JP2001287439A - Recording medium excellent in weatherability, water resistance and visibility - Google Patents
Recording medium excellent in weatherability, water resistance and visibilityInfo
- Publication number
- JP2001287439A JP2001287439A JP2000105052A JP2000105052A JP2001287439A JP 2001287439 A JP2001287439 A JP 2001287439A JP 2000105052 A JP2000105052 A JP 2000105052A JP 2000105052 A JP2000105052 A JP 2000105052A JP 2001287439 A JP2001287439 A JP 2001287439A
- Authority
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- Japan
- Prior art keywords
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- weight
- recording medium
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- receiving layer
- 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
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TWJYXMZUQAMMKA-UHFFFAOYSA-N n,n-dimethyl-1-(oxiran-2-yl)methanamine Chemical compound CN(C)CC1CO1 TWJYXMZUQAMMKA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ADGFKRMKSIAMAI-UHFFFAOYSA-L oxygen(2-);zirconium(4+);chloride;hydroxide Chemical compound [OH-].[O-2].[Cl-].[Zr+4] ADGFKRMKSIAMAI-UHFFFAOYSA-L 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 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
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- BZJNMKDNHPKBHE-UHFFFAOYSA-J tetrasodium 3-amino-5-oxido-7-sulfo-6-[[7-sulfonato-4-[(4-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C=1C=C2C=C(S([O-])(=O)=O)C(N)=CC2=C(O)C=1N=NC(C1=CC(=CC=C11)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 BZJNMKDNHPKBHE-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鮮明で光沢があ
り、且つ耐候性、耐水性、及び視認性に優れた画像が得
られる記録媒体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium capable of obtaining a clear and glossy image having excellent weather resistance, water resistance and visibility.
【０００２】[0002]
【従来の技術】インクジェット記録方式は、インク等の
記録用の液体（記録液）の微小液滴を飛翔させて紙や樹
脂シートなどの記録媒体に画像や文字などを記録するも
のであり、作業時間の低減、多色化の容易性、且つ鮮明
な画像が得られる等の優位性よりパーソナルコンピュー
ター、複写機、ワードプロセッサー、ＦＡＸ、プロッタ
ー等の様々な情報機器のプリンターとして急速に展開さ
れている。また、近年高性能のデジタルカメラ、デジタ
ルビデオ、スキャナー普及と相まって、これらから得ら
れた画像情報をインクジェット記録方式で出力する機会
が増大している。2. Description of the Related Art The ink jet recording system records images and characters on a recording medium such as paper or a resin sheet by flying fine droplets of a recording liquid (recording liquid) such as ink. Due to advantages such as reduction of time, easiness of multicoloring, and obtaining clear images, printers for various information devices such as personal computers, copiers, word processors, faxes, plotters, etc. are rapidly being developed. Further, in recent years, with the spread of high-performance digital cameras, digital videos, and scanners, opportunities for outputting image information obtained from these devices by an ink jet recording method have been increasing.
【０００３】他方、記録の高速化、高精細化、フルカラ
ー化など記録装置、記録方式が大きく発展する中で、記
録媒体にも、耐候性、耐水性、耐ＮＯｘ性、耐傷性、視
認性等の高度な特性が要求されるようになってきた。こ
のような要求に対し従来から多種多様の記録媒体が提案
されてきた。例えば、特開昭６１−６１８８７号公報に
は、インク受容層に特定のポリアリルアミン誘導体を、
また特開平８−１７４９９０号公報には、反応型紫外線
吸収性単量体から誘導した紫外線吸収性カチオンポリマ
ーを含有させることにより、画像の耐水性、耐候性を向
上させる方法が記載されている。特開昭６２−５６１８
４号公報、特開昭６２−２７３８９０号公報、及び特開
昭６２−２８００８５号公報等には、インク受容層に種
々の紫外線吸収剤を含有する樹脂層を積層する方法、特
開平７−２３７３４８号公報及び特開平８−２０９０号
公報には、インク受容層の上に熱可塑性樹脂粒子を含む
層を積層し、記録後に表層を被膜化して画像の耐水性、
耐湿性、耐擦過性を向上させる方法が記載されている。On the other hand, as recording apparatuses and recording methods have been greatly developed, such as high-speed recording, high-definition recording, and full-color recording, weather resistance, water resistance, NOx resistance, scratch resistance, visibility, etc. Advanced characteristics have been required. In response to such demands, various types of recording media have been conventionally proposed. For example, JP-A-61-61887 discloses that a specific polyallylamine derivative is used for an ink receiving layer.
JP-A-8-174990 describes a method for improving the water resistance and weather resistance of an image by including an ultraviolet absorbing cationic polymer derived from a reactive ultraviolet absorbing monomer. JP-A-62-5618
No. 4, JP-A-62-273890, JP-A-62-280085, and the like disclose a method of laminating resin layers containing various ultraviolet absorbents on an ink receiving layer. JP-A-8-2090 and JP-A-8-2090, a layer containing thermoplastic resin particles is laminated on an ink-receiving layer, and after recording, the surface layer is coated to form a water-resistant image.
A method for improving moisture resistance and scratch resistance is described.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、インク
受容層に特異的なカチオン性化合物を導入して画像の耐
候性及び耐水性を改善する方法はカチオン種が限られて
しまうため、逆に得られた画像の画質が大きく低下する
という問題があり、またインク受容層の上に保護層とし
て種々の紫外線吸収剤を含有する樹脂層を積層する方法
は、その紫外線吸収剤に由来するいくつかの問題を抱え
ている。例えば、有機系の紫外線吸収剤の多くは低分子
量であり、且つまた結晶性が高く樹脂との相容性が低い
ため、施工後に保護層表面からブリードアウトする虞が
ある。従って画像に長期耐候性を付与することができな
いだけでなく、画像表面が粉吹き状態になったり、表面
光沢が低下したりすることがある。また無機系の紫外線
吸収剤を用いた場合は、保護層のフェーズを低下して画
像の鮮明度を低下させるため大量に使用することができ
ない。However, the method of improving the weather resistance and water resistance of an image by introducing a specific cationic compound into the ink receiving layer is limited because the cationic species is limited. However, the method of laminating a resin layer containing various UV absorbers as a protective layer on the ink receiving layer has several problems derived from the UV absorbers. I have For example, many of the organic UV absorbers have a low molecular weight, and also have high crystallinity and low compatibility with the resin, and thus may bleed out from the surface of the protective layer after construction. Therefore, not only is it not possible to impart long-term weather resistance to the image, but also the image surface may be in a dusted state or the surface gloss may be reduced. Further, when an inorganic ultraviolet absorber is used, the phase of the protective layer is lowered to lower the sharpness of an image, so that it cannot be used in a large amount.
【０００５】本発明の課題は、記録後に得られる記録画
像が極めて耐候性、耐水性、視認性及び耐傷性に優れた
記録媒体を提供することにある。An object of the present invention is to provide a recording medium in which a recorded image obtained after recording is extremely excellent in weather resistance, water resistance, visibility and scratch resistance.
【０００６】[0006]
【課題を解決するための手段】本発明は基材層の表面に
インク受容層と表層としての保護層が積層され、更に該
基材層の裏面に裏打ち層を有する記録媒体において、基
材層、インク受容層、保護層及び裏打ち層の少なくとも
いずれか一層に式（１）で表わされるベンゾトリアゾ−
ル系紫外線吸収剤を０.１〜５０重量％含有することを
特徴とする記録媒体に係る。According to the present invention, there is provided a recording medium comprising a substrate layer, on which an ink receiving layer and a protective layer as a surface layer are laminated, and further comprising a backing layer on the back surface of the substrate layer. A benzotriazo compound represented by the formula (1) in at least one of an ink receiving layer, a protective layer and a backing layer.
The present invention relates to a recording medium comprising 0.1 to 50% by weight of a UV-based ultraviolet absorbent.
【０００７】[0007]
【化２】 Embedded image
【０００８】〔式中Ｒ１及びＲ２は同一又は異なって、
水素原子又は炭素数１〜１０のアルキル基を示す。ｎ、
ｎ’は同一又は異なって４〜８の数、ｍ、ｍ’は同一又
は異なって０〜２０の数を示す。〕[Wherein R 1 and R 2 are the same or different,
It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n,
n ′ is the same or different and represents a number of 4 to 8, and m and m ′ represent the same or different and represents a number of 0 to 20. ]
【０００９】本発明の記録媒体は、極めて優れた長期耐
候性、耐水性、視認性、耐傷性を有すると共に、複数の
シート状の記録媒体を表層と裏打ち層とが接触された状
態で重ね合せて、あるいはロール状として保管、搬送等
を行った場合でも、これらの層のブロッキングや裏打ち
層からのその構成成分の表層への転移（裏うつり現象）
を効果的に防止することができる。The recording medium of the present invention has extremely excellent long-term weather resistance, water resistance, visibility, and scratch resistance, and a plurality of sheet-like recording media are superposed in a state where a surface layer and a backing layer are in contact with each other. Even when stored, transported, etc., in the form of a roll or in the form of a roll, the blocking of these layers and the transfer of the components from the backing layer to the surface layer (back-filling phenomenon)
Can be effectively prevented.
【００１０】[0010]
【発明の実施の形態】本発明の記録媒体は、基材層の表
面にインク受容層と表層としての保護層が積層され、更
に該基材層の裏面に裏打ち層を有するものである。BEST MODE FOR CARRYING OUT THE INVENTION The recording medium of the present invention has a structure in which an ink receiving layer and a protective layer as a surface layer are laminated on the surface of a base material layer, and further has a backing layer on the back surface of the base material layer.
【００１１】本発明の記録媒体に用いる基材層は、透明
でも不透明でも良く、記録媒体に所望の形態維持性能を
付与できるものであれば良い。このような基材層として
は特に限定されるものではないが、具体的には上質紙、
中質紙、アート紙、ボンド紙、レジンコート紙、バライ
タ紙などの紙類、ポリエチレンテレフタレート、テレフ
タル酸−エチレングリコール−シクロヘキサンジメタノ
ール共重合体、ジアセテート、トリアセテート、ポリカ
ーボネート、ポリエチレン、ポリアクリレート、ポリ塩
化ビニル、ポリスチレン、ＡＢＳ、エチレン−酢酸ビニ
ル共重合体、エチレン−ビニルアルコール共重合体など
のプラスチック材料及びそれらの複合材料からなるフィ
ルム、シート、板状物等を挙げることができる。また用
途によっては、金属、硝子、セラミック、木材等も適す
る。The base material layer used in the recording medium of the present invention may be transparent or opaque, and may be any as long as it can impart a desired form maintaining performance to the recording medium. Such a substrate layer is not particularly limited, but specifically, high-quality paper,
Paper such as medium paper, art paper, bond paper, resin coated paper, baryta paper, polyethylene terephthalate, terephthalic acid-ethylene glycol-cyclohexane dimethanol copolymer, diacetate, triacetate, polycarbonate, polyethylene, polyacrylate, poly Examples thereof include films, sheets, and plates made of plastic materials such as vinyl chloride, polystyrene, ABS, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and composite materials thereof. Depending on the application, metal, glass, ceramic, wood, and the like are also suitable.
【００１２】これらの基材層は、磁気記録、光記録、バ
ーコード等の他の記録媒体を積層して使用することも出
来るし、接着層及び剥離層を積層して使用することも可
能である。基材層として紙を用いる場合、一般的に繊維
状物質からなる基紙の表面を硫酸バリウムを含む層でコ
ートし使用することが知られているが、銀塩写真に匹敵
するような画像を得るためには、表面のベック平滑度を
４００秒以上、かつ白色度を８７％以上に調整してなる
基材層を使用することがとりわけ好ましい。These base layers can be used by laminating other recording media such as magnetic recording, optical recording, barcode, etc., or can be used by laminating an adhesive layer and a release layer. is there. When paper is used as the base layer, it is generally known that the surface of a base paper made of a fibrous substance is coated and used with a layer containing barium sulfate, but an image comparable to a silver salt photograph is used. In order to obtain, it is particularly preferable to use a base material layer whose surface Beck smoothness is adjusted to 400 seconds or more and whiteness is adjusted to 87% or more.
