JPH0813570B2 - Method for manufacturing inkjet recording medium - Google Patents
Method for manufacturing inkjet recording mediumInfo
- Publication number
- JPH0813570B2 JPH0813570B2 JP62252513A JP25251387A JPH0813570B2 JP H0813570 B2 JPH0813570 B2 JP H0813570B2 JP 62252513 A JP62252513 A JP 62252513A JP 25251387 A JP25251387 A JP 25251387A JP H0813570 B2 JPH0813570 B2 JP H0813570B2
- Authority
- JP
- Japan
- Prior art keywords
- antioxidant
- ink
- recording medium
- inkjet recording
- alumina sol
- 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 - Lifetime
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
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- 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］ 本発明はインクジェット用記録媒体の製造方法、特に
アゾ基を有する黒色染料を変色することなく記録し得る
インクジェット用記録媒体の製造方法に係るものであ
る。The present invention relates to a method for manufacturing an inkjet recording medium, and more particularly to a method for manufacturing an inkjet recording medium capable of recording a black dye having an azo group without discoloration. Is.
［従来の技術］ インクを用いて記録する記録用紙、特にインクジェッ
トプリンター用紙は、その記録媒体として紙の表面に多
孔性シリカ等の微細粒子をポリビニルアルコール等のバ
インダーを用いて塗布し、これにインクを吸収せしめて
発色させるようになされている。[Prior Art] Recording paper for recording with ink, particularly inkjet printer paper, has fine particles of porous silica or the like coated on the surface of the paper as a recording medium by using a binder such as polyvinyl alcohol, and the like. It is designed to absorb and develop color.
［発明が解決しようとする問題点］ しかしながら、この様な記録用紙にあっては、アゾ基
を有する黒色染料を用いたインクによって印刷を行なう
と、短期間のうちに黒色が褐色に変色する現象が生ずる
欠点を有している。[Problems to be Solved by the Invention] However, in such a recording paper, when printing is performed using an ink containing a black dye having an azo group, the phenomenon that black color turns brown in a short period of time Has a drawback.
かかる現象は、インクが主に空気中の酸素によって酸
化される為であり、これを防止する為に、インクの吸収
体であるシリカ等の多孔性粒子に予め各種の酸化防止剤
を付与せしめておくことが提案されている。Such a phenomenon is because the ink is mainly oxidized by oxygen in the air, and in order to prevent this, various antioxidants are previously added to the porous particles such as silica, which is the absorber of the ink. It is suggested to leave.
この様な酸化防止剤としては、例えばフェノール系，
アミン系、有機硫黄系、ホスファイト系等の酸化防止剤
があるが、これらは何れも常温下では固体であり、通常
適当な界面活性剤を用いて水性エマルジョンを形成せし
め、これに多孔性粒子を浸漬せしめて付与していた。Examples of such antioxidants include phenol-based antioxidants,
There are amine-based, organic sulfur-based, phosphite-based antioxidants, etc., but these are all solid at room temperature, and usually an appropriate surfactant is used to form an aqueous emulsion. Was dipped and applied.
しかしながら、これら酸化防止剤は何れもどの界面活
性剤ともそれ程なじみが良くなく、エマルジョンが不安
定であり、酸化防止剤が局在化したり、エマルジョン自
身が壊れてしまい、多孔性粒子表面で部分的に酸化防止
剤が析出分離する等の不都合が生じ易かった。However, none of these antioxidants are so well compatible with any of the surfactants, the emulsion is unstable, and the antioxidant is localized, or the emulsion itself is broken, so that the surface of the porous particles is partially broken. However, it is easy to cause inconveniences such as precipitation and separation of the antioxidant.
［問題点を解決するための手段］ 本発明はこれら不都合を解決し、本来インクの酸化防
止効果のある酸化防止剤を有効に作用させる為に均一且
安定したエマルジョンを形成せしめることを目的として
種々研究、検討した結果、特定の分散媒体を用いること
により前記目的を達成し得ることを見出した。[Means for Solving Problems] The present invention solves these inconveniences and aims to form a uniform and stable emulsion in order to effectively act an antioxidant that originally has an antioxidant effect on ink. As a result of research and study, it was found that the above object can be achieved by using a specific dispersion medium.
