JPH0745257B2 - Ink jet recording paper - Google Patents
Ink jet recording paperInfo
- Publication number
- JPH0745257B2 JPH0745257B2 JP61193387A JP19338786A JPH0745257B2 JP H0745257 B2 JPH0745257 B2 JP H0745257B2 JP 61193387 A JP61193387 A JP 61193387A JP 19338786 A JP19338786 A JP 19338786A JP H0745257 B2 JPH0745257 B2 JP H0745257B2
- Authority
- JP
- Japan
- Prior art keywords
- recording paper
- ink jet
- jet recording
- water
- ink
- 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.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は支持体の表面にインク受理層を設けたインクジ
エツト記録用紙に関するものであり、この記録紙上に水
溶性酸性染料および／または水溶性直接染料を含有する
インクを用いて記録した際に、画像が耐水性に優れ、か
つ保存時における退色の少ないインクジエツト記録用紙
に関するものである。The present invention relates to an ink jet recording paper in which an ink receiving layer is provided on the surface of a support, on which a water-soluble acid dye and / or a water-soluble direct dye is directly applied. The present invention relates to an ink jet recording paper having an image that is excellent in water resistance and less discolored during storage when recorded using an ink containing a dye.
近年、インクジエツト記録方式はフルカラーが可能なノ
ンインパクトタイプの記録方式として各種プリンターへ
の応用が急速におこなわれている。In recent years, the ink jet recording system has been rapidly applied to various printers as a non-impact type recording system capable of full color.
一方、これに使用されるインクには、ノズル先端の目づ
まり防止の点から水溶性酸性染料および／または水溶性
直接染料が一般に使われている。On the other hand, in the ink used for this purpose, a water-soluble acid dye and / or a water-soluble direct dye is generally used from the viewpoint of preventing clogging of the nozzle tip.
このため、通常のノンコートタイプ（低サイズ紙）の記
録紙や、微粉末の合成シリカ、カオリン、炭酸カルシユ
ウム等の顔料と、ポリビニルアルコール、酸化でんぷ
ん、ヒドロキシエチルセルロース等の水溶性バインダー
とからなる塗剤を支持体に塗布し乾燥して支持体表面に
インク受容層を設けたコートタイプの記録紙に記録され
た画像は、水により容易に流出してしまう欠点がある。For this reason, ordinary non-coated type (low-sized paper) recording paper, coating agent consisting of fine powder of synthetic silica, kaolin, calcium carbonate and other pigments, and water-soluble binder such as polyvinyl alcohol, starch starch and hydroxyethyl cellulose. An image recorded on a coat type recording paper having an ink receiving layer provided on the surface of the support after being coated on a support and dried is easily discharged by water.
このため、記録紙上の画像を耐水化する方法として、前
述の記録紙またはそのインク受容層に、ポリビニルピリ
ジウムブロマイド、ポリエチレンイミン（特開昭56−84
992号）、ジメチルジアリルアンモニウムクロライド
（特開昭59−20696号）、ポリエチレンイミン有機酸塩
（特開昭59−198186号）、ポリアルキレンポリアミンジ
シアンジアミドアンモニウム塩縮合物（特開昭60−4999
0号）、ポリエチレンイミン第４級アンモニウム化合物
（特開昭60−76386号）等のポリカチオン高分子電解質
を耐水化剤としてインク受容層中に含有させることが提
案されている。For this reason, as a method for making an image on a recording paper water resistant, polyvinylpyridinium bromide and polyethyleneimine (JP-A-56-84) are used for the recording paper or the ink receiving layer thereof.
992), dimethyldiallylammonium chloride (JP 59-20696), polyethyleneimine organic acid salt (JP 59-198186), polyalkylene polyamine dicyandiamide ammonium salt condensate (JP 60-4999).
No. 0), polyethyleneimine quaternary ammonium compounds (JP-A-60-76386), and the like have been proposed to be contained in the ink receiving layer as a waterproofing agent.
しかしながら、これらの化合物はその耐水性の効果が劣
るか、耐水性が十分な程含有させると画像の耐光性が著
しく低下するという欠点や、前述コートタイプの記録紙
に用いられる塗料に配合した場合に、増粘やゲル化の問
題を生じるため低濃度の塗剤しか得られない欠点を有
し、かならずしも満足のいくものではない。However, these compounds are inferior in their water resistance effect, or have the disadvantage that the light resistance of the image is remarkably deteriorated if they are contained to such an extent that the water resistance is sufficient, and when compounded in the coating used for the above-mentioned recording paper of the coating type. In addition, it has a drawback that only a low concentration of the coating agent can be obtained due to problems of thickening and gelation, and it is not always satisfactory.