【００１３】ここで用いる硫酸バリウムとしては、その
平均粒径が０.４〜１.０μｍが好ましく、０.４〜０.８
μｍのものがより好ましい。硫酸バリウムを結着させる
ためのバインダーとしては、ゼラチンが好ましく、硫酸
バリウム１００重量部に対して１〜２０重量部、好まし
くは６〜１２重量部の割合で用いることができる。硫酸
バリウムを含む層の基紙への塗工量は、インクの溶媒成
分に対する吸収性を更に好ましいものとし、また表面の
平滑性をより良好とするために、２０〜４０ｇ／ｍ２の
範囲が好ましい。また、硫酸バリウムを含む層のベック
平滑度の上限は、インクの溶媒成分に対する吸収性をよ
り好適なものとする上で、４００〜６００秒が好まし
く、４５０〜５５０秒がより好ましく、４７５〜５２５
秒が特に好ましい。The barium sulfate used herein preferably has an average particle size of 0.4 to 1.0 μm, and 0.4 to 0.8 μm.
μm is more preferred. As a binder for binding barium sulfate, gelatin is preferable, and it can be used in a proportion of 1 to 20 parts by weight, preferably 6 to 12 parts by weight, based on 100 parts by weight of barium sulfate. The coating amount of the layer containing barium sulfate on the base paper is preferably in the range of 20 to 40 g / m 2 in order to make the ink absorbability to the solvent component more favorable and to make the surface smoothness better. preferable. Further, the upper limit of the Beck smoothness of the layer containing barium sulfate is preferably 400 to 600 seconds, more preferably 450 to 550 seconds, and more preferably 475 to 525 in order to make the ink absorbability to the solvent component more suitable.
Seconds are particularly preferred.
【００１４】インク受容層としては特に制限はなく、様
々な形態のものとすることができるが、銀塩写真に匹敵
するような画像が求められる場合に好ましい例を挙げれ
ば、アルミナ水和物とバインダーである水溶性高分子物
質を含有するもの、吸水性及び／又は吸溶剤性樹脂より
選ばれる少なくとも一種と、無機粒子から選ばれる固形
部材の少なくとも一種を含有するものを例示できる。The ink receiving layer is not particularly limited and may be in various forms. When an image comparable to a silver halide photograph is required, preferred examples include alumina hydrate and alumina hydrate. Examples thereof include those containing a water-soluble polymer substance as a binder, at least one selected from water-absorbing and / or solvent-absorbing resins, and one containing at least one solid member selected from inorganic particles.
【００１５】アルミナ水和物としては、市販のもの、あ
るいはアルミニウムアルコキシド、アルミン酸ナトリウ
ムなどを公知の方法によって加水分解して製造されたも
のを用いることができる。その粒子形状は繊毛状または
針状、板状、紡錘状等に限定されず、また、配向性の有
無も問わないが、透明性、光沢性、染料定着性の高いも
ので、且つ被膜形成時にクラック等が入らず、塗工性の
良いものであればより好ましい。工業的に市販されてい
るものとしては、例えば、触媒化成工業社製の「カタロ
イドＡＳ−２」、「カタロイドＡＳ−３」、日産化学社
製「アルミナゾル−５２０」等が挙げられる。これらの
アルミナ水和物は、通常粒子径が１μｍ以下と細かいも
のであり、優れた分散性を有するものであるため、記録
媒体に非常に良好な平滑性、光沢性を保持させることが
できる。As the alumina hydrate, commercially available ones or those produced by hydrolyzing aluminum alkoxide, sodium aluminate or the like by a known method can be used. The particle shape is not limited to cilia-like or needle-like, plate-like, spindle-like, etc., and it does not matter whether or not it has orientation, but it has high transparency, gloss, dye fixability, and It is more preferable that the material does not crack or the like and has good coating properties. Examples of commercially available products include "Cataloid AS-2" and "Cataloid AS-3" manufactured by Catalyst Chemical Industry Co., Ltd., and "Alumina Sol-520" manufactured by Nissan Chemical Industries, Ltd. These alumina hydrates are usually fine, having a particle size of 1 μm or less, and have excellent dispersibility, so that the recording medium can maintain very good smoothness and gloss.
【００１６】アルミナ水和物を結着するために使用され
るバインダーとしては、水溶性高分子物質であれば特に
限定されるものではない。具体的には、例えば、ポリビ
ニルアルコールまたはその変性体、澱粉またはその変性
体、ゼラチンまたはその変性体、カゼインまたはその変
性体、アラビアゴム、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、ヒドロキシプロピルメチル
セルロースなどのセルロース誘導体、ＳＢＲラテック
ス、ＮＢＲラテックス、メチルメタクリレート−ブタジ
エン共重合体などの共役ジエン系共重合体ラテックス、
メチルメタクリレート−ブタジエン共重合体のケン化
物、（メタ）アクリル酸エステルと（メタ）アクリル酸
との共重合体のケン化物、エチレン酢酸ビニル共重合体
のケン化物等の官能基変性重合体ラテックス、エチレン
酢酸ビニル共重合体及びその鹸化物などのビニル系共重
合体ラテックス、ポリビニルピロリドン、ポリビニルア
セトアミド、無水マレイン酸またはその共重合体、アク
リル酸エステル共重合体などが好ましい。これらのバイ
ンダーは単独あるいは複数種混合して用いることができ
る。The binder used for binding the alumina hydrate is not particularly limited as long as it is a water-soluble polymer substance. Specifically, for example, polyvinyl alcohol or its modified product, starch or its modified product, gelatin or its modified product, casein or its modified product, gum arabic, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, SBR Latex, NBR latex, conjugated diene copolymer latex such as methyl methacrylate-butadiene copolymer,
Functional group-modified polymer latex such as saponified methyl methacrylate-butadiene copolymer, saponified copolymer of (meth) acrylic acid ester and (meth) acrylic acid, saponified ethylene vinyl acetate copolymer, Preferred are vinyl copolymer latex such as ethylene-vinyl acetate copolymer and saponified product thereof, polyvinylpyrrolidone, polyvinylacetamide, maleic anhydride or a copolymer thereof, and acrylate copolymer. These binders can be used alone or in combination of two or more.
【００１７】アルミナ水和物とバインダーの混合比は、
重量比で、１：１〜３０：１の範囲で使用されることが
好ましく、５：１〜２５：１の範囲で使用されることが
より好ましい。バインダーの量をこれらの範囲とするこ
とで、インク受容層の機械的強度を好ましいものとする
ことができ、ひび割れや粉落ちの発生の防止や、好適な
細孔容積の維持が可能となる。The mixing ratio of the alumina hydrate and the binder is as follows:
It is preferably used in a weight ratio of 1: 1 to 30: 1, more preferably 5: 1 to 25: 1. By setting the amount of the binder in these ranges, the mechanical strength of the ink receiving layer can be made favorable, and it becomes possible to prevent the occurrence of cracks and powder dropping and maintain a suitable pore volume.
【００１８】アルミナ水和物を含む層を形成するための
塗工液には、アルミナ水和物及びバインダーに加え、必
要に応じて分散剤、増粘剤、ｐＨ調整剤、潤滑剤、流動
性変性剤、界面活性剤、消泡剤、耐水化剤、離型剤、蛍
光増白剤、酸化防止剤などを、本発明の効果を損なわな
い範囲内で添加することも可能である。アルミナ水和物
を含む層の塗工量としては、染料定着性をもたせ且つ必
要な平滑性を持たせる為にも乾燥固形分換算で３０ｇ／
ｍ２以下が好ましく、２０〜３０ｇ／ｍ２の範囲がより
好ましい。塗工乾燥方法は特に限定されないが、必要に
応じてアルミナ水和物及びバインダーを含む層を形成し
た後に焼成処理を施すことも可能である。かかる焼成処
理を施すことにより、バインダーの架橋強度が上がり、
インク受容層の機械的強度が向上し、また、アルミナ水
和物層の表面光沢が向上する。また、ポリビニルアミ
ン、ジメチルアミン−エピクロルヒドリン共重合物、ア
クリルアミド−ジアリルアミン共重合物、ジシアンジア
ミド−ホルムアルデヒド共重合物、ポリビニルアミン−
アクリロニトリル共重合物、ポリアクリルアミド重合
物、ジメチルアミノエチルアクリレート重合物、グリシ
ジルジメチルアミン重合物等のポリアミンやポリアミド
等の第四級アンモニウム塩等のカチオン性化合物を併用
し、インクの定着性を向上させることもできる。The coating liquid for forming the layer containing alumina hydrate includes, in addition to the alumina hydrate and the binder, a dispersant, a thickener, a pH adjuster, a lubricant, a fluid It is also possible to add a modifier, a surfactant, an antifoaming agent, a water-proofing agent, a release agent, a fluorescent whitening agent, an antioxidant, and the like within a range that does not impair the effects of the present invention. The coating amount of the layer containing alumina hydrate is 30 g / dry solid equivalent in order to impart dye fixing property and to provide necessary smoothness.
m 2 or less, and the range of 20 to 30 g / m 2 is more preferable. The coating and drying method is not particularly limited, but if necessary, a baking treatment may be performed after forming a layer containing alumina hydrate and a binder. By performing such a baking treatment, the crosslinking strength of the binder increases,
The mechanical strength of the ink receiving layer is improved, and the surface gloss of the alumina hydrate layer is improved. Further, polyvinylamine, dimethylamine-epichlorohydrin copolymer, acrylamide-diallylamine copolymer, dicyandiamide-formaldehyde copolymer, polyvinylamine-
Improve the fixability of the ink by using in combination a cationic compound such as a quaternary ammonium salt such as a polyamine such as an acrylonitrile copolymer, a polyacrylamide polymer, a dimethylaminoethyl acrylate polymer, or a glycidyl dimethylamine polymer. You can also.
【００１９】さらに、上記のアルミナ水和物を含む層を
形成するための塗工液に、特開平７−７６１６１号公報
で記載されているような、ホウ酸またはホウ酸塩などの
バインダーの架橋剤を含有させても、インク受容層の機
械的強度が向上するので好ましい。なお、本発明におけ
るインク受容層は、記録媒体に付与されたインクを主に
吸収する部分であり、上述したように基材層の表面に硫
酸バリウムを含む層などのインク吸収性の層が予め設け
られている場合、この基材層側の層もインク受容層の一
部として解釈することができる。Further, a coating solution for forming a layer containing the above-mentioned alumina hydrate is crosslinked with a binder such as boric acid or borate as described in JP-A-7-76161. The addition of an agent is preferred because the mechanical strength of the ink receiving layer is improved. Incidentally, the ink receiving layer in the present invention is a portion that mainly absorbs the ink applied to the recording medium, and as described above, an ink absorbing layer such as a layer containing barium sulfate is previously formed on the surface of the base material layer. When provided, the layer on the substrate layer side can also be interpreted as a part of the ink receiving layer.
【００２０】他方、吸水性及び／又は吸溶剤性樹脂より
選ばれる少なくとも一種と、無機粒子から選ばれる固形
部材の少なくとも一種を含有するものを本発明のインク
受容層として用いる場合に、用いられる無機粒子として
は特に限定されるものではなく、具体的にはシリカ、ク
レー、タルク、ケイソウ土、炭酸カルシウム、硫酸バリ
ウム、ケイ酸アルミニウム、合成ゼオライト、アルミ
ナ、酸化亜鉛、雲母等が挙げられる。中でもシリカ、ア
ルミナ、炭酸カルシウムが好ましく、さらに湿式法のゲ
ルタイプのシリカが最適である。On the other hand, when the ink receiving layer of the present invention contains at least one selected from a water-absorbing and / or solvent-absorbing resin and at least one solid member selected from inorganic particles, The particles are not particularly limited, and specific examples include silica, clay, talc, diatomaceous earth, calcium carbonate, barium sulfate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, mica and the like. Among them, silica, alumina and calcium carbonate are preferable, and gel type silica obtained by a wet method is most suitable.
【００２１】また、吸水性及び／又は吸溶剤性を有する
樹脂としては、前記固形部材を結着する機能と油性もし
くは水溶性インクを吸収する機能を有するもので有れば
特に限定されるものではないが、膨潤性を有するものが
望ましく、具体的には高松油脂（株）製の商品名ＮＳ−
１２０ＸＫ、ＮＳ−２８２ＬＫ、ＮＳ−１４１ＬＸ等が
挙げられる。これらの樹脂は、前記と同様の第四級アン
モニウム塩等のカチオン性化合物を併用し、インクの定
着性を向上させることもできる。The resin having water absorbency and / or solvent absorbency is not particularly limited as long as it has a function of binding the solid member and a function of absorbing oily or water-soluble ink. However, those having a swelling property are desirable, and specifically, a trade name NS- manufactured by Takamatsu Yushi Co., Ltd.
120XK, NS-282LK, NS-141LX and the like. These resins can be used together with a cationic compound such as a quaternary ammonium salt as described above to improve the fixability of the ink.
