermoplastic resin capable of forming a film on both sides of a paper base material containing natural pulp as a main component. As the thermoplastic resin to be coated, resins such as hydrocarbon-based plastics, polar vinyl-based plastics, linear structure plastics, and cellulosic-based plastics are preferable. Examples of hydrocarbon-based plastics include polyethylene, polypropylene, polymethylpentene, polybutene, crystalline polybutadiene, polystyrene, polybutadiene, and styrene-butadiene copolymers. Examples of the polar vinyl-based plastic include polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, ethylene-vinyl acetate copolymer, ionomer, polymethyl methacrylate and the like. Examples of linear structural plastics include polyacetal, polyamide, polycarbonate, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyimide, polyamideimide, polyphenylene sulfide, polyoxybenzoyl, polyetheretherketone, polyetherimide, etc. Can be mentioned. Examples of cellulosic plastics include cellulose acetate, cellulose butyrate acetate, cellophane, celluloid and the like. The thickness of the resin coating layer is preferably 5 to 60 μm per side. The thickness of the support is preferably 50 to 300 μm.
本発明における電子写真記録材料は、熱可塑性樹脂被覆紙支持体上にトナー受理層の塗液を塗布、乾燥してトナー受理層を形成することにより、製造することができる。支持体上にトナー受理層の塗液を塗布するには、ダイレクトグラビアコーター、オフセットグラビアコーター、リバースグラビアコーター、リバースロールコーター、エクストルージョンバーコーター、カーテンコーター、エアナイフコーター、バーコーター、コンマコーター、ダイコーター、リップコーター、ワイヤーバーコーター、ブレードコーター、スライドホッパーコーターおよびそれらの組み合わせ等を用いることができる。塗布された塗液の乾燥には、直線トンネル乾燥機、アーチドライヤー、エアループドライヤー、サインカーブエアフロートドライヤー等の熱風乾燥機、赤外線、加熱ドライヤー、マイクロ波等を利用した乾燥機等各種乾燥装置を用いることができる。 The electrophotographic recording material of the present invention can be produced by applying a coating liquid of a toner receiving layer on a thermoplastic resin-coated paper support and drying it to form a toner receiving layer. To apply the coating liquid of the toner receiving layer on the support, direct gravure coater, offset gravure coater, reverse gravure coater, reverse roll coater, extrusion bar coater, curtain coater, air knife coater, bar coater, comma coater, Daiko Tar, lip coater, wire bar coater, blade coater, slide hopper coater and combinations thereof can be used. For drying the applied coating liquid, various drying devices such as straight tunnel dryers, arch dryers, air loop dryers, hot air dryers such as sine curve air float dryers, and dryers using infrared rays, heating dryers, microwaves, etc. Can be used.
本発明の電子写真記録材料は、乾式電子写真方式、湿式電子写真方式の記録のいずれにも使用することができるが、特に、湿式電子写真方式の記録に適している。 The electrophotographic recording material of the present invention can be used for both dry electrophotographic recording and wet electrophotographic recording, and is particularly suitable for wet electrophotographic recording.
以下では、本発明を実施例により詳細に説明する。なお、本発明は実施例に限定されるものではないことは言うまでもない。以下、「％」は、特に説明のない限り、固形分換算の質量％である。「部」は、特に説明のない限り、固形分換算の質量部である。 Hereinafter, the present invention will be described in detail with reference to Examples. Needless to say, the present invention is not limited to the examples. Hereinafter, "%" is a mass% in terms of solid content unless otherwise specified. Unless otherwise specified, "part" is a mass part in terms of solid content.