本発明は、特定の第４級アンモニウム塩型高分子電解質
をインク受理層に含ませることにより、耐水性に優れ、
画像の光による退色性の少ないインクジエツト記録紙を
提供する。The present invention has excellent water resistance by including a specific quaternary ammonium salt type polymer electrolyte in the ink receiving layer,
Provided is an ink jet recording paper which is less likely to be faded by the light of an image.
すなわち、本発明は紙、樹脂フイルム等の支持体表面に
設けられたインク受理層に、下記構造式で示される構成
単位を少なくとも60重量％以上の割合で含有する第４級
アンモニウム塩型高分子電解質を含有させたインクジエ
ツト記録用紙を提供するものである。That is, the present invention is a quaternary ammonium salt type polymer containing a constitutional unit represented by the following structural formula at a ratio of at least 60% by weight or more in an ink receiving layer provided on the surface of a support such as paper or resin film. An ink jet recording paper containing an electrolyte is provided.
〔式中、R1;HもしくはCH3、 A;OもしくはNH、 R2；C2〜C4のアルキレン基もしくは R1，R4，R5，R6；C1〜C3のアルキル基、 R7；C1〜C18好ましくはC1〜C8のアルキル基もしくはベ
ンジル基、 n;1〜３の整数である。〕 本発明に用いられる第４級アンモニウム塩型高分子電解
質は、下記一般式〔Ｉ〕に示される第３級アミン含有モ
ノマーと、一般式〔II〕に示される変性剤とを反応して
得られる第４級アンモニウム塩型モノマーを単独、もし
くは他の共重合しうるモノマーと重合するか、あるいは
前述一般式〔Ｉ〕で示される第三級アミン含有モノマー
を単独、もしくは他の共重合しうるモノマーと重合した
後、一般式〔II〕の変性剤と反応する事により得られ
る。 [In the formula, R 1 ; H or CH 3 , A; O or NH, R 2 ; C 2 to C 4 alkylene group or R 1 , R 4 , R 5 , R 6 ; C 1 to C 3 alkyl group, R 7 ; C 1 to C 18, preferably C 1 to C 8 alkyl group or benzyl group, n; integer of 1 to 3 Is. The quaternary ammonium salt type polymer electrolyte used in the present invention is obtained by reacting a tertiary amine-containing monomer represented by the following general formula [I] with a modifying agent represented by the general formula [II]. The quaternary ammonium salt type monomer may be polymerized alone or with other copolymerizable monomers, or the tertiary amine-containing monomer represented by the above general formula [I] may be polymerized alone or with other copolymerization. It is obtained by polymerizing with a monomer and then reacting with a modifier of the general formula [II].
一般式〔Ｉ〕 〔式中、R1;HもしくはCH3 A;OもしくはNH R2；C2〜C4のアルキレン基もしくは R3，R4；C1〜C3のアルキル基〕 一般式〔II〕 〔式中、R5，R6；C1〜C3のアルキル基 R7；C1〜C18好ましくはC1〜C6のアルキル基もしくはベ
ンジル基、 X;ハロゲン原子 n;1〜３の整数〕 ここで一般式〔Ｉ〕で示される第３級アミン含有モノマ
ーとしては、N,N−ジメチルアミノエチル（メタ）アク
リレート、N,N−ジエチルアミノエチル（メタ）アクリ
レート、N,N−ジメチルアミノプロピル（メタ）アクリ
レート、N,N−ジメチル−２−ヒドロキシプロピル（メ
タ）アクリレート、N,N−ジメチルアミノプロピル（メ
タ）アクリルアミドが挙げられる。又、この第３級アミ
ン含有モノマーあるいはその変性化された第４級アンモ
ニウム塩型モノマーと共重合可能な他のモノマーとして
は、メチル（メタ）アクリレート、エチル（メタ）アク
リレートなどの（メタ）アクリル酸エステル類、スチレ
ン、ビニルトルエン、（メタ）アクリルアミドなどが挙
げられる。General formula [I] [In the formula, R 1 ; H or CH 3 A; O or NH R 2 ; C 2 to C 4 alkylene group or R 3 , R 4 ; C 1 -C 3 alkyl group] General formula [II] [In the formula, R 5 and R 6 ; C 1 to C 3 alkyl group R 7 ; C 1 to C 18, preferably C 1 to C 6 alkyl group or benzyl group, X; halogen atom n; Integer] Here, as the tertiary amine-containing monomer represented by the general formula [I], N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Examples include propyl (meth) acrylate, N, N-dimethyl-2-hydroxypropyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylamide. Further, other monomers copolymerizable with the tertiary amine-containing monomer or the modified quaternary ammonium salt type monomer include (meth) acryl such as methyl (meth) acrylate and ethyl (meth) acrylate. Examples thereof include acid esters, styrene, vinyltoluene, (meth) acrylamide and the like.