【００２２】上記固形部材の使用量は、吸水性及び／又
は吸溶剤性を有する樹脂の合計量１００重量部に対して
１０〜３００重量部の範囲とするのが好ましく、さらに
２０〜１５０重量部の範囲で使用するのがより好まし
い。The amount of the solid member used is preferably in the range of 10 to 300 parts by weight, more preferably 20 to 150 parts by weight, based on 100 parts by weight of the total amount of the resin having water absorbing and / or solvent absorbing properties. It is more preferable to use it in the range.
【００２３】表層としての保護層としては特に制限はな
く、様々な形態のものとすることができるが、好ましい
例としては、多孔質熱可塑性樹脂層であって樹脂粒子間
に保持される空隙により多孔質となっており、必要によ
り記録後に加圧及び／又は加熱により整膜処理するも
の、及び、あらかじめ剥離シートに施工された樹脂層を
転写することにより形成されるもの等を例示できる。The protective layer as the surface layer is not particularly limited, and may be in various forms. A preferred example is a porous thermoplastic resin layer, which is formed by voids held between resin particles. Examples thereof include those which are porous and which are subjected to film-regulating treatment by pressurizing and / or heating after recording as required, and those which are formed by transferring a resin layer previously applied to a release sheet.
【００２４】表層としての保護層として多孔質熱可塑性
樹脂層を用いる場合、該多孔質熱可塑性樹脂層は、記録
操作におけるインク付与時にはインクの透過性を有する
ことでその下に設けられたインク受容層へインクを通過
せる機能を有し、記録終了後に加熱により平滑な連続性
のあるフィルムに変化させることが可能なものである。
ここで多孔質熱可塑性樹脂層は、熱可塑性樹脂粒子を用
いて、各粒子間を、適度な多孔質性を維持できるように
結合して層形態を保持する構成を有している。In the case where a porous thermoplastic resin layer is used as a protective layer as a surface layer, the porous thermoplastic resin layer has an ink permeability at the time of application of ink in a recording operation, so that an ink receiving layer provided thereunder is provided. It has a function of allowing ink to pass through the layer, and can be changed into a smooth continuous film by heating after recording.
Here, the porous thermoplastic resin layer has a configuration in which thermoplastic resin particles are used to bond the respective particles so as to maintain appropriate porosity, thereby maintaining the layer form.
【００２５】該多孔質熱可塑性樹脂層の構成成分として
用いることのできる熱可塑性樹脂粒子としては、各種の
熱可塑性樹脂材料からなるものを用いることができる。
熱可塑性樹脂粒子としては、例えば、塩化ビニル系、塩
化ビニリデン系、スチレン系、アクリル系、ウレタン
系、ポリエステル系、エチレン系、塩化ビニル−酢酸ビ
ニル系、塩化ビニル−酢酸ビニル−アクリル酸系、ＳＢ
Ｒ系、ＮＢＲ系などのラテックス（ここで「ラテック
ス」とは分散媒中に樹脂粒子を分散させたものを意味
し、所謂ラテックスの他、エマルジョン、スラリー等を
含む。）に含まれる熱可塑性樹脂粒子としてのラテック
ス粒子を好適に用いることができ、必要に応じてラテッ
クスの固形分量を調整して用いることができる。これら
の粒子は、成膜性等を損なわない範囲内で単独あるいは
複数種混合して用いることもできる。熱可塑性樹脂粒子
の粒径としては、好ましくは０.１〜５.０μｍの範囲で
あり、０.２μｍ〜０.８μｍの範囲がより好ましい。As the thermoplastic resin particles that can be used as a component of the porous thermoplastic resin layer, those made of various thermoplastic resin materials can be used.
Examples of the thermoplastic resin particles include vinyl chloride, vinylidene chloride, styrene, acrylic, urethane, polyester, ethylene, vinyl chloride-vinyl acetate, vinyl chloride-vinyl acetate-acrylic acid, and SB.
R-type, NBR-type or other latex (herein, "latex" means a dispersion of resin particles in a dispersion medium, and includes so-called latex, emulsion, slurry, etc.) thermoplastic resin Latex particles can be suitably used as the particles, and the solid content of the latex can be adjusted and used as necessary. These particles may be used alone or as a mixture of two or more as long as the film formability or the like is not impaired. The particle size of the thermoplastic resin particles is preferably in the range of 0.1 to 5.0 μm, and more preferably in the range of 0.2 μm to 0.8 μm.
【００２６】熱可塑性樹脂粒子を含む塗工液を調製する
には、熱可塑性樹脂粒子を適当な溶媒、例えば水性溶媒
中に分散させ、その固形分を１０〜５０重量％の範囲と
することが好ましいが、塗工方法に合わせて適宜調整す
ることが可能である。塗工量としては、表面光沢を付与
し、干渉色の発現を抑え、且つ保護膜として充分な機能
を有する程度の厚さを得る上で、乾燥層厚で通常２〜１
０μｍになるように調整するのが好ましい。表層の形成
においては、各粒子間の空隙が保持された多孔質の層と
なるように、乾燥条件等を設定する。多孔質の状態で表
層を形成する方法としては、例えば、熱可塑性樹脂粒子
を含む塗工液をインク受容層上に塗工した後、熱可塑性
樹脂粒子のガラス転移温度（Ｔｇ）以上であり、かつ最
低造膜温度以下の温度で熱処理して多孔質層を形成する
方法が利用できる。To prepare a coating liquid containing thermoplastic resin particles, the thermoplastic resin particles are dispersed in an appropriate solvent, for example, an aqueous solvent, and the solid content is adjusted to 10 to 50% by weight. Although it is preferable, it can be appropriately adjusted according to the coating method. The coating amount is usually 2 to 1 in terms of dry layer thickness in order to impart a surface gloss, suppress the appearance of interference colors, and obtain a thickness having a sufficient function as a protective film.
It is preferable to adjust the thickness to 0 μm. In forming the surface layer, drying conditions and the like are set so as to form a porous layer in which voids between the particles are maintained. As a method of forming the surface layer in a porous state, for example, after applying a coating liquid containing thermoplastic resin particles on the ink receiving layer, the glass transition temperature of the thermoplastic resin particles (Tg) or more, In addition, a method of forming a porous layer by performing a heat treatment at a temperature equal to or lower than the minimum film forming temperature can be used.
【００２７】表層には必要に応じて分散剤、増粘剤、ｐ
Ｈ調整剤、潤滑剤、流動性変性剤、界面活性剤、消泡
剤、耐水化剤、離型剤、蛍光増白剤、酸化防止剤など
を、本発明の効果を損なわない範囲内で添加してもよ
い。If necessary, a dispersant, a thickener, p
H adjusters, lubricants, fluidity modifiers, surfactants, defoamers, water-proofing agents, mold release agents, fluorescent brighteners, antioxidants, etc. are added as long as the effects of the present invention are not impaired. May be.
【００２８】保護層として、あらかじめ剥離シートに施
工された樹脂層を転写することにより形成されるもの
は、例えばＰＥＴフィルム等の剥離シートに積層された
転写可能な樹脂層の形で用いられる。該樹脂層は、加熱
圧着ロール等により、基材層上に積層された画像が形成
されたインク受容層の表面に圧着した後、剥離シートを
剥離することにより形成される。該樹脂層はどの様な機
能を備えたものであっても良く、具体的には耐候性、耐
ＮＯｘ性、耐水性、視認性、耐傷性、耐溶剤性、防汚
性、帯電防止性等が挙げられる。また、該樹脂層は、エ
ネルギー線や熱などによる硬化機能を有していても良
い。A protective layer formed by transferring a resin layer previously applied to a release sheet is used in the form of a transferable resin layer laminated on a release sheet such as a PET film. The resin layer is formed by pressing the surface of the ink receiving layer on which the image laminated on the base material layer is formed with a heat-pressing roll or the like, and then peeling off the release sheet. The resin layer may have any function, specifically, weather resistance, NOx resistance, water resistance, visibility, scratch resistance, solvent resistance, stain resistance, antistatic property, etc. Is mentioned. Further, the resin layer may have a curing function using energy rays, heat, or the like.
【００２９】該樹脂層は、インク受容層に転写可能なも
のであれば、特に限定されるものではないが、具体的に
は、塩化ビニル系、塩化ビニリデン系、スチレン系、ア
クリル系、ウレタン系、ポリエステル系、エチレン系、
塩化ビニル−酢酸ビニル系、塩化ビニル−酢酸ビニル−
アクリル酸系、ＳＢＲ系、ＮＢＲ系、メラミン系、アル
キド樹脂系、フッ素樹脂系、シリコン樹脂系、アクリル
シリコン系、ブチラール樹脂系等が挙げられ、これらの
１種以上を用いることができる。これらは裏打ち層その
他、本発明の記録媒体に用いられる材料（特に樹脂）と
熱収縮率がほぼ同等のものを用いるのが好ましい。ま
た、これらの樹脂は、転写フィルムとして単独で使用す
ることもできるし、より透明性の優れた熱可塑性接着剤
を積層して使用することもできる。熱可塑性接着剤は、
透明性、熱圧着性に優れていれば何ら限定されるもので
はないが、具体的には東和合成化学工業（株）製「アロ
ンメルト」、日信化学工業（株）製「日信ホットメル
ト」、「ビニブラン」等が挙げられる。The resin layer is not particularly limited as long as it can be transferred to the ink receiving layer, and specific examples thereof include vinyl chloride, vinylidene chloride, styrene, acrylic and urethane. , Polyester, ethylene,
Vinyl chloride-vinyl acetate system, vinyl chloride-vinyl acetate-
Acrylic acid type, SBR type, NBR type, melamine type, alkyd resin type, fluororesin type, silicone resin type, acrylic silicon type, butyral resin type and the like can be mentioned, and one or more of these can be used. It is preferable to use a material having a heat shrinkage almost equal to that of the material (particularly, resin) used for the recording medium of the present invention, such as a backing layer. Further, these resins can be used alone as a transfer film, or can be used by laminating a thermoplastic adhesive having better transparency. Thermoplastic adhesives
It is not particularly limited as long as it is excellent in transparency and thermocompression bonding property. Specifically, “Alon Melt” manufactured by Towa Gosei Chemical Industry Co., Ltd., “Nissin Hot Melt” manufactured by Nissin Chemical Industry Co., Ltd. , “Vinibulan” and the like.
【００３０】裏打ち層としては特に制限はなく、様々な
形態のものとすることができるが、好ましい具体例とし
ては、熱可塑性樹脂粒子が被膜化されたものを例示でき
る。かかる熱可塑性樹脂粒子としては、表層の保護層と
して用いることが可能な熱可塑性樹脂粒子をそのまま用
いることができる。その際、裏打ち層は加熱等によりあ
らかじめ被膜化を行うのが好ましい。裏打ち層の塗工時
に使用する熱可塑性樹脂粒子の量は、特に限定されるわ
けではないが、経済性及びカール防止性能を考慮に入れ
ると、例えば５〜１５ｇ／ｍ２程度となるように調整す
ることが好ましい。The backing layer is not particularly limited and may be of various forms. Preferred examples include those in which thermoplastic resin particles are coated. As such thermoplastic resin particles, thermoplastic resin particles that can be used as a surface protective layer can be used as they are. At this time, it is preferable that the backing layer is previously formed into a film by heating or the like. The amount of the thermoplastic resin particles used for coating the backing layer is not particularly limited, but is adjusted to be, for example, about 5 to 15 g / m 2 in consideration of economy and anti-curl performance. Is preferred.
【００３１】裏打ち層には、必要に応じて分散剤、増粘
剤、ｐＨ調整剤、潤滑剤、流動性変性剤、界面活性剤、
消泡剤、耐水化剤、離型剤、蛍光増白剤、酸化防止剤な
どを、本発明の効果を損なわない範囲内で添加してもよ
い。更に、裏打ち層には筆記性、難燃性、強度付与、着
色等を目的として無機顔料を添加することもできる。そ
の添加量は、１〜３０重量％程度が好ましい。無機顔料
としては、例えば、炭酸カルシウム、カオリン、タル
ク、クレー、硫酸バリウム、チタンホワイト、非晶質シ
リカ、コロイダルシリカ、コロイダルアルミナ、擬ベー
マイト、アルミナ、炭酸マグネシウム、酸化チタン等が
挙げられ、これらの１種以上を用いることができる。In the backing layer, if necessary, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant,
An antifoaming agent, a waterproofing agent, a release agent, a fluorescent whitening agent, an antioxidant, and the like may be added as long as the effects of the present invention are not impaired. Further, an inorganic pigment can be added to the backing layer for the purpose of writing properties, flame retardancy, imparting strength, coloring and the like. The addition amount is preferably about 1 to 30% by weight. Examples of the inorganic pigments include calcium carbonate, kaolin, talc, clay, barium sulfate, titanium white, amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, alumina, magnesium carbonate, titanium oxide, and the like. One or more can be used.