かくして本発明は、インクの酸化防止剤、界面活性
剤、アルミナゾルを含有するエマルジョンを、インクの
吸収体と共に基材に塗布するインクジェット用記録媒体
の製造方法を提供するにある。Thus, the present invention provides a method for producing an inkjet recording medium in which an emulsion containing an ink antioxidant, a surfactant and an alumina sol is applied to a substrate together with an ink absorber.
本発明において用いられるアルミナゾルの使用量は、
これをAl2O3に換算してインクの酸化防止剤とアルミナ
ゾルの合計量に対し、５〜90重量％程度を採用するのが
適当である。The amount of alumina sol used in the present invention is
It is appropriate to convert this into Al 2 O 3 and use about 5 to 90% by weight with respect to the total amount of the antioxidant and the alumina sol of the ink.
前記量を逸脱する場合には、均一且安定なエマルジョ
ンが得られなかったり、コート紙としての特性を著しく
阻害する虞れがあるので好ましくない。そしてこれら使
用量の範囲のうち前記表示に従って10〜80重量％を採用
する場合には、均一且安定なエマルジョンが得られ、又
インクの吸収等の多孔性粒子に対しても悪影響を実質的
に及ぼさないので特に好ましい。If the amount deviates from the above range, a uniform and stable emulsion may not be obtained, or the properties as coated paper may be significantly impaired, which is not preferable. When 10 to 80% by weight is used in accordance with the above indication in the range of these usage amounts, a uniform and stable emulsion is obtained, and there is substantially no adverse effect on the porous particles such as ink absorption. It is particularly preferable because it does not extend.
用いるアルミナゾルの濃度としては、Al2O3に換算し
て５〜10重量％程度を採用するのが適当である。濃度が
前記範囲に満たないと酸化防止剤の効果的な均一分散を
阻害したり、逆に前記範囲を越える場合には粘度が高く
なり酸化防止剤の均一分散を阻害する虞れがあるので何
れも好ましくない。As the concentration of the alumina sol used, it is suitable to adopt about 5 to 10% by weight in terms of Al 2 O 3 . If the concentration is less than the above range, the effective uniform dispersion of the antioxidant may be hindered. On the contrary, if the concentration exceeds the above range, the viscosity may increase and the uniform dispersion of the antioxidant may be hindered. Is also not preferable.
次に本発明に用いられるインクの酸化防止剤として
は、例えばフェノール系、有機硫黄系、ホスファイト系
等の酸化防止剤であり、具体的にはフェノール系酸化防
止剤としては例えば2,6−ジ−ｔ−ブチル−４−メチル
フェノール、ｎ−オクタデシル−３−（3,5−ジ−ｔ−
ブチル−４′−ヒドロキシフェニル）プルオピオネー
ト、2,2′−メチレンビス（４−メチル−６−ｔ−ブチ
ルフェノール）、4,4′−ブチリデンビス（３−メチル
−６−ｔ−ブチルフェノール）、4,4′−チオビス（３
−メチル−６−ｔ−ブチルフェノール）、1,3,5−トリ
ス（４−ｔ−ブチル−３−ヒドロキシ−2,6−ジメチル
ベンジル）イソシアヌレート、テトラキス［メチレン−
３−（３′,5′−ジ−ｔ−ブチル−４′−ヒドロキシフ
ェニル）プロピオネート］メタン、3,9−ビス［1,1−ジ
メチル−２−｛３−（３−ｔ−ブチル−４−ヒドロキシ
−５−メチルフェニル）プロピオニロキシ｝エチル］2,
4,8,10−テトラオキサスピロ［5,5］ウンデカンが、ま
た有機硫黄系酸化防止剤としては例えば、ジラウリル3,
3′−チオジプロピオネート、ジミリスチル3,3′−チオ
ジプロピオネート、ジステアリル3,3′−チオジプロピ
オネート、ベンタエリスリトールテトラキス（β−ラウ
リルチオプロピオネート）、２−メルカプトベンズイミ
ダゾールが、またホスファイト系酸化防止剤としては例
えば、トリス（2,4−ジ−ｔ−ブチルフェニル）ホスフ
ァイト等が挙げられる。Next, as the ink antioxidant used in the present invention, for example, phenol-based, organic sulfur-based, phosphite-based antioxidants, and the like, specifically, phenol-based antioxidants such as 2,6- Di-t-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-t-