重合は通常の溶液重合、例えばα，α′−アゾビスイソ
ブチロニトリルなどのラジカル開始剤の存在下、水、ア
ルコール類などの溶媒中で行なわれる。The polymerization is carried out by a conventional solution polymerization, for example, in the presence of a radical initiator such as α, α′-azobisisobutyronitrile, in a solvent such as water or alcohol.
ここで、高分子電解質に含まれる前記第４級アンモニウ
ム塩構成単位は60重量％以上、好ましくは80重量％以上
含む必要があり、60重量％未満であると、水性インクで
記録された画像の耐水化が不充分となる。Here, the quaternary ammonium salt constitutional unit contained in the polymer electrolyte must be contained in an amount of 60% by weight or more, preferably 80% by weight or more. Water resistance becomes insufficient.
また、この第４級アンモニウム塩型高分子電解質の平均
分子量は特に限定されないが、２千〜50万である。The average molecular weight of the quaternary ammonium salt type polymer electrolyte is not particularly limited, but is 2,000 to 500,000.
この第４級アンモニウム塩型高分子電解質は水に可溶で
あり、ノンコートタイプの公知のインクジエツト記録用
紙にはそのまま塗布するか、インク吸収層を塗工した公
知のコートタイプの記録用紙には、そのインク吸収層の
塗剤に混合して支持体に塗工することができる。特に、
後者のコートタイプの方が、画像の鮮明性、吸収性の点
からも好適であるが、本第４級アンモニウム塩型高分子
電解質はインク吸収層として塗工される微粉末の合成シ
リカなどの顔料とポリビニルアルコールなどのバインダ
ーおよび水とからなる塗料に配合した際、ゲル化や増粘
などの問題もなく、良好な配合適性を持つている。This quaternary ammonium salt-type polymer electrolyte is soluble in water, and can be applied as it is to a known non-coat type ink jet recording paper, or to a known coat-type recording paper coated with an ink absorbing layer, It can be mixed with the coating agent for the ink absorbing layer and applied to the support. In particular,
The latter coat type is more preferable in terms of image sharpness and absorption, but the quaternary ammonium salt-type polymer electrolyte is used as an ink absorbing layer such as fine powder synthetic silica. When compounded in a paint consisting of a pigment, a binder such as polyvinyl alcohol, and water, it has no problem of gelation or thickening and has good compounding suitability.
インクジエツト記録用紙のインク受理層中の当該高分子
電解質の含有割合は、画像の耐水性の実用範囲から0.1
〜3g/m2（固型分）である。The content ratio of the polymer electrolyte in the ink receiving layer of the ink jet recording paper is 0.1 from the practical range of water resistance of the image.
~ 3g / m 2 (solid content).
尚、当該高分子電解質の他に、前述の顔料、バインダ
ー、必要に応じて消泡剤、酸化防止剤、紫外線吸収剤、
他の耐水化剤などを塗剤に配合することができる。In addition to the polymer electrolyte, the above-mentioned pigment, binder, if necessary, defoaming agent, antioxidant, ultraviolet absorber,
Other waterproofing agents and the like can be added to the coating material.
以下に実施例によつて本発明を詳細に説明するが、本発
明はこれらの実施例に限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
電解質の製造例 〔合成例１（本発明品）〕 攪拌機、温度計、冷却管および滴下ロートのついて１
フラスコに、N,N−ジメチルアミノエチルメタクリレー
ト200部、イソプロピルアルコール200部およびα，α′
−アゾビスイソプチロニトリル1.2部を仕込み、系内を
窒素ガス置換した後、80℃で４時間重合をおこなつた。Production Example of Electrolyte [Synthesis Example 1 (Product of the Present Invention)] About Stirrer, Thermometer, Cooling Tube and Dropping Funnel 1
In a flask, 200 parts of N, N-dimethylaminoethyl methacrylate, 200 parts of isopropyl alcohol and α, α '
-1.2 parts of azobisisobutyronitrile was charged, the system was replaced with nitrogen gas, and then polymerization was carried out at 80 ° C for 4 hours.