【００３２】本発明の記録媒体のうち、保護層と裏打ち
層とがともに熱可塑性樹脂粒子を含む材料から形成され
るものは、多孔質熱可塑性樹脂層からなる保護層を被膜
化するための加熱処理を行う場合も、保護層が転写によ
って形成される樹脂層で形成され熱転写される場合も、
表層と裏打ち層との収縮率等に差が生じにくく、記録画
像のカールの発生が効果的に防止されるため好ましい。In the recording medium of the present invention, the protective layer and the backing layer, both of which are formed of a material containing thermoplastic resin particles, are formed by heating for forming a protective layer of a porous thermoplastic resin layer. Even when performing the treatment, even when the protective layer is formed of a resin layer formed by transfer and thermally transferred,
It is preferable because a difference in shrinkage ratio or the like between the surface layer and the backing layer hardly occurs, and curling of the recorded image is effectively prevented.
【００３３】本発明の記録媒体で使用される式（１）で
表されるベンゾトリアゾール系紫外線吸収剤（以下、
「紫外線吸収剤（１）」ということがある）は優れた紫
外線吸収能を有するだけでなく様々な優れた特性を有し
ている。例えば、紫外線吸収剤（１）は極めて反応性が
高い２個のヒドロキシアルキル基を有するため、必要あ
れば樹脂に化学結合で導入することが可能である。ま
た、紫外線吸収剤（１）のうち２個の長鎖ポリエステル
を分子内に有するものは様々な樹脂、特にここでは保護
層やインク受容層のバインダーに使用される樹脂との相
溶性に優れるという優れた特徴を有している。また、紫
外線吸収剤（１）は、極めて水に難溶であるため、画像
に高度な長期耐候性を与えるだけでなく、優れた耐水性
及び視認性を付与することが可能となる。また、紫外線
吸収剤（１）は高分子量であり、耐熱性や耐熱蒸散性に
優れるため、保護層を熱により被膜化したり熱転写する
際、熱による分解、蒸散することが極めて少ない。The benzotriazole-based ultraviolet absorber represented by the formula (1) used in the recording medium of the present invention (hereinafter referred to as “absorbent”)
The "ultraviolet absorber (1)") has not only excellent ultraviolet absorbing ability but also various excellent properties. For example, since the ultraviolet absorber (1) has two hydroxyalkyl groups having extremely high reactivity, it can be introduced into the resin by a chemical bond if necessary. Among the ultraviolet absorbers (1), those having two long-chain polyesters in the molecule are said to be excellent in compatibility with various resins, in particular, a resin used as a binder of a protective layer and an ink receiving layer. Has excellent features. Further, since the ultraviolet absorbent (1) is extremely hardly soluble in water, it is possible to impart not only high long-term weather resistance to an image but also excellent water resistance and visibility. Further, since the ultraviolet absorber (1) has a high molecular weight and is excellent in heat resistance and heat-resistant transpiration, it hardly decomposes and evaporates by heat when the protective layer is formed into a film by thermal transfer or thermal transfer.
【００３４】本発明の記録媒体に使用される紫外線吸収
剤（１）の具体例としては、２,２’−メチレンビス
［６−（２Ｈ−１,２,３−ベンゾトリアゾ−ル−２−イ
ル）−４−（２−ヒドロキシエチル）フェノール］、
２,２’−メチレンビス［６−（２Ｈ−１,２,３−ベン
ゾトリアゾール−２−イル）−４−（グリコロイルオキ
シエチル）フェノール］、２,２’−メチレンビス［６
−（２Ｈ−１,２,３−ベンゾトリアゾール−２−イル）
−４−（３−ヒドロキシプロパノイルオキシエチル）フ
ェノール］、２,２’−メチレンビス［６−（２Ｈ−１,
２,３−ベンゾトリアゾール−２−イル）−４−（４−
ヒドロキシブタノイルオキシエチル）フェノール］、
２,２’−メチレンビス［６−（２Ｈ−１,２,３−ベン
ゾトリアゾール−２−イル）−４−（５−ヒドロキシヘ
プタノイルオキシエチル）フェノール］、２,２’−メ
チレンビス［６−（２Ｈ−１,２,３−ベンゾトリアゾー
ル−２−イル）−４−（６−ヒドロキシヘキサノイルオ
キシエチル）フェノール］、２,２’−メチレンビス
［６−（２Ｈ−１,２,３−ベンゾトリアゾール−２−イ
ル）−４−（１６−ヒドロキシ−４,１１−ジオキソ−
３,１０−ジオキサヘキサデシル）フェノール］、２,
２’−メチレンビス［６−（２Ｈ−１,２,３−ベンゾト
リアゾール−２−イル）−４−（２４−ヒドロキシ−
４,１１,１８−トリオキソ−３,１０,１７−トリオキサ
トリコシル）フェノール］、２,２’−メチレンビス
［６−（２Ｈ−１,２,３−ベンゾトリアゾール−２−イ
ル）−４−（３１−ヒドロキシ−４,１１,１８,２５−
テトラオキソ−３,１０,１７,２４−テトラオキサヘキ
サデシル）フェノール］、２,２’−メチレンビス［６
−（２Ｈ−１,２,３−ベンゾトリアゾール−２−イル）
−４−（３７−ヒドロキシ−４,１１,１８,２５,３２−
ヘプタオキソ−３,１０,２４,３１−ヘプタオキサヘプ
タトリアコンチル）フェノール］等が挙げられる。Specific examples of the ultraviolet absorbent (1) used for the recording medium of the present invention include 2,2'-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl). -4- (2-hydroxyethyl) phenol],
2,2′-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (glycoloyloxyethyl) phenol], 2,2′-methylenebis [6
-(2H-1,2,3-benzotriazol-2-yl)
-4- (3-hydroxypropanoyloxyethyl) phenol], 2,2'-methylenebis [6- (2H-1,
2,3-benzotriazol-2-yl) -4- (4-
Hydroxybutanoyloxyethyl) phenol],
2,2′-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (5-hydroxyheptanoyloxyethyl) phenol], 2,2′-methylenebis [6- ( 2H-1,2,3-benzotriazol-2-yl) -4- (6-hydroxyhexanoyloxyethyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-benzotriazole -2-yl) -4- (16-hydroxy-4,11-dioxo-
3,10-dioxahexadecyl) phenol], 2,
2'-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (24-hydroxy-
4,11,18-trioxo-3,10,17-trioxatricosyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (31-hydroxy-4,11,18,25-
Tetraoxo-3,10,17,24-tetraoxahexadecyl) phenol], 2,2′-methylenebis [6
-(2H-1,2,3-benzotriazol-2-yl)
-4- (37-hydroxy-4,11,18,25,32-
Heptaoxo-3,10,24,31-heptaoxaheptatricontyl) phenol] and the like.
【００３５】紫外線吸収剤（１）は、本発明の記録媒体
のいずれの層に含有させて使用してもよい。即ち、表層
である保護層に含有させて保護層に耐候性を付与するこ
ともできるだけでなく、大量に含有させて紫外線を遮蔽
することも可能である。基材層に含有させて画像に高度
な長期耐候性、耐水性及び視認性を付与させることが出
来る。また紫外線吸収剤（１）をインク受容層に含有さ
せて直接画像に高度な長期耐候性、耐水性及び視認性を
付与することができる。さらには、紫外線吸収剤（１）
は、本発明の記録媒体の裏面に構成される裏打ち層に含
有させ、裏打ち層に長期耐候性を付与することもでき
る。もちろん、これらの複数に同時に配合してもよい。
これらの中でも、保護層、インク受容層及び裏打ち層の
少なくとも一層に紫外線吸収剤（１）を含有させるのが
好ましい。The ultraviolet absorbent (1) may be used in any layer of the recording medium of the present invention. That is, it is possible not only to add weather resistance to the protective layer by including it in the protective layer, which is the surface layer, but also to block ultraviolet rays by including it in a large amount. It can be added to the base material layer to impart high long-term weather resistance, water resistance and visibility to the image. Further, by incorporating the ultraviolet absorbent (1) into the ink receiving layer, it is possible to directly impart high long-term weather resistance, water resistance and visibility to an image. Furthermore, an ultraviolet absorber (1)
Can be contained in a backing layer formed on the back surface of the recording medium of the present invention to impart long-term weather resistance to the backing layer. Of course, you may mix | blend with these several simultaneously.
Among these, it is preferable that at least one of the protective layer, the ink receiving layer and the backing layer contains the ultraviolet absorbent (1).
【００３６】紫外線吸収剤（１）を表層としての保護層
に含有させて使用する場合、その使用量は保護層の膜厚
に応じて適宜選択されるが、保護層の部材１００重量部
に対して好ましくは０.１〜５０重量部、より好ましく
は１〜２０重量部の範囲で使用するのがよい。使用量が
０.１〜５０重量部の場合、保護層の耐候性及び下層の
画像の耐候性が十分であり、また画像の視認性及び保護
層の機械的物性も良好である。When the ultraviolet absorbent (1) is used by being contained in the protective layer as a surface layer, the amount of the ultraviolet absorbent is appropriately selected according to the thickness of the protective layer. It is preferably used in the range of 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight. When the amount is 0.1 to 50 parts by weight, the weather resistance of the protective layer and the weather resistance of the lower layer image are sufficient, and the visibility of the image and the mechanical properties of the protective layer are also good.
【００３７】また、紫外線吸収剤（１）をインク受容層
に含有させる場合は、インク受容層に用いられるバイン
ダーと混合することにより含有させるのが好ましく、そ
の際の使用量としては、バインダー１００重量部に対し
て０.１〜５０重量部、好ましくは０.３〜１０重量部、
より好ましくは１〜７重量部の範囲とするのがよい。紫
外線吸収剤の使用量が０.１〜５０重量部の場合、画像
に十分な耐候性を付与することが容易で、また画像の解
像度も低下することがないので好ましい。When the ultraviolet absorbing agent (1) is contained in the ink receiving layer, it is preferable that the ultraviolet absorbing agent (1) is contained by mixing with the binder used in the ink receiving layer. 0.1 to 50 parts by weight, preferably 0.3 to 10 parts by weight,
More preferably, the content is in the range of 1 to 7 parts by weight. When the amount of the ultraviolet absorber is 0.1 to 50 parts by weight, sufficient weather resistance can be easily imparted to the image, and the resolution of the image is not reduced.
【００３８】紫外線吸収剤（１）を本発明の記録媒体の
裏打ち層に含有させて使用する場合、裏打ち層の構成材
料１００重量部に対して好ましくは０.１〜５重量部、
より好ましくは０.２〜３重量部の範囲で使用するのが
よい。紫外線吸収剤の使用量が０.１〜５重量部の場合
は、配合の効果が十分に発揮され、また経済的にも有利
である。紫外線吸収剤（１）は、単独で使用することも
できるし、また２種以上混合して使用することもでき
る。また本発明の効果を損なわない範囲で、一般的なベ
ンゾトリアゾール系、ベンゾフェノン系、トリアジン
系、ベンゾエート系、及び桂皮酸系紫外線吸収剤、さら
にはヒンダードアミン等の光安定剤や硫黄系、リン系、
ヒンダードフェノール系の酸化防止剤と併用することも
できる。When the ultraviolet absorbent (1) is used by being contained in the backing layer of the recording medium of the present invention, it is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the constituent material of the backing layer.
More preferably, it is used in the range of 0.2 to 3 parts by weight. When the amount of the ultraviolet absorber is 0.1 to 5 parts by weight, the effect of the compounding is sufficiently exhibited, and it is economically advantageous. The ultraviolet absorber (1) can be used alone or in combination of two or more. In addition, within the range not impairing the effects of the present invention, general benzotriazole-based, benzophenone-based, triazine-based, benzoate-based, and cinnamic acid-based ultraviolet absorbers, as well as light stabilizers such as hindered amines and sulfur-based, phosphorus-based,
It can be used in combination with a hindered phenol-based antioxidant.