Butyl-4'-hydroxyphenyl) puropionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4 ' -Thiobis (3
-Methyl-6-t-butylphenol), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 3,9-bis [1,1-dimethyl-2- {3- (3-t-butyl-4) -Hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,
4,8,10-Tetraoxaspiro [5,5] undecane, and examples of the organic sulfur-based antioxidant include dilauryl 3,
3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, bentaerythritol tetrakis (β-lauryl thiopropionate), 2-mercaptobenzimidazole Examples of the phosphite-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite and the like.
実際アルミナゾル中にこれら酸化防止剤を分散せしめ
る手段としては、例えば酸化防止剤をフロン類やアセト
ン等の低沸点溶媒中に一旦溶解せしめ、これを界面活性
剤と共にアルミナゾルと混合せしめたり、或は酸化防止
剤をアルミナゾル及び界面活性剤と共に、酸化防止剤の
融点以上の温度に加温して混合する等の方法を採用し得
る。Actually, as a means for dispersing these antioxidants in the alumina sol, for example, the antioxidant is once dissolved in a low boiling point solvent such as fluorocarbons or acetone, and this is mixed with the surfactant together with the alumina sol, or is oxidized. A method of heating the antioxidant together with the alumina sol and the surfactant to a temperature equal to or higher than the melting point of the antioxidant and mixing them may be employed.
これらの方法に用いられる界面活性剤としては、例え
ばポリエチレングリコールエーテル脂肪酸エステル、ポ
リオキシエチレンアルキルフェニルエーテル、ポリオキ
シエチレンアルキルエーテル、ソルビタン脂肪酸エステ
ル、ポリオキシエチレンソルビタン脂肪酸モノエステル
等が挙げられる。Examples of the surfactant used in these methods include polyethylene glycol ether fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid monoester, and the like.
これら界面活性剤の使用量は、酸化防止剤に対し、10
重量％以下であることが好ましい。酸化防止剤の使用量
が10重量％を超える場合には記録紙の特性を著しく阻害
する虞れがあるので好ましくない。The amount of these surfactants used is 10% with respect to the antioxidant.
It is preferable that the content be not more than weight%. If the amount of the antioxidant used exceeds 10% by weight, the characteristics of the recording paper may be significantly impaired, which is not preferable.
かくして得られた混合液はこれをそのまま或は所定量
の水を加えて攪拌し、エマルジョン化せしめる。この時
例えばポリビニルアルコールやカルボキシメチルセルロ
ース等の水溶性高分子バインダーとして加えたり、その
他の添加物を所望により加えることが出来る。The mixture thus obtained is emulsified as it is or by adding a predetermined amount of water and stirring. At this time, for example, a water-soluble polymer binder such as polyvinyl alcohol or carboxymethyl cellulose may be added, or other additives may be added as desired.
得られたエマルジョンには更にインクの吸収体となる
多孔性粒子が混合される。The emulsion thus obtained is further mixed with porous particles to serve as an ink absorber.
かかる多孔性粒子としては、インクを吸収し得る様な
多孔体であり、具体的には多孔性シリカが最も好ましい
が、更にこれに20重量％以下のボリア、マグネシア、ジ
ルコニア、チタニア等含有せしめ得る。As such a porous particle, a porous body capable of absorbing ink, specifically, porous silica is most preferable, but further 20% by weight or less of boria, magnesia, zirconia, titania, etc. may be contained. .