ついで、３−クロロ−２−ヒドロキシプロピルトリメチ
ルアンモニウムクロリド50重量％水溶液を478部（N,N−
ジメチルアミノエチルメタクリレートに対し等モル）添
加し、ついで80℃で６時間反応をおこなつた後、水を滴
下しながらイソプロピルアルコールを留去し、最終的に
固型分30重量％の高分子電解質水溶液を得た。Then, 478 parts of a 50% by weight aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (N, N-
(Equal moles relative to dimethylaminoethylmethacrylate), followed by reacting at 80 ° C. for 6 hours, then isopropyl alcohol was distilled off while adding water dropwise, and finally a polymer electrolyte having a solid content of 30% by weight was added. An aqueous solution was obtained.
〔合成例２（本発明品）〕 合成例１と同様に、N,N−ジメチルアミノエチルメタク
リレート120部、メチルメタクリレート80部からなる前
駆重合体を得たのち、３−クロロ−２−ヒドロキシプロ
ピルトリメチルアンモニウムクロリドで反応し、最終的
に固型分30重量％の高分子電解質水溶液を得た。[Synthesis Example 2 (Product of the present invention)] In the same manner as in Synthesis Example 1, after obtaining a precursor polymer consisting of 120 parts of N, N-dimethylaminoethyl methacrylate and 80 parts of methyl methacrylate, 3-chloro-2-hydroxypropyl was obtained. The reaction was carried out with trimethylammonium chloride to finally obtain a polymer electrolyte aqueous solution having a solid content of 30% by weight.
〔合成例３（比較例品）〕 合成例１と同様に、N,N−ジメチルアミノエチルメタク
リレート60部、メチルメタアクリレート140部からなる
前駆重合体を得たのち、３−クロロ−２−ヒドロキシプ
ロピルトリメチルアンモニウムクロリドで反応し、最終
的に固型分30重量％の高分子電解質水溶液を得た。[Synthesis Example 3 (Comparative Example Product)] In the same manner as in Synthesis Example 1, after obtaining a precursor polymer composed of 60 parts of N, N-dimethylaminoethyl methacrylate and 140 parts of methyl methacrylate, 3-chloro-2-hydroxy was obtained. The reaction was performed with propyltrimethylammonium chloride to finally obtain a polymer electrolyte aqueous solution having a solid content of 30% by weight.
〔合成例４（本発明品）〕 合成例１の前駆体ポリマーを３−クロロ−２−ヒドロキ
シプロピルジメチルベンジルアンモニウムクロリドで反
応し、最終的に固型分30重量％の高分子電解質水溶液を
得た。[Synthesis Example 4 (Product of the Present Invention)] The precursor polymer of Synthesis Example 1 was reacted with 3-chloro-2-hydroxypropyldimethylbenzylammonium chloride to finally obtain a polymer electrolyte aqueous solution having a solid content of 30% by weight. It was
〔合成例５（本発明品）〕 合成例１の前駆体ポリマーの代りに、N,N−ジメチルア
ミノプロピルメタクリルアミドの単独重合体を用い、同
様に３−クロロ−２−ヒドロキトリメチルアンモニウム
クロリドで反応し、最終的に固型分30重量％の高分子電
解質水溶液を得た。[Synthesis Example 5 (Product of the Present Invention)] Instead of the precursor polymer of Synthesis Example 1, a homopolymer of N, N-dimethylaminopropylmethacrylamide was used, and similarly, 3-chloro-2-hydroxytrimethylammonium chloride was used. After the reaction, a polymer electrolyte aqueous solution having a solid content of 30% by weight was finally obtained.
〔実施例１〜４、比較例１〜３〕 コートタイプのインクジエツト記録用紙用塗料液として
は、ホワイトカーボン（塩野義製薬（株）製カープレツ
クス80）、ポリビニルアルコール（日本合成化学（株）
製ゴーセノールＮ−300）、および各種高分子電解質を
固型分重量比で75/25/5からなる固型分濃度15重量％の
塗剤水溶液を調製した。Examples 1 to 4 and Comparative Examples 1 to 3 As coating liquids for coat type ink jet recording paper, white carbon (Carplex 80 manufactured by Shionogi Pharmaceutical Co., Ltd.), polyvinyl alcohol (Nippon Gosei Kagaku Co., Ltd.)
GOSENOL N-300) and various polymer electrolytes were prepared in a solid content weight ratio of 75/25/5 to prepare a coating solution having a solid content concentration of 15% by weight.