【００３９】本発明の記録媒体は、記録情報に応じてイ
ンク滴を表層を介してインク受容層に付与することによ
って画像を形成することができる。記録終了後に、表層
を加熱処理してこれを非多孔質の連続した透明なフィル
ム状の保護層に変化させるか、もしくはあらかじめ別の
基材層に積層させた樹脂層を熱転写して保護層を形成さ
せることにより、耐候性、耐水性、視認性、耐傷性、及
び耐ＮＯｘ性が向上した画像を得ることができる。記録
媒体にインクを付与する方法としては、特に制限はない
が、高速印字、高精細印字を可能とする点で、インクジ
ェット方式が好ましい。またインクとしては、水系、溶
剤系等、特に限定されるものではなく、また色素として
は染料もしくは顔料のどちらでも使用可能である。The recording medium of the present invention can form an image by applying ink droplets to the ink receiving layer via the surface layer according to the recording information. After the recording is completed, the surface layer is heat-treated to change it into a non-porous continuous transparent film-like protective layer, or the resin layer previously laminated on another base material layer is thermally transferred to form the protective layer. By forming, an image having improved weather resistance, water resistance, visibility, scratch resistance, and NOx resistance can be obtained. The method for applying ink to the recording medium is not particularly limited, but an ink jet method is preferable in that high-speed printing and high-definition printing can be performed. The ink is not particularly limited, such as a water-based ink or a solvent-based ink, and either a dye or a pigment can be used as a pigment.
【００４０】本発明の記録媒体の用途としては、特に限
定されず、具体的にはパーソナルコンピューター、複写
機、ワープロ、ＦＡＸ、プロッター等の様々な情報機器
のプリンターの記録材用途、デジタルカメラ、デジタル
ビデオ、スキャナー、医療機器、分析機器、測定機器等
の画像情報の出力機の記録材用途、看板、バックライト
の看板、ポスター、マーキングフィルム、標識、標示板
等のディスプレー用途、衣料、絨毯、カーテン等の繊維
用途、建材の内外装用途、自動車部材用途、キャッシュ
カード、ＩＤカード等カード類の絵柄用途、食品、化学
品、医薬品、その他あらゆる商品の容器、ラベル又は包
装材の絵柄用途、その他家具、スポーツ用品、レジャー
用品、玩具や文房具の絵柄用途などが挙げられる。The use of the recording medium of the present invention is not particularly limited. Specifically, it is used as a recording material for printers of various information devices such as a personal computer, a copying machine, a word processor, a facsimile, a plotter, a digital camera, and a digital camera. Recording materials for image information output machines such as video, scanners, medical equipment, analytical equipment, measuring equipment, etc., signs, signs for backlights, posters, marking films, signs, signs, signboards, clothing, carpets, curtains For textiles, interior and exterior of building materials, automotive parts, cash cards, ID cards and other card designs, food, chemicals, pharmaceuticals, and any other product containers, labels or packaging materials, and other furniture. , Sporting goods, leisure goods, toys and stationery designs.
【００４１】[0041]
【実施例】以下実施例を挙げ、本発明を具体的に詳細に
説明するが、これに限定されるものではない。The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００４２】合成例１ 冷却管、窒素導入管、温度計及び撹拌装置を備えた四口
フラスコに２,２’−メチレンビス［６−（２Ｈ−１,
２,３−ベンゾトリアゾール−２−イル）−４−（２−
ヒドロキシエチル）フェノール］（「ＲＵＶＡ−１０
０」、大塚化学（株）製）１２９.３ｇ、ε−カプロラ
クトン［ダイセル化学工業（株）製］１７０.３ｇ、モ
ノ−ｎ−ブチルスズ脂肪酸塩［「ＳＣＡＴ−２４」、三
共有機合成（株）製］５０ｐｐｍを加えた。反応温度を
１５０℃に保ちながら６時間反応させると酸価（ｍｇＫ
ＯＨ／ｇ）１.８、粘度２６４５ｃｐ（６０℃）、数平
均分子量１３９１、重量平均分子量１６８８、Ｍｗ／Ｍ
ｎ＝１.２１３の目的物である２,２’−メチレンビス
［６−（２Ｈ−１,２,３−ベンゾトリアゾール−２−イ
ル）−４−（２３−ヒドロキシ−４,１１,１８−トリオ
キソ−３,１０,１７−トリオキサトリコシル）フェノー
ル］が粘調オイルとして得られた（収率９８％）。Synthesis Example 1 A four-necked flask equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer was charged with 2,2'-methylenebis [6- (2H-1,
2,3-benzotriazol-2-yl) -4- (2-
Hydroxyethyl) phenol] (“RUVA-10
0 ", Otsuka Chemical Co., Ltd.), 129.3 g, ε-caprolactone [Daicel Chemical Industries, Ltd.], 170.3 g, mono-n-butyltin fatty acid salt [“ SCAT-24 ”, Sankyoki Gosei Co., Ltd. 50 ppm). When the reaction is performed for 6 hours while maintaining the reaction temperature at 150 ° C., the acid value (mgK
OH / g) 1.8, viscosity 2645 cp (60 ° C.), number average molecular weight 1391, weight average molecular weight 1688, Mw / M
2,2′-Methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (23-hydroxy-4,11,18-trioxo) which is the target compound of n = 1.213 -3,10,17-trioxatricosyl) phenol] was obtained as a viscous oil (98% yield).
【００４３】合成例２ 冷却管、窒素導入管、温度計及び撹拌装置を備えた四口
フラスコに２,２’−メチレンビス［６−（２Ｈ−１,
２,３−ベンゾトリアゾール−２−イル）−４−（２−
ヒドロキシエチル）フェノール］［ＲＵＶＡ−１０
０」、大塚化学（株）製］９３.７ｇ、ε−カプロラク
トン［ダイセル化学工業（株）製］２０６.３ｇ、モノ
−ｎ−ブチルスズ脂肪酸塩［「ＳＣＡＴ−２４」、三共
有機合成（株）製］５０ｐｐｍを加えた。反応温度を１
５０℃に保ちながら６時間反応すると酸価（ｍｇＫＯＨ
／ｇ）２.５、粘度９８７ｃｐ（６０℃）、数平均分子
量２０１７、重量平均分子量２４６５、Ｍｗ／Ｍｎ＝
１.２２２の目的物である２,２’−メチレンビス［６−
（２Ｈ−１,２,３−ベンゾトリアゾール−２−イル）−
４−（３７−ヒドロキシ−４,１１,１８,２５,３２−ヘ
プタオキソ−３,１０,２４,３１−ヘプタオキサヘプタ
トリアコンチル）フェノール］がワックス状固体として
得られた（収率９８％）。Synthesis Example 2 In a four-necked flask equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer, 2,2'-methylenebis [6- (2H-1,
2,3-benzotriazol-2-yl) -4- (2-
Hydroxyethyl) phenol] [RUVA-10
0 ", manufactured by Otsuka Chemical Co., Ltd.] 93.7 g, ε-caprolactone [manufactured by Daicel Chemical Industries, Ltd.] 206.3 g, mono-n-butyltin fatty acid salt [" SCAT-24 ", Sankyoki Gosei Co., Ltd. 50 ppm). Reaction temperature 1
When the reaction is performed for 6 hours while maintaining the temperature at 50 ° C., the acid value (mg KOH
/ G) 2.5, viscosity 987 cp (60 ° C.), number average molecular weight 2017, weight average molecular weight 2465, Mw / Mn =
2,2′-methylenebis [6-
(2H-1,2,3-benzotriazol-2-yl)-
4- (37-Hydroxy-4,11,18,25,32-heptaoxo-3,10,24,31-heptaoxaheptatriacontyl) phenol] was obtained as a waxy solid (98% yield). .
【００４４】実施例１ 米国特許第４２４２２７１号に記載された方法に従って
アルミニウムアルコキシドを合成し、これを加水分解す
ることによりアルミナコロイダルゾルを得た。このコロ
イダルゾルを脱塩処理した後、酢酸を添加して解膠処理
を行った。このコロイダルゾルを乾燥して得たアルミナ
水和物をＸ線回折により測定したところ、擬ベーマイト
であった。次に、このアルミナ水和物のコロイダルゾル
を濃縮して１５重量％の溶液を得た。一方、ポリビニル
アルコール（ＰＶＡ１１７、クラレ社製）をイオン交換
水に溶解して１０重量％の溶液を得た。これらの２種の
溶液を、アルミナ水和物とポリビニルアルコールの固形
分が重量比で１０：１になるように混合し、攪拌して分
散させた。得られたアルミナ水和物とポリビニルアルコ
ールとの溶液１００重量部に対し、ポリビニルアルコー
ルの架橋剤としてホウ酸１２重量部を添加して塗工液を
得た。基材層は、坪量１５０ｇ／ｍ２、ステキヒトサイ
ズ度２２０秒、ベック平滑度３６０秒の木材パルプと填
剤とからなるロール状の原紙（幅３０ｃｍ、長さ５０
ｍ）を用いた。このロール状の原紙の表面に、ダイコー
ターにより上記の分散液を乾燥塗工量３０ｇ／ｍ２とな
るように塗工し、乾燥させてインク受容層を形成させ
た。Example 1 An aluminum alkoxide was synthesized according to the method described in US Pat. No. 4,242,271 and hydrolyzed to obtain an alumina colloidal sol. After desalting the colloidal sol, deflocculation was performed by adding acetic acid. An alumina hydrate obtained by drying the colloidal sol was measured by X-ray diffraction and found to be pseudo-boehmite. Next, the colloidal sol of the alumina hydrate was concentrated to obtain a 15% by weight solution. On the other hand, polyvinyl alcohol (PVA117, manufactured by Kuraray) was dissolved in ion-exchanged water to obtain a 10% by weight solution. These two solutions were mixed so that the solid content of alumina hydrate and polyvinyl alcohol was 10: 1 by weight ratio, and were dispersed by stirring. To 100 parts by weight of the obtained solution of alumina hydrate and polyvinyl alcohol, 12 parts by weight of boric acid as a crosslinking agent for polyvinyl alcohol was added to obtain a coating liquid. The base material layer is a roll-shaped base paper (width 30 cm, length 50 cm) composed of wood pulp and filler having a basis weight of 150 g / m 2 , a Steckigt sizing degree of 220 seconds, and a Beck smoothness of 360 seconds.
m) was used. The above dispersion was applied to the surface of the roll-shaped base paper by a die coater so as to have a dry coating amount of 30 g / m 2, and dried to form an ink receiving layer.
【００４５】次に、この基材層の裏面に、ラテックス
［日信化学工業社製、製品名：ビニブラン６０２、ＭＦ
Ｔ（最低造膜温度）：１３０℃］の２０重量部液中に合
成例１の紫外線吸収剤０.２重量部、シリカゲル（グレ
ース・デビゾン社製、製品名：サイロイドＰ−４１２）
１重量部を添加した塗工液をダイコーターによって乾燥
塗工量が１０ｇ／ｍ２となるように塗布し、更に、１４
０℃で加熱被膜化して裏打ち層を形成させた。更に、イ
ンク受容層の上に表層として、固形分１５重量％の塩化
ビニル−酢酸ビニル−アクリル酸系ラテックス（平均粒
子径：０.６μｍ、０.１２μｍ以下の粒子の割合が７.
５重量％、Ｔｇ：６５℃、ＭＦＴ：１２７℃）１００重
量部に対して合成例１の紫外線吸収剤５重量部を分散さ
せた液をダイコーターで塗布し、更に、ＭＦＴより低い
６５℃で乾燥して、約５μｍの多孔質ラテックス層を形
成した。以上のようにして、インク受容層、裏打ち層、
表層の順に３段階の塗工を行い、記録媒体を調製した。Next, a latex [manufactured by Nissin Chemical Industry Co., Ltd., product name: VINIBLAN 602, MF]
T (minimum film forming temperature): 130 ° C.] in a liquid of 20 parts by weight, 0.2 parts by weight of the ultraviolet absorbent of Synthesis Example 1, silica gel (product name: Syloid P-412, manufactured by Grace Devison)
The coating liquid to which 1 part by weight was added was applied by a die coater so that the dry coating amount was 10 g / m 2 ,
The film was heated at 0 ° C. to form a backing layer. Further, as a surface layer on the ink receiving layer, a vinyl chloride-vinyl acetate-acrylic acid-based latex having a solid content of 15% by weight (average particle diameter: 0.6 μm, the ratio of particles having a particle size of 0.12 μm or less is 7.
(5% by weight, Tg: 65 ° C., MFT: 127 ° C.) A solution in which 5 parts by weight of the ultraviolet absorbent of Synthesis Example 1 was dispersed with respect to 100 parts by weight was applied by a die coater, and further, at 65 ° C. lower than MFT. After drying, a porous latex layer of about 5 μm was formed. As described above, the ink receiving layer, the backing layer,
A three-stage coating was performed in the order of the surface layer to prepare a recording medium.