（実施例１）
エチレン−不飽和カルボン酸共重合体のアイオノマー樹脂水分散液（住友精化（株）製、ザイクセンＡ）に、アイオノマー樹脂の１００部に対して、一般式（Ｉ）で示される化合物としてオクチルジメチルエチルアンモニウムエチルサルフェートが５部となるように添加し、さらに水を添加して濃度を１７％に調整してトナー受理層の塗液を得た。
(Example 1)
Ionomer resin aqueous dispersion of ethylene-unsaturated carboxylic acid copolymer (Zyxen A, manufactured by Sumitomo Seika Co., Ltd.) contains octyldimethyl as a compound represented by the general formula (I) with respect to 100 parts of the ionomer resin. Ethylene ammonium ethyl sulfate was added so as to form 5 parts, and water was further added to adjust the concentration to 17% to obtain a coating liquid for the toner receiving layer.
ポリプロピレン樹脂を上質紙の両面に溶融ラミネートした坪量１７０ｇ／ｍ２の熱可塑性樹脂被覆紙を支持体とし、該熱可塑性樹脂被覆紙の一方の面にトナー受理層の塗液をトナー受理層の厚みが１μｍになるようにマイクログラビア（登録商標）コーターを用いて塗布を行い、乾燥して、実施例１の電子写真記録材料を得た。 A thermoplastic resin-coated paper having a basis weight of 170 g / m 2 in which polypropylene resin is melt-laminated on both sides of high-quality paper is used as a support, and a coating liquid of a toner receiving layer is applied to one surface of the thermoplastic resin-coated paper. The coating material was applied using a Microgravia (registered trademark) coater so as to have a thickness of 1 μm, and dried to obtain an electrophotographic recording material of Example 1.
（実施例２）
実施例１において、一般式（Ｉ）で示される化合物をラウリルジメチルエチルアンモニウムエチルサルフェートに変更した以外は、実施例１と同様の方法で実施例２の電子写真記録材料を得た。
(Example 2)
In Example 1, the electrophotographic recording material of Example 2 was obtained in the same manner as in Example 1 except that the compound represented by the general formula (I) was changed to lauryldimethylethylammonium ethyl sulfate.
（比較例１）
実施例１において、トナー受理層の塗液に一般式（Ｉ）で示される化合物のラウリルジメチルエチルアンモニウムエチルサルフェートを添加しなかった以外は、実施例１と同様の方法で比較例１の電子写真記録材料を得た。
(Comparative Example 1)
In Example 1, the electrograph of Comparative Example 1 was carried out in the same manner as in Example 1 except that lauryldimethylethylammonium ethyl sulfate, a compound represented by the general formula (I), was not added to the coating solution of the toner receiving layer. Recording material was obtained.
（比較例２）
実施例１において、トナー受理層の塗液のアイオノマー樹脂水分散液（住友精化（株）製、ザイクセンＡ）をアクリル系樹脂水分散物（日信化学工業（株）製、ビニブラン（登録商標）２７７２）に変更した以外は、実施例１と同様の方法で比較例２の電子写真記録材料を得た。
(Comparative Example 2)
In Example 1, the ionomer resin aqueous dispersion (manufactured by Sumitomo Seika Co., Ltd., Zyxen A) of the coating liquid of the toner receiving layer was used as an acrylic resin aqueous dispersion (manufactured by Nissin Chemical Industry Co., Ltd., Viniblanc (registered trademark). ) 2772), the electrophotographic recording material of Comparative Example 2 was obtained in the same manner as in Example 1.
（比較例３）
実施例１において、トナー受理層の塗液のアイオノマー樹脂水分散液（住友精化（株）製、ザイクセンＡ）をポリエステル系樹脂水分散物（東洋紡（株）製、バイロナール（登録商標）ＭＤ−１４８０）に変更した以外は、実施例１と同様の方法で比較例３の電子写真記録材料を得た。
(Comparative Example 3)
In Example 1, the ionomer resin aqueous dispersion (manufactured by Sumitomo Seika Co., Ltd., Zyxen A) used as the coating liquid for the toner receiving layer was used as a polyester resin aqueous dispersion (manufactured by Toyobo Co., Ltd. The electrophotographic recording material of Comparative Example 3 was obtained in the same manner as in Example 1 except that the material was changed to 1480).