多孔性粒子の平均粒子径は２〜50μ程度、平均細孔径
120〜500Å、平均細孔容積0.8〜2.0cc/gを有するのが適
当である。粒子がこれら物性を逸脱する場合には、鮮明
な発色が阻害されたりにじみを生じたりする虞れがある
ので好ましくない。The average particle size of the porous particles is about 2 to 50μ, the average pore size
It is suitable to have 120 to 500Å and an average pore volume of 0.8 to 2.0 cc / g. If the particles deviate from these physical properties, vivid coloration may be hindered or bleeding may occur, which is not preferable.
本発明が効果的に発現されるインクとしては、アゾ系
黒色染料を用いた水性インクであり、特にC.I.Food Bla
ck2と呼ばれるアゾ系黒色インクに対する褐変を効果的
に防止することが出来る。The ink in which the present invention is effectively expressed is a water-based ink using an azo black dye, and particularly CIFood Bla
It is possible to effectively prevent browning of the azo black ink called ck2.
本発明に用いられる酸化防止剤の使用量は、厳密には
用いられる酸化防止剤の種類等により決定されるが、一
般にはインクの吸収体となる多孔性粒子とアルミナゾル
中のAl2O3の合計量に対し10〜50重量％、好ましくは10
〜35重量％程度を採用するのが適当である。The amount of the antioxidant used in the present invention is strictly determined by the kind of the antioxidant used, etc., but in general, the porous particles that become the ink absorber and Al 2 O 3 in the alumina sol are used. 10 to 50% by weight, preferably 10 based on the total amount
It is suitable to use about 35% by weight.
使用量は前記範囲に満たない場合には、褐変を効果的
に防止し得ず、逆に前記範囲を越える場合には各種の色
の発色を阻害する虞れがあるので何れも好ましくない。If the amount used is less than the above range, browning cannot be effectively prevented, and if the amount exceeds the above range, color development of various colors may be hindered.
かくして得られたこれら混合物は紙やプラスチック等
の基材表面に例えばバーコーターやエアナイフコータ
ー、ドクターブレード等により適当な厚さに塗布される
等設けられ、乾燥して使用に供される。The mixture thus obtained is provided on the surface of a base material such as paper or plastic by a bar coater, an air knife coater, a doctor blade or the like so as to have an appropriate thickness, and then dried and used.
［実施例］ 水300gに界面活性剤としてソルビタン脂肪酸エステル
0.18g及びポリオキシエチレンアルキルフェニルエーテ
ル0.42g、アルミナゾル（Al2O3換算濃度７重量％）43g
（Al2O3固形分3g）を入れ、60℃に保持しつつ攪拌し、
これに酸化防止剤としてジラウリル3,3′チオジプロピ
オネート（住友化学社製スミライザーTPL−Ｒ）30gを添
加して溶融し、エマルジョン化せしめた。このエマルジ
ョン中に球状シリカ（平均粒子径22μ、平均細孔径200
Å、平均細孔容積1.6cc/g）100gを入れ、よく攪拌し、
これを上質紙（坪量85g/m2）に塗布量20g/m2となるよう
塗布して乾燥し、ベース紙とした。[Example] Sorbitan fatty acid ester as a surfactant in 300 g of water
0.18 g and polyoxyethylene alkylphenyl ether 0.42 g, alumina sol (Al 2 O 3 conversion concentration 7% by weight) 43 g
(Al 2 O 3 solid content 3g) was added and stirred while maintaining at 60 ° C,
To this, 30 g of dilauryl 3,3 'thiodipropionate (Sumilyzer TPL-R manufactured by Sumitomo Chemical Co., Ltd.) was added as an antioxidant and melted to form an emulsion. Spherical silica (average particle size 22μ, average pore size 200
Å, average pore volume 1.6cc / g) 100g, put well,
This was applied to high-quality paper (basis weight 85 g / m 2 ) so that the application amount was 20 g / m 2, and dried to obtain a base paper.