【００４６】次に上記方法で得た記録媒体をジェットプ
リンタ［ＢＪＣ６１０ＪＷ、キヤノン（株）社製］に搭
載して画像を形成した後、１４０℃でサンプルを熱処理
して、表層を透明被膜化して銀塩写真画質でカールのな
い平面性の良好な印字物を得た。インク組成は、以下の
通りである。 染料 ３重量部 Ｙ：Ｃ.Ｉ.ダイレクトイエロー８６ Ｍ：Ｃ.Ｉ.アシッドレッド３５ Ｃ：Ｃ.Ｉ.ダイレクトブルー１９９ ＢＫ：Ｃ.Ｉ.フードブラック２ グリセリン ７重量部 チオジグリコール ７重量部 水 ８３重量部Next, after the recording medium obtained by the above method was mounted on a jet printer [BJC610JW, manufactured by Canon Inc.] to form an image, the sample was heat-treated at 140 ° C. to form a transparent coating on the surface layer. A printed matter having a silver salt photographic quality and a good flatness without curl was obtained. The ink composition is as follows. Dye 3 parts by weight Y: CI Direct Yellow 86 M: CI Acid Red 35 C: CI Direct Blue 199 BK: CI Food Black 2 Glycerin 7 parts by weight Thiodiglycol 7 parts by weight 83 parts by weight of water
【００４７】実施例２ 実施例１と同様に、アルミナ水和物のコロイダルゾルの
１５重量％の溶液とポリビニルアルコール（ＰＶＡ１１
７）１０重量％の水溶液を、アルミナ水和物とポリビニ
ルアルコールの固形分が重量比で１０：１になるように
混合し、攪拌して分散させた。得られたアルミナ水和物
とポリビニルアルコールとの溶液１００重量部に対し、
ポリビニルアルコールの架橋剤としてホウ酸１２重量部
を添加して塗工液を得た。基材層も実施例１と同様に、
坪量１５０ｇ／ｍ２、ステキヒトサイズ度２２０秒、ベ
ック平滑度３６０秒の木材パルプと填剤とからなるロー
ル状の原紙（幅３０ｃｍ、長さ５０ｍ）を用い、同じく
同様の方法でインク受容層を形成させた。次に、この基
材層の裏面に、ラテックス［ビニブラン６０２、ＭＦＴ
（最低造膜温度）：１３０℃］の２０重量部液中に合成
例２の紫外線吸収剤０.２重量部、シリカゲル（サイロ
イドＰ−４１２）１重量部を添加した塗工液をダイコー
ターによって乾燥塗工量が１０ｇ／ｍ２となるように塗
布し、更に、１４０℃で加熱被膜化して裏打ち層を形成
させた。Example 2 As in Example 1, a 15% by weight solution of a colloidal sol of alumina hydrate was mixed with polyvinyl alcohol (PVA11).
7) A 10% by weight aqueous solution was mixed so that the solid content of alumina hydrate and polyvinyl alcohol was 10: 1 by weight, and the mixture was stirred and dispersed. For 100 parts by weight of the solution of the obtained alumina hydrate and polyvinyl alcohol,
A coating liquid was obtained by adding 12 parts by weight of boric acid as a crosslinking agent for polyvinyl alcohol. The base material layer is also the same as in Example 1,
A roll-shaped base paper (width: 30 cm, length: 50 m) composed of wood pulp and filler having a basis weight of 150 g / m 2 , a Steckigt sizing degree of 220 seconds, and a Beck smoothness of 360 seconds was used, and ink was received in the same manner. A layer was formed. Next, a latex [Viniblanc 602, MFT
(Minimum film forming temperature: 130 ° C.) A coating liquid obtained by adding 0.2 parts by weight of the ultraviolet absorbent of Synthesis Example 2 and 1 part by weight of silica gel (Syloid P-412) to 20 parts by weight of a liquid by a die coater. Coating was performed so that the dry coating amount was 10 g / m 2, and the coating was further heated at 140 ° C. to form a backing layer.
【００４８】更に、インク受容層の上に表層として合成
例２の紫外線吸収剤５重量部を分散させた固形分１５重
量％の実施例１で用いた塩化ビニル−酢酸ビニル−アク
リル酸系ラテックスをダイコーターで塗布し、更に、Ｍ
ＦＴより低い６５℃で乾燥して、約５μｍの多孔質ラテ
ックス層を形成した。以上のようにして、インク受容
層、裏打ち層、表層の順に３段階の塗工を行い、記録媒
体を調製し、実施例１と同様の方法で銀塩写真画質でカ
ールのない平面性の良好な印字物を得た。Further, a vinyl chloride-vinyl acetate-acrylic acid type latex used in Example 1 having a solid content of 15% by weight in which 5 parts by weight of the ultraviolet absorbent of Synthesis Example 2 was dispersed as a surface layer on the ink receiving layer was used. Apply with a die coater.
Drying at 65 ° C. lower than the FT formed a porous latex layer of about 5 μm. As described above, the ink receiving layer, the backing layer, and the surface layer are applied in three steps to prepare a recording medium, and the image quality is excellent in silver halide photography and curl-free in the same manner as in Example 1. Prints were obtained.
【００４９】実施例３ 実施例１と同様に、アルミナ水和物のコロイダルゾルの
１５重量％の溶液、ポリビニルアルコール（ＰＶＡ１１
７）１０重量％の水溶液、さらに合成例１の紫外線吸収
剤を、アルミナ水和物、ポリビニルアルコール、及び合
成例１の紫外線吸収剤の固形分が重量比で１０：１：
０.２になるように混合し、攪拌して分散させた。得ら
れたアルミナ水和物、ポリビニルアルコール及び上記紫
外線吸収剤との溶液１００重量部に対し、ポリビニルア
ルコールの架橋剤としてホウ酸１２重量部を添加して塗
工液を得た。基材層も実施例１で用いたロール状の原紙
（幅３０ｃｍ、長さ５０ｍ）を用い、同じく同様の方法
でインク受容層を形成させた。Example 3 As in Example 1, a 15% by weight solution of a colloidal sol of alumina hydrate, polyvinyl alcohol (PVA11)
7) A 10% by weight aqueous solution, furthermore, the ultraviolet absorbent of Synthesis Example 1 was mixed with alumina hydrate, polyvinyl alcohol, and the ultraviolet absorbent of Synthesis Example 1 in a solid content of 10: 1 by weight:
The mixture was mixed to 0.2 and stirred for dispersion. To 100 parts by weight of the solution of the obtained alumina hydrate, polyvinyl alcohol and the ultraviolet absorber, 12 parts by weight of boric acid was added as a crosslinking agent for polyvinyl alcohol to obtain a coating liquid. As the base layer, the ink receiving layer was formed in the same manner using the roll-shaped base paper (width 30 cm, length 50 m) used in Example 1.
【００５０】次に、この基材層の裏面に、ラテックス
［ビニブラン６０２、ＭＦＴ（最低造膜温度）：１３０
℃］の２０重量部液中に合成例１の紫外線吸収剤０.２
重量部、シリカゲル（サイロイドＰ−４１２）１重量部
を添加した塗工液をダイコーターによって乾燥塗工量が
１０ｇ／ｍ２となるように塗布し、更に、１４０℃で加
熱被膜化して裏打ち層を形成させた。更に、インク受容
層の上に表層として固形分１５重量％の実施例１で用い
た塩化ビニル−酢酸ビニル−アクリル酸系ラテックスを
ダイコーターで塗布し、更に、ＭＦＴより低い６５℃で
乾燥して、約５μｍの多孔質ラテックス層を形成した。
以上のようにして、インク受容層、裏打ち層、表層の順
に３段階の塗工を行い、記録媒体を調製し、実施例１と
同様の方法で銀塩写真画質でカールのない平面性の良好
な印字物を得た。Next, on the back surface of this base material layer, a latex [Vinibulan 602, MFT (minimum film forming temperature): 130
° C] in 20 parts by weight of a solution.
Parts by weight, and a coating solution containing 1 part by weight of silica gel (Syloid P-412) was applied by a die coater so as to have a dry coating amount of 10 g / m 2, and further heated at 140 ° C. to form a backing layer. Was formed. Further, the vinyl chloride-vinyl acetate-acrylic acid type latex used in Example 1 having a solid content of 15% by weight as a surface layer was applied on the ink receiving layer by a die coater, and further dried at 65 ° C. lower than MFT. , About 5 μm of a porous latex layer was formed.
As described above, the ink receiving layer, the backing layer, and the surface layer are applied in three steps to prepare a recording medium, and the image quality is excellent in silver halide photography and curl-free in the same manner as in Example 1. Prints were obtained.
【００５１】実施例４ 実施例１と同様に、アルミナ水和物のコロイダルゾルの
１５重量％の溶液とポリビニルアルコール（ＰＶＡ１１
７）１０重量％の水溶液を、アルミナ水和物とポリビニ
ルアルコールの固形分が重量比で１０：１になるように
混合し、攪拌して分散させた。得られたアルミナ水和物
とポリビニルアルコールとの溶液１００重量部に対し、
ポリビニルアルコールの架橋剤としてホウ酸１２重量部
を添加して塗工液を得た。基材層も実施例１で用いたロ
ール状の原紙（幅３０ｃｍ、長さ５０ｍ）を用い、同じ
く同様の方法でインク受容層を形成させた。次に、この
基材層の裏面に、ラテックス［ビニブラン６０２、ＭＦ
Ｔ（最低造膜温度）：１３０℃］の２０重量部液中に微
粉砕した２,２’−メチレンビス［６−（２Ｈ−１,２,
３−ベンゾトリアゾール−２−イル）−４−（２−ヒド
ロキシエチル）フェノール］［「ＲＵＶＡ−１００」、
大塚化学（株）製］０.２重量部、シリカゲル（サイロ
イドＰ−４１２）１重量部を添加した塗工液をダイコー
ターによって乾燥塗工量が１０ｇ／ｍ２となるように塗
布し、更に、１４０℃で加熱被膜化して裏打ち層を形成
させた。Example 4 As in Example 1, a 15% by weight solution of colloidal sol of alumina hydrate and polyvinyl alcohol (PVA11) were used.
7) A 10% by weight aqueous solution was mixed so that the solid content of alumina hydrate and polyvinyl alcohol was 10: 1 by weight, and the mixture was stirred and dispersed. For 100 parts by weight of the solution of the obtained alumina hydrate and polyvinyl alcohol,
A coating liquid was obtained by adding 12 parts by weight of boric acid as a crosslinking agent for polyvinyl alcohol. As the base layer, the ink receiving layer was formed in the same manner using the roll-shaped base paper (width 30 cm, length 50 m) used in Example 1. Next, a latex [Viniblanc 602, MF
T (minimum film formation temperature): 130 ° C.], 2,2′-methylenebis [6- (2H-1,2,
3-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] [“RUVA-100”,
Otsuka Chemical Co., Ltd.], and a coating liquid containing 0.2 parts by weight of silica gel and 1 part by weight of silica gel (Syloid P-412) was applied by a die coater so that the dry coating amount was 10 g / m 2. At 140 ° C. to form a backing layer.
【００５２】更に、インク受容層の上に表層として微粉
砕した２,２’−メチレンビス［６−（２Ｈ−１,２,３
−ベンゾトリアゾール−２−イル）−４−（２−ヒドロ
キシエチル）フェノール］（「ＲＵＶＡ−１００」）５
重量部を分散させた固形分１５重量％の実施例１で用い
た塩化ビニル−酢酸ビニル−アクリル酸系ラテックスを
ダイコーターで塗布し、更に、ＭＦＴより低い６５℃で
乾燥して、約５μｍの多孔質ラテックス層を形成した。
以上のようにして、インク受容層、裏打ち層、表層の順
に３段階の塗工を行い、記録媒体を調製し、実施例１と
同様の方法で銀塩写真画質でカールのない平面性の良好
な印字物を得た。Further, 2,2'-methylenebis [6- (2H-1,2,3) finely pulverized as a surface layer on the ink receiving layer.
-Benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] ("RUVA-100") 5
A vinyl chloride-vinyl acetate-acrylic acid-based latex used in Example 1 having a solid content of 15% by weight in which a part by weight is dispersed is applied with a die coater, and further dried at 65 ° C. lower than MFT to obtain about 5 μm. A porous latex layer was formed.