（比較例４）
濃度を１０％に調整した部分ケン化型ポリビニルアルコール（（株）クラレ製、ＰＶＡ２１７）に、部分ケン化型ポリビニルアルコールの１００部に対して、一般式（Ｉ）で示される化合物のラウリルジメチルエチルアンモニウムエチルサルフェートが５部となるように添加し、さらに水を添加して濃度を７％に調整してトナー受理層の塗液を得た。
(Comparative Example 4)
Partially saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA217) whose concentration was adjusted to 10%, and lauryldimethylethyl of the compound represented by the general formula (I) with respect to 100 parts of the partially saponified polyvinyl alcohol. Ammonium ethyl sulfate was added so as to form 5 parts, and water was further added to adjust the concentration to 7% to obtain a coating liquid for the toner receiving layer.
ポリプロピレン樹脂を上質紙の両面に溶融ラミネートした坪量１７０ｇ／ｍ２の熱可塑性樹脂被覆紙を支持体とし、該熱可塑性樹脂被覆紙の一方の面に上記ポリビニルアルコールを有するトナー受理層の塗液をトナー受理層の厚みが１μｍになるようにマイクログラビアコーターを用いて塗布を行い、乾燥して比較例４の電子写真記録材料を得た。 A coating liquid for a toner receiving layer having a thermoplastic resin-coated paper having a basis weight of 170 g / m 2 , in which polypropylene resin is melt-laminated on both sides of high-quality paper, as a support and having polyvinyl alcohol on one surface of the thermoplastic resin-coated paper. Was applied using a microgravia coater so that the thickness of the toner receiving layer was 1 μm, and dried to obtain the electrophotographic recording material of Comparative Example 4.
（比較例５）
実施例１において、一般式（Ｉ）で示される化合物を、ラウリルトリメチルアンモニウムクロライドに変更した以外は、実施例１と同様の方法で比較例５の電子写真記録材料を得た。
(Comparative Example 5)
In Example 1, the electrophotographic recording material of Comparative Example 5 was obtained in the same manner as in Example 1 except that the compound represented by the general formula (I) was changed to lauryltrimethylammonium chloride.
（比較例６）
実施例１において、一般式（Ｉ）で示される化合物を、ステアリルトリメチルアンモニウムクロライドに変更した以外は、実施例１と同様の方法で比較例６の電子写真記録材料を得た。
(Comparative Example 6)
In Example 1, the electrophotographic recording material of Comparative Example 6 was obtained in the same manner as in Example 1 except that the compound represented by the general formula (I) was changed to stearyltrimethylammonium chloride.
（比較例７）
実施例１において、一般式（Ｉ）で示される化合物を、ジデシルジメチルアンモニウムクロライドに変更した以外は、実施例１と同様の方法で比較例７の電子写真記録材料を得た。
(Comparative Example 7)
In Example 1, the electrophotographic recording material of Comparative Example 7 was obtained in the same manner as in Example 1 except that the compound represented by the general formula (I) was changed to didecyldimethylammonium chloride.
（比較例８）
実施例１において、一般式（Ｉ）で示される化合物を、ポリスルホン酸ソーダを主成分とする水溶液（三洋化成工業（株）製、ケミスタット（登録商標）ＳＡ−７）に変更した以外は、実施例１と同様の方法で比較例８の電子写真記録材料を得た。
(Comparative Example 8)
In Example 1, the compound represented by the general formula (I) was changed to an aqueous solution containing sodium polysulfonic acid as a main component (Chemistat (registered trademark) SA-7, manufactured by Sanyo Chemical Industries, Ltd.). The electrophotographic recording material of Comparative Example 8 was obtained in the same manner as in Example 1.
（比較例９）
実施例１において、一般式（Ｉ）で示される化合物を、ベタイン型両性界面活性剤を主成分とする水溶液（花王（株）製、アンヒトール（登録商標）５５ＡＢ）に変更した以外は、実施例１と同様の方法で比較例９の電子写真記録材料を得た。
(Comparative Example 9)
Example 1 except that the compound represented by the general formula (I) was changed to an aqueous solution containing a betaine-type amphoteric surfactant as a main component (manufactured by Kao Corporation, Anchtor (registered trademark) 55AB). The electrophotographic recording material of Comparative Example 9 was obtained in the same manner as in 1.