これら塗剤水溶液を市販の秤量63g/m2の上質紙の上に、
NO.22のバーコーターを用いて塗布し（固型分5g/m2）、
105℃で１分間乾燥し、記録用紙を得た。On a commercially available fine wood paper weighing 63 g / m 2 of these coating solutions,
Apply using NO.22 bar coater (solid content 5g / m 2 ),
It was dried at 105 ° C for 1 minute to obtain a recording paper.
これらの記録用紙上に、シヤープ（株）製インクジエツ
トプリンターIO−700（商品名）を用いて水溶性直接染
料または水溶性酸性染料を含有するインクジエツト記録
した。耐水性は、被記録紙を水に１分間浸漬し、浸漬前
のものと比較して評価した。又、耐光性は被記録紙をキ
セノンフエードメーターにて24時間照射し、照射前のも
のと比較して評価した。An ink jet recording containing a water-soluble direct dye or a water-soluble acid dye was recorded on these recording papers using an ink jet printer IO-700 (trade name) manufactured by Sharp Corporation. The water resistance was evaluated by immersing the recording paper in water for 1 minute and comparing it with that before immersion. The light resistance was evaluated by irradiating the recording paper with a xenon fade meter for 24 hours and comparing it with that before irradiation.
評価結果を表１に示す。The evaluation results are shown in Table 1.
Claims (1)
染料を含有するインクを用いて記録するインクジエツト
記録紙において、支持体表面に設けられるインク受理層
に、下記構造式で示される構成単位を60重量％以上の割
合で有する第４級アンモニウム塩型高分子電解質を含有
させることを特徴とするインクジエツト記録用紙。 〔式中、R1;HもしくはCH3 A;OもしくはNH R2；C2〜C4のアルキレン基もしくは R3，R4，R5，R6；C1〜C3のアルキル基 R7；C1〜C18好ましくはC1〜C8のアルキル基もしくはベ
ンジル基， n;1〜３の整数である。〕1. In an ink jet recording paper for recording using an ink containing a water-soluble acid dye and / or a water-soluble direct dye, an ink receiving layer provided on the surface of a support is provided with a constitutional unit represented by the following structural formula. An ink jet recording paper containing a quaternary ammonium salt type polymer electrolyte in an amount of 60% by weight or more. [In the formula, R 1 ; H or CH 3 A; O or NH R 2 ; C 2 to C 4 alkylene group or R 3 , R 4 , R 5 , R 6 ; C 1 to C 3 alkyl group R 7 ; C 1 to C 18, preferably C 1 to C 8 alkyl group or benzyl group, n; an integer of 1 to 3 is there. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61193387A JPH0745257B2 (en) | 1986-08-19 | 1986-08-19 | Ink jet recording paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61193387A JPH0745257B2 (en) | 1986-08-19 | 1986-08-19 | Ink jet recording paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6349478A JPS6349478A (en) | 1988-03-02 |
| JPH0745257B2 true JPH0745257B2 (en) | 1995-05-17 |
Family
ID=16307087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61193387A Expired - Fee Related JPH0745257B2 (en) | 1986-08-19 | 1986-08-19 | Ink jet recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745257B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213873A (en) * | 1989-10-20 | 1993-05-25 | Oji Paper Co., Ltd. | Aqueous ink-jet recording sheet |
| JP3130806B2 (en) * | 1996-10-24 | 2001-01-31 | 日華化学株式会社 | Dye fixing agent for ink jet printing and recording paper using the same |
| US6458876B1 (en) | 1999-08-09 | 2002-10-01 | Air Products And Chemicals, Inc. | Ink jet paper coatings containing polyvinyl alcohol-alkylated polyamine blends |
| US20070128349A1 (en) | 2004-02-03 | 2007-06-07 | Norimasa Miyachi | Process for preparing ink-jet recording material |
| US7700170B2 (en) | 2004-10-12 | 2010-04-20 | Mitsubishi Paper Mills Limited | Ink-jet recording material and method for preparing the same |
| JP2006198973A (en) | 2005-01-24 | 2006-08-03 | Konica Minolta Photo Imaging Inc | Inkjet recording paper |
| DE112007001519B4 (en) | 2006-06-22 | 2022-03-10 | Mitsubishi Paper Mills Limited | Method of making a conductive material |
| JP2010000775A (en) | 2008-03-31 | 2010-01-07 | Fujifilm Corp | Inkjet recording medium and method of manufacturing the same |
-
1986
- 1986-08-19 JP JP61193387A patent/JPH0745257B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6349478A (en) | 1988-03-02 |
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| LAPS | Cancellation because of no payment of annual fees |