As described above, the ink receiving layer, the backing layer, and the surface layer are applied in three steps to prepare a recording medium, and the image quality is excellent in silver halide photography and curl-free in the same manner as in Example 1. Prints were obtained.
【００５３】実施例５ 膨潤性ポリエステル樹脂［「ＮＳ１４１ＬＸ」、高松樹
脂（株）製］、ジルコニウム系硬化剤［「ジルコゾール
ＺＣ−２」、第一希元素化学工業（株）製）、及びシリ
カ［「ミズカシルＰ７０５」、水澤化学（株）製］が固
形分重量比で１００：２：４０となるように含水メタノ
ール（６０重量％）に溶解、分散し、固形分２０重量％
の塗工液を得た。実施例１で使用したロール状の原紙
（幅３０ｃｍ、長さ５０ｍ）に、乾燥塗工量３０ｇ／ｍ
２となるように塗工し、１２０℃で乾燥させてインク受
容層を形成させた。次に、この基材層の裏面に、ラテッ
クス［ビニブラン６０２、ＭＦＴ（最低造膜温度）：１
３０℃］の２０重量部液中に合成例１の紫外線吸収剤
０.２重量部、シリカゲル（サイロイドＰ−４１２）１
重量部を添加した塗工液をダイコーターによって乾燥塗
工量が１０ｇ／ｍ２となるように塗布し、更に、１４０
℃で加熱被膜化して裏打ち層を形成させ、記録媒体を調
製した。Example 5 A swellable polyester resin [NS141LX, manufactured by Takamatsu Resin Co., Ltd.], a zirconium-based curing agent [Zircosol ZC-2, manufactured by Dai-ichi Rare Element Chemical Industry Co., Ltd.], and silica [ Mizukasil P705 ", manufactured by Mizusawa Chemical Co., Ltd.] is dissolved and dispersed in water-containing methanol (60% by weight) so as to have a solid content weight ratio of 100: 2: 40, and the solid content is 20% by weight.
Was obtained. The roll-shaped base paper (width 30 cm, length 50 m) used in Example 1 was dried at a coating amount of 30 g / m 2.
2 and dried at 120 ° C. to form an ink receiving layer. Next, a latex [Vinibulan 602, MFT (minimum film forming temperature): 1]
30 ° C.] in a liquid of 20 parts by weight, 0.2 parts by weight of the ultraviolet absorbent of Synthesis Example 1 and silica gel (Syloid P-412) 1
The coating liquid to which the parts by weight were added was applied by a die coater so that the dry coating amount was 10 g / m 2, and 140
A recording medium was prepared by heating to form a backing layer at ℃.
【００５４】また、画像形成ののち受容層上に熱転写す
る保護層は以下のようにして調製した。剥離シートであ
る厚さ５０μｍのＰＥＴフィルム［「テトロンＳ」、帝
人（株）製］上に、合成例１の紫外線吸収剤を固形分重
量比で１０重量％含有させたアクリル系樹脂の固形分含
量４０重量％トルエン溶液［「ダイヤナールＬＲ−２１
６」、三菱レーヨン（株）製］をバーコーターを用いて
乾燥後の厚さが５μｍになるように塗布し、熱風乾燥に
より１２０℃で５分間乾燥した。次に上記樹脂層の上に
熱可塑性接着剤（「ビニブラン２４０」、日信化学工業
（株）製）を同じくバーコーダーを用いて乾燥後の厚さ
が１０μｍになるように塗布して１２０℃で乾燥し接着
層を形成した。上記方法で得た記録媒体は、実施例１と
同様の方法で画像を形成させた。次にラミネート機を用
いて保護層を基材層であるＰＥＴフィルムごと、画像を
形成した記録媒体にラミネートしたのち、基材層フィル
ムのみを剥離すると銀塩写真画質でカールのない平面性
の良好な印字物を得た。ラミネートの条件は、線圧１５
ｋｇ／ｃｍ、温度１４０℃、速度１ｍ／ｍｉｎである。A protective layer to be thermally transferred onto the receiving layer after image formation was prepared as follows. Solid content of acrylic resin containing 10% by weight of UV absorber of Synthesis Example 1 on a 50 μm-thick PET film [“Tetron S”, manufactured by Teijin Limited] as a release sheet 40% by weight toluene solution ["Dianal LR-21"
6 ", manufactured by Mitsubishi Rayon Co., Ltd.] using a bar coater so that the thickness after drying was 5 μm, and dried by hot air drying at 120 ° C. for 5 minutes. Next, a thermoplastic adhesive ("ViniBlan 240", manufactured by Nissin Chemical Industry Co., Ltd.) is applied onto the resin layer using a bar coder in the same manner so that the thickness after drying becomes 10 μm, and the resin is heated to 120 ° C. To form an adhesive layer. An image was formed on the recording medium obtained by the above method in the same manner as in Example 1. Next, using a laminating machine, the protective layer is laminated on the recording medium on which the image has been formed together with the PET film as the base layer, and then the base layer film alone is peeled off to obtain a silver salt photographic image with good curl-free flatness. Prints were obtained. The laminating condition was a linear pressure of 15
kg / cm, temperature 140 ° C., speed 1 m / min.
【００５５】実施例６ 実施例１と同様に、アルミナ水和物のコロイダルゾルの
１５重量％の溶液とポリビニルアルコール（ＰＶＡ１１
７）１０重量％の水溶液を、アルミナ水和物とポリビニ
ルアルコールの固形分が重量比で１０：１になるように
混合し、攪拌して分散させた。得られたアルミナ水和物
とポリビニルアルコールとの溶液１００重量部に対し、
ポリビニルアルコールの架橋剤としてホウ酸１２重量部
を添加して塗工液を得た。基材も実施例１と同様のロー
ル状の原紙（幅３０ｃｍ、長さ５０ｍ）を用い、同じく
同様の方法でインク受容層を形成させた。Example 6 As in Example 1, a 15% by weight solution of a colloidal sol of alumina hydrate was mixed with polyvinyl alcohol (PVA11).
7) A 10% by weight aqueous solution was mixed so that the solid content of alumina hydrate and polyvinyl alcohol was 10: 1 by weight, and the mixture was stirred and dispersed. For 100 parts by weight of the solution of the obtained alumina hydrate and polyvinyl alcohol,
A coating liquid was obtained by adding 12 parts by weight of boric acid as a crosslinking agent for polyvinyl alcohol. As a base material, the same roll-shaped base paper (30 cm in width and 50 m in length) as in Example 1 was used, and an ink receiving layer was formed in the same manner.
【００５６】次に、この基材の裏面に、ラテックス［ビ
ニブラン６０２、ＭＦＴ（最低造膜温度）１３０℃］の
２０重量部液中に、シリカゲル（サイロイドＰ−４１
２）１重量部を添加した塗工液をダイコーターによって
乾燥塗工量が１０ｇ／ｍ２となるように塗布し、更に、
１４０℃で加熱皮膜化して裏打ち層を形成させた。更
に、インク受容層の上に表層として合成例１の紫外線吸
収剤５重量部を分散させた固形分１５重量％の実施例１
で用いた塩化ビニル−酢酸ビニル-アクリル酸系ラテッ
クスをダイコーターで塗布し、更に、ＭＦＴより低い６
５℃で乾燥して、約５μｍの多孔質ラテックス層を形成
した。以上のようにして、インク受容層、裏打ち層、表
層の順に３段階の塗工を行い、記録媒体を調製し、実施
例１と同様の方法で銀塩写真画質でカールのない平面性
の良好な印字物を得た。Next, a silica gel (Syloid P-41) was placed on the back surface of this base material in a 20 parts by weight liquid of latex [Viniblanc 602, MFT (minimum film formation temperature) 130 ° C.].
2) The coating liquid to which 1 part by weight was added was applied by a die coater so that the dry coating amount was 10 g / m 2 .
The film was heated at 140 ° C. to form a backing layer. Further, Example 1 having a solid content of 15% by weight in which 5 parts by weight of the ultraviolet absorbent of Synthesis Example 1 was dispersed as a surface layer on the ink receiving layer.
The vinyl chloride-vinyl acetate-acrylic acid-based latex used in the above was applied with a die coater, and further, 6 lower than MFT.
After drying at 5 ° C., a porous latex layer of about 5 μm was formed. As described above, the ink receiving layer, the backing layer, and the surface layer are applied in three steps to prepare a recording medium, and the image quality is excellent in silver halide photography and curl-free in the same manner as in Example 1. Prints were obtained.
【００５７】比較例１ 実施例１と同様に、アルミナ水和物のコロイダルゾルの
１５重量％の溶液、ポリビニルアルコール（ＰＶＡ１１
７）１０重量％の水溶液、さらに微粉砕した市販の紫外
線吸収剤［「チヌビン３２６」、チバ・スペシャルティ
ー・ケミカルズ（株）製］を、アルミナ水和物、ポリビ
ニルアルコール、及び上記紫外線吸収剤の固形分が重量
比で１０：１：０.２になるように混合し、攪拌して分
散させた。得られたアルミナ水和物、ポリビニルアルコ
ール及び上記紫外線吸収剤との溶液１００重量部に対
し、ポリビニルアルコールの架橋剤としてホウ酸１２重
量部を添加して塗工液を得た。Comparative Example 1 As in Example 1, a 15% by weight solution of colloidal sol of alumina hydrate, polyvinyl alcohol (PVA11)
7) A 10% by weight aqueous solution, and a finely pulverized commercially available ultraviolet absorber [“Tinuvin 326”, manufactured by Ciba Specialty Chemicals Co., Ltd.] were added to alumina hydrate, polyvinyl alcohol, and the above ultraviolet absorber. The solids were mixed so that the weight ratio became 10: 1: 0.2, and dispersed by stirring. To 100 parts by weight of the solution of the obtained alumina hydrate, polyvinyl alcohol and the ultraviolet absorber, 12 parts by weight of boric acid was added as a crosslinking agent for polyvinyl alcohol to obtain a coating liquid.
【００５８】基材層も実施例１で使用したロール状の原
紙（幅３０ｃｍ、長さ５０ｍ）を用い、同じく同様の方
法でインク受容層を形成させた。次に、この基材層の裏
面に、ラテックス［ビニブラン６０２、ＭＦＴ（最低造
膜温度）：１３０℃］の２０重量部液中に市販の紫外線
吸収剤（チヌビン３２６）０.２重量部、シリカゲル
（サイロイドＰ−４１２）１重量部を添加した塗工液を
ダイコーターによって乾燥塗工量が１０ｇ／ｍ２となる
ように塗布し、更に、１４０℃で加熱被膜化して裏打ち
層を形成させた。以上のようにして、インク受容層、裏
打ち層の順に２段階の塗工を行い、記録媒体を調製し、
実施例１と同様の方法で印字物を得た。As the base layer, the ink receiving layer was formed in the same manner using the roll-shaped base paper (width 30 cm, length 50 m) used in Example 1. Next, 0.2 part by weight of a commercially available ultraviolet absorber (tinuvin 326) in 20 parts by weight of a latex [Vinibulan 602, MFT (minimum film-forming temperature): 130 ° C.] (Syloid P-412) A coating liquid to which 1 part by weight was added was applied by a die coater so that the dry coating amount was 10 g / m 2, and further, the coating was heated at 140 ° C. to form a backing layer. . As described above, two-stage coating is performed in the order of the ink receiving layer and the backing layer to prepare a recording medium,
A printed matter was obtained in the same manner as in Example 1.
【００５９】比較例２ 実施例１と同様に、アルミナ水和物のコロイダルゾルの
１５重量％の溶液とポリビニルアルコール（ＰＶＡ１１
７）１０重量％の水溶液を、アルミナ水和物とポリビニ
ルアルコールの固形分が重量比で１０：１になるように
混合し、攪拌して分散させた。得られたアルミナ水和物
とポリビニルアルコールとの溶液１００重量部に対し、
ポリビニルアルコールの架橋剤としてホウ酸１２重量部
を添加して塗工液を得た。基材層も実施例１で使用した
ロール状の原紙（幅３０ｃｍ、長さ５０ｍ）を用い、同
じく同様の方法でインク受容層を形成させた。Comparative Example 2 As in Example 1, a 15% by weight solution of a colloidal sol of alumina hydrate was mixed with polyvinyl alcohol (PVA11).
7) A 10% by weight aqueous solution was mixed so that the solid content of alumina hydrate and polyvinyl alcohol was 10: 1 by weight, and the mixture was stirred and dispersed. For 100 parts by weight of the solution of the obtained alumina hydrate and polyvinyl alcohol,
A coating liquid was obtained by adding 12 parts by weight of boric acid as a crosslinking agent for polyvinyl alcohol. As the base layer, the ink receiving layer was formed in the same manner using the roll-shaped base paper (width 30 cm, length 50 m) used in Example 1.