（比較例１０）
実施例１において得られた、ポリプロピレン樹脂を上質紙の両面に溶融ラミネートした坪量１７０ｇ／ｍ２の熱可塑性樹脂被覆紙の一方の面に、ポリエチレンイミンを主成分とするサファイヤコート液をサファイヤコート層の厚みが０．６μｍになるようにマイクログラビアコーターを用いて塗布を行い、乾燥して比較例１０の電子写真記録材料を得た。
(Comparative Example 10)
A sapphire coating solution containing polyethyleneimine as a main component is sapphire coated on one surface of a thermoplastic resin-coated paper having a basis weight of 170 g / m 2 obtained by melt-laminating polypropylene resin on both sides of a high-quality paper obtained in Example 1. The layer was coated with a microgravia coater so that the thickness of the layer was 0.6 μm, and dried to obtain an electrophotographic recording material of Comparative Example 10.
（比較例１１）
比較例４において得られた電子写真記録材料のトナー受理層面に、ポリエチレンイミンを主成分とするサファイヤコート液をサファイヤコート層の厚みが０．６μｍになるようにマイクログラビアコーターを用いて塗布を行い、乾燥して比較例１１の電子写真記録材料を得た。
(Comparative Example 11)
A sapphire coating solution containing polyethyleneimine as a main component was applied to the toner receiving layer surface of the electrophotographic recording material obtained in Comparative Example 4 using a microgravure coater so that the thickness of the sapphire coating layer was 0.6 μm. , The electrophotographic recording material of Comparative Example 11 was obtained.
（トナー定着強度の評価）
湿式電子写真方式のプリンターとして、ＨＰ Ｉｎｄｉｇｏ ７０００ Ｄｉｇｉｔａｌ Ｐｒｅｓｓを用い、標準４色、８ビットモード、１２１９ｄｐｉにて、上記のようにして得られた電子写真記録材料に印刷を行った。ブラック、シアン、マゼンタ、イエローの単色、色濃度１００％（色の光学濃度）のベタ印刷部にセロハンテープを貼り付けて、テープを剥がしてテープに付着したトナーを観察し、トナー定着強度を評価した。トナー接着強度は、以下の４段階の評価基準で判定した。評価が◎または○である場合は、本発明の電子写真記録材料として基準を満たしていることとする。
◎：テープにトナーの付着がなく、トナー定着強度に優れている。
○：テープに僅かにトナーの付着が見られるが、トナー定着強度は良好である。
△：テープにトナーの付着が見られ、トナー定着強度は実用限度のレベルである。
×：トナーの多くはテープに付着し、トナー定着強度は実用不可能なレベルである。
(Evaluation of toner fixing strength)
HP Index 7000 Digital Press was used as a wet electrophotographic printer, and printing was performed on the electrophotographic recording material obtained as described above in standard 4-color, 8-bit mode, 1219 dpi. A cellophane tape is attached to a solid printing part of black, cyan, magenta, and yellow with a single color and 100% color density (optical density of color), the tape is peeled off, and the toner attached to the tape is observed to evaluate the toner fixing strength. did. The toner adhesive strength was judged by the following four evaluation criteria. If the evaluation is ⊚ or ◯, it is considered that the criteria are satisfied as the electrophotographic recording material of the present invention.
⊚: No toner adheres to the tape, and the toner fixing strength is excellent.
◯: Toner adhesion is slightly observed on the tape, but the toner fixing strength is good.
Δ: Toner adhesion was observed on the tape, and the toner fixing strength was at the practical limit level.
X: Most of the toner adheres to the tape, and the toner fixing strength is at an impractical level.