【００６０】次に、この基材層の裏面に、ラテックス
［ビニブラン６０２、ＭＦＴ（最低造膜温度）：１３０
℃］の２０重量部液中に市販の紫外線吸収剤（チヌビン
２１３）０.２重量部、シリカゲル（サイロイドＰ−４
１２）１重量部を添加した塗工液をダイコーターによっ
て乾燥塗工量が１０ｇ／ｍ２となるように塗布し、更
に、１４０℃で加熱被膜化して裏打ち層を形成させた。
更に、インク受容層の上に表層として市販の紫外線吸収
剤（チヌビン２１３）５重量部を分散させた固形分１５
重量％の実施例１で用いた塩化ビニル−酢酸ビニル−ア
クリル酸系ラテックスをダイコーターで塗布し、更に、
ＭＦＴより低い６５℃で乾燥して、約５μｍの多孔質ラ
テックス層を形成した。以上のようにして、インク受容
層、裏打ち層、表層の順に３段階の塗工を行い、記録媒
体を調製し、実施例１と同様の方法で写真画質の印字物
を得た。Next, a latex [Vinibulan 602, MFT (minimum film forming temperature): 130]
° C], 0.2 parts by weight of a commercially available ultraviolet absorber (Tinuvin 213) and silica gel (Syloid P-4)
12) The coating liquid to which 1 part by weight was added was applied by a die coater so that the dry coating amount was 10 g / m 2, and further, it was heated at 140 ° C. to form a backing layer to form a backing layer.
Further, on the ink receiving layer, 5 parts by weight of a commercially available ultraviolet absorber (tinuvin 213) was dispersed as a surface layer to obtain a solid content of 15%.
% By weight of a vinyl chloride-vinyl acetate-acrylic acid-based latex used in Example 1 was applied by a die coater.
Drying at 65 ° C., lower than the MFT, formed a porous latex layer of about 5 μm. As described above, three-stage coating was performed in the order of the ink receiving layer, the backing layer, and the surface layer to prepare a recording medium, and a photographic quality print was obtained in the same manner as in Example 1.
【００６１】試験例１ 実施例１〜６と比較例１〜２の印字物をキセノンウェザ
オメーター（ＣＩ３０００、ＡＴＬＡＳ社製）を用いて
温度６３℃、湿度７０％の条件で２００時間耐候促進試
験にかけた後、色彩計［商品名ＣＲ−３００、ミノルタ
（株）製］により促進試験前後の色差を測定して耐候性
の評価を行った（Ｌ＊値、ａ＊値、ｂ＊値、ΔＥ＊
値）。表１〜２には、各値の（３０時間耐促進試験後の
値）−（初期値）を示しており、その値が小さい程、変
色が小さい（耐候性が高い）と評価できる。さらに耐候
性試験前後の視認性の変化についても目視で評価した。
結果を表１〜２に示した。Test Example 1 The printed matter of Examples 1 to 6 and Comparative Examples 1 and 2 was subjected to a 200-hour weathering acceleration test using a xenon weatherometer (CI3000, manufactured by ATLAS) at a temperature of 63 ° C. and a humidity of 70%. After the application, the weather resistance was evaluated by measuring the color difference before and after the acceleration test using a colorimeter (trade name: CR-300, manufactured by Minolta Co., Ltd.) (L * value, a * value, b * value, ΔE). *
value). Tables 1 and 2 show (value after 30-hour acceleration test)-(initial value) of each value, and the smaller the value, the smaller the discoloration (higher weather resistance). Further, the change in visibility before and after the weather resistance test was also visually evaluated.
The results are shown in Tables 1 and 2.
【００６２】[0062]
【表１】 [Table 1]
【００６３】[0063]
【表２】 [Table 2]
【００６４】表１の本発明の実施例１〜６のものは、表
２の比較例１〜２と比較すると、紫外線による変色が非
常に少ない、耐候性に優れた記録媒体である。The recording media of Examples 1 to 6 of the present invention in Table 1 are recording media having very little discoloration due to ultraviolet rays and having excellent weather resistance as compared with Comparative Examples 1 and 2 in Table 2.
【００６５】試験例２ 実施例１〜６と比較例１〜２の印字物を２５℃の水中で
約１５分間放置したのち、布を用いて水分を良く拭き取
り、さらに風乾させた。次にマクベス反射濃度計（ＲＤ
−９１８）を用いて試験前後の反射濃度を測定し、反射
濃度の残存率により記録媒体の耐水性を評価した。この
値が１００％に近いほど、耐水性が優れていると評価で
きる。さらに耐水性試験前後の視認性の変化についても
目視で評価した。結果を表３に示した。 反射濃度残存率（％）＝１００×試験後の反射濃度／反
射前の残存率Test Example 2 The prints of Examples 1 to 6 and Comparative Examples 1 and 2 were allowed to stand in water at 25 ° C. for about 15 minutes, and then sufficiently wiped off with a cloth and air-dried. Next, a Macbeth reflection densitometer (RD
-918), the reflection density before and after the test was measured, and the water resistance of the recording medium was evaluated based on the residual ratio of the reflection density. The closer this value is to 100%, the better the water resistance can be evaluated. Further, the change in visibility before and after the water resistance test was also visually evaluated. The results are shown in Table 3. Reflection density residual ratio (%) = 100 × reflection density after test / residual ratio before reflection
【００６６】[0066]
【表３】 [Table 3]
【００６７】表３の本発明の実施例１〜６のものは、比
較例１〜２と比較すると、水分による退色が極めて少な
い、耐水性に優れた記録媒体である。The recording media of Examples 1 to 6 of the present invention in Table 3 are excellent in water resistance and have very little fading due to moisture as compared with Comparative Examples 1 and 2.
【００６８】試験例３ 実施例１〜６と比較例１〜２の印字物を８００ｇの重り
を載せてこすり、目視により耐傷性を評価した。傷のつ
かないものを○、若干傷のつくものを△、傷のつくもの
を×とした。結果を表４に示した。Test Example 3 The printed materials of Examples 1 to 6 and Comparative Examples 1 and 2 were rubbed with a weight of 800 g and visually evaluated for scratch resistance.な い indicates no damage, Δ indicates slight damage, and × indicates damage. The results are shown in Table 4.
【００６９】[0069]
【表４】 [Table 4]
【００７０】表４の本発明の実施例１〜６のものは、比
較例１〜２と比較すると、表面の傷つきが極めて少な
い、耐傷性に優れた記録媒体である。The recording media of Examples 1 to 6 of the present invention in Table 4 are recording media excellent in scratch resistance and having very little surface damage as compared with Comparative Examples 1 and 2.
【００７１】[0071]
【発明の効果】本発明の記録媒体は、基材層の表面にイ
ンク受容層と表層としての保護層が積層され、更に該基
材層の裏面に裏打ち層を有するものであって、その各層
の少なくとも1層に特定の紫外線吸収剤（１）を含有さ
せることにより、極めて優れた長期耐候性、耐水性、視
認性、耐傷性を有すると共に、複数のシート状の記録媒
体を表層と裏打ち層とが接触された状態で重ね合せて、
あるいはロール状として保管、搬送等を行った場合で
も、これらの層のブロッキングや裏打ち層からのその構
成成分の表層への転移（裏うつり現象）を効果的に防止
することができる。The recording medium of the present invention has an ink receiving layer and a protective layer as a surface layer laminated on the surface of a base material layer, and further has a backing layer on the back surface of the base material layer. By containing a specific ultraviolet absorber (1) in at least one layer of the recording medium, it has extremely excellent long-term weather resistance, water resistance, visibility, and scratch resistance, and a plurality of sheet-like recording media can be used as a surface layer and a backing layer. Are superimposed in contact with
Alternatively, even when the layer is stored or transported in the form of a roll, it is possible to effectively prevent the blocking of these layers and the transfer of the component from the backing layer to the surface layer (back fogging phenomenon).
Claims (6)
ての保護層が積層され、更に該基材層の裏面に裏打ち層
を有する記録媒体において、基材層、インク受容層、保
護層及び裏打ち層の少なくともいずれか一層に式（１）
で表わされるベンゾトリアゾール系紫外線吸収剤を０.
１〜５０重量％含有することを特徴とする記録媒体。 【化１】 〔式中Ｒ１及びＲ２は同一又は異なって、水素原子又は
炭素数１〜１０のアルキル基を示す。ｎ、ｎ’は同一又
は異なって４〜８の数、ｍ、ｍ’は同一又は異なって０
〜２０の数を示す。〕1. A recording medium having an ink receiving layer and a protective layer as a surface layer laminated on the surface of a substrate layer and further having a backing layer on the back surface of the substrate layer. And at least one of the backing layers has the formula (1)
The benzotriazole-based UV absorber represented by
A recording medium containing 1 to 50% by weight. Embedded image Wherein R 1 and R 2 are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n and n 'are the same or different and 4 to 8; m and m' are the same or different and 0
Shows the number of ~ 20. ]
なくともいずれか一層に、式（１）で表されるベンゾト
リアゾール系紫外線吸収剤を０.１〜５０重量％含有す
る請求項１に記載の記録媒体。2. The method according to claim 1, wherein at least one of the ink receiving layer, the protective layer and the backing layer contains 0.1 to 50% by weight of the benzotriazole-based ultraviolet absorber represented by the formula (1). Recording medium.
層であり、且つ該多孔質熱可塑性樹脂層は熱可塑性樹脂
粒子間に保持された空隙を有することで多孔質となって
おり、また該裏打ち層のみが加圧及び／又は加熱により
整膜処理を施されていることを特徴とする請求項１に記
載の記録媒体。3. The protective layer and the backing layer are porous thermoplastic resin layers, and the porous thermoplastic resin layer is porous by having voids held between thermoplastic resin particles. 2. The recording medium according to claim 1, wherein only the backing layer has been subjected to a film-thinning treatment by pressurizing and / or heating.
ダーである水溶性高分子物質を含有することを特徴とす
る請求項１〜３に記載の記録媒体。4. The recording medium according to claim 1, wherein the ink receiving layer contains alumina hydrate and a water-soluble polymer substance as a binder.
剤性樹脂より選ばれる少なくとも一種と、無機粒子から
選ばれる固形部材の少なくとも一種を含有することを特
徴とする請求項１〜４に記載の記録媒体。5. The ink receiving layer according to claim 1, wherein the ink receiving layer contains at least one selected from water-absorbing and / or solvent-absorbing resins and at least one solid member selected from inorganic particles. The recording medium according to the above.
れた樹脂層を転写することにより形成されたものである
請求項１〜５に記載の記録媒体。6. The recording medium according to claim 1, wherein the protective layer is formed by transferring a resin layer previously applied to a release sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000105052A JP3425588B2 (en) | 2000-04-06 | 2000-04-06 | Recording medium with excellent weather resistance, water resistance and visibility |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000105052A JP3425588B2 (en) | 2000-04-06 | 2000-04-06 | Recording medium with excellent weather resistance, water resistance and visibility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001287439A true JP2001287439A (en) | 2001-10-16 |
| JP3425588B2 JP3425588B2 (en) | 2003-07-14 |
Family
ID=18618490
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004291568A (en) * | 2003-03-28 | 2004-10-21 | Nisshinbo Ind Inc | Ink jet recording member |
| US7381762B2 (en) | 2004-08-20 | 2008-06-03 | Milliken & Company | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
| JP2009196373A (en) * | 2002-07-31 | 2009-09-03 | Eastman Kodak Co | Inkjet recording element and printing method |
| JP2010234677A (en) * | 2009-03-31 | 2010-10-21 | Hokuetsu Kishu Paper Co Ltd | Semi-gloss oil-based inkjet recording sheet |
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| JP2000053754A (en) * | 1998-06-03 | 2000-02-22 | Otsuka Chem Co Ltd | Infrared ray-absorptive polymer and weatherproof resin composition using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009196373A (en) * | 2002-07-31 | 2009-09-03 | Eastman Kodak Co | Inkjet recording element and printing method |
| JP2004291568A (en) * | 2003-03-28 | 2004-10-21 | Nisshinbo Ind Inc | Ink jet recording member |
| US7381762B2 (en) | 2004-08-20 | 2008-06-03 | Milliken & Company | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
| JP2010234677A (en) * | 2009-03-31 | 2010-10-21 | Hokuetsu Kishu Paper Co Ltd | Semi-gloss oil-based inkjet recording sheet |
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