（記録材料の捌き性の評価）
湿式電子写真方式のプリンターとして、ＨＰ Ｉｎｄｉｇｏ ７０００ Ｄｉｇｉｔａｌ Ｐｒｅｓｓを用い、印刷後の記録材料の捌き性を評価した。評価の指標として、１０枚連続印刷後に排紙トレーに出力されたＡ４サイズ記録材料束の短辺と長辺を揃えて、記録材料束を一定に揃える際の容易さについて以下の基準で評価を行った。
○：記録材料束が容易に揃う。
△：記録材料同士が弱く貼りつき、揃えるのに時間がかかる。
×：記録材料同士が貼りつき、記録材料束が全く揃わない。
(Evaluation of handleability of recording materials)
HP Index 7000 Digital Press was used as a wet electrophotographic printer, and the handleability of the recording material after printing was evaluated. As an evaluation index, the ease of aligning the short side and long side of the A4 size recording material bundle output to the output tray after continuous printing of 10 sheets and aligning the recording material bundle is evaluated according to the following criteria. went.
◯: A bundle of recording materials can be easily arranged.
Δ: The recording materials are weakly stuck to each other, and it takes time to align them.
X: Recording materials stick to each other, and the recording material bundles are not aligned at all.
（黄変耐性の評価）
電子写真記録材料においてトナー受理層の白紙面にキセノン・フェードメーター２３℃／６５％ＲＨ環境下にて７０，０００ｌｕｘのキセノン光を１２０時間照射する前後でのｂ＊の変動量をΔｂとし、下記のように３段階で評価した。
○：Δｂが１．００未満であり、黄変耐性に優れている。
△：Δｂが１．００以上、２．００未満であり、黄変耐性に劣り、印刷後の色再現に影響がある。
×：Δｂが２．００以上であり、黄変耐性に劣り、実用に適さない。
(Evaluation of yellowing resistance)
In the electrophotographic recording material, the fluctuation amount of b * before and after irradiating the blank surface of the toner receiving layer with xenon light of 70,000 lux for 120 hours under a xenon fade meter 23 ° C./65% RH environment is defined as Δb, and is as follows. It was evaluated on a three-point scale.
◯: Δb is less than 1.00, and the yellowing resistance is excellent.
Δ: Δb is 1.00 or more and less than 2.00, is inferior in yellowing resistance, and affects color reproduction after printing.
X: Δb is 2.00 or more, which is inferior in yellowing resistance and is not suitable for practical use.
各実施例および各比較例の評価結果を表１に示す。 Table 1 shows the evaluation results of each Example and each Comparative Example.
表１の結果から、本発明の電子写真記録材料は、黄変耐性及び高いトナー定着性を有し、印刷後の記録材料の捌き性に優れていることがわかる。 From the results in Table 1, it can be seen that the electrophotographic recording material of the present invention has yellowing resistance and high toner fixability, and is excellent in handling of the recording material after printing.
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| JP3683974B2 (en) * | 1996-03-14 | 2005-08-17 | キヤノン株式会社 | Coating liquid, inkjet recording medium, method for producing inkjet recording medium, and inkjet recording method |
| JPH09272258A (en) * | 1996-04-05 | 1997-10-21 | Oji Paper Co Ltd | Medium to be recorded |
| JP3436351B2 (en) * | 1999-08-20 | 2003-08-11 | 荒川化学工業株式会社 | Additive for inkjet recording and recording medium for inkjet recording |
| JP4013658B2 (en) * | 2002-06-04 | 2007-11-28 | 富士ゼロックス株式会社 | Laminate film for electrophotography and image forming method |
| JP2005173231A (en) * | 2003-12-11 | 2005-06-30 | Canon Inc | Electrophotographic retransfer material |
| JP2005274611A (en) * | 2004-03-22 | 2005-10-06 | Fuji Photo Film Co Ltd | Support for recording material |
| KR20140131548A (en) * | 2012-02-28 | 2014-11-13 | 미쓰비시 세이시 가부시키가이샤 | Electrophotographic recording material |
| JP2014163957A (en) * | 2013-02-21 | 2014-09-08 | Mitsubishi Paper Mills Ltd | Electrophotographic recording material |
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2017
- 2017-11-17 JP JP2017221586A patent/JP6845788B2/en active Active
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