次に、アセトンとフロン113との1:1混合溶媒250gに、
酸化防止剤として3,9−ビス［1,1−ジメチル−２−｛３
−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェ
ニル）プロピオニロキシ｝エチル］2,4,8,10−テトラオ
キサスピロ［5,5］ウンデカン（住友化学社製スミライ
ザーGA80）を25g溶解せしめた。Next, to 250 g of a 1: 1 mixed solvent of acetone and Freon 113,
3,9-bis [1,1-dimethyl-2- {3 as antioxidant
25 g of-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane (Sumitomo Chemical Sumilizer GA80) Dissolved.
他方、アルミナゾル（Al2O3換算濃度７重量％）1430g
（Al2O3固形分100g）及びポリビニルアルコール143g及
び界面活性剤としてポリオキシエチレンアルキルフェニ
ルエーテル0.5gを60℃に保持しつつ攪拌混合し、これに
先の酸化防止剤溶液を滴下攪拌してエマルジョンを得
た。On the other hand, alumina sol (Al 2 O 3 conversion concentration 7% by weight) 1430 g
(Al 2 O 3 solid content 100 g) and polyvinyl alcohol 143 g and 0.5 g of polyoxyethylene alkylphenyl ether as a surfactant are stirred and mixed while being maintained at 60 ° C., and the above antioxidant solution is added dropwise to this by stirring. An emulsion was obtained.
このエマルジョン中に球状シリカ（平均粒子径６μ、
平均細孔径200Å、平均細孔容積1.6cc/g）40gを入れて
よく攪拌し、これを前記ベース紙のシリカ面に塗布量4g
/m2となる様に塗布して乾燥し、記録紙を得た。Spherical silica (average particle size 6μ,
Put 40g of average pore size 200Å and average pore volume 1.6cc / g) and stir well, then apply 4g of this on the silica side of the base paper.
A coating paper was obtained by coating so as to have a thickness of / m 2 and drying.
得られた記録紙にキャノン社スチルビデオプリンター
RP-601によりアゾ系黒色染料であるFood Black2を含む
黒色インクを常法に従ってインクジェット印字し、印字
特性、耐候性評価を行なった。その結果良好な色濃度、
解像度、吸インク速度が得られた。又、耐候性試験とし
ては直射日光の当らない風通しの良好な室内に１ケ月間
掲示して色差計（日本電色工業）を用いて黒ベタ印字部
分の掲示前後での色差ΔＥを測定した処2.6と微かであ
った。Canon still video printer on the obtained recording paper
A black ink containing Food Black 2, which is an azo black dye, was ink-jet printed by RP-601 according to a conventional method, and printing characteristics and weather resistance were evaluated. As a result, good color density,
The resolution and ink absorption speed were obtained. As a weather resistance test, the color difference ΔE before and after the black solid printed portion was displayed was measured by using a color difference meter (Nippon Denshoku Industries Co., Ltd.) by displaying it in a well-ventilated room without direct sunlight for one month. It was as small as 2.6.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−111782（ＪＰ，Ａ) 特開 昭62−174183（ＪＰ，Ａ) 特開 昭62−170381（ＪＰ，Ａ) 特開 昭60−56587（ＪＰ，Ａ) 特開 昭60−171190（ＪＰ，Ａ) 特公 昭62−26319（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-111782 (JP, A) JP 62-174183 (JP, A) JP 62-170381 (JP, A) JP 60- 56587 (JP, A) JP 60-171190 (JP, A) JP 62-26319 (JP, B2)
Claims (3)
ナゾルを含有するエマルジョンを、インクの吸収体と共
に基材に塗布するインクジェット用記録媒体の製造方
法。1. A method for producing an inkjet recording medium, wherein an emulsion containing an ink antioxidant, a surfactant and an alumina sol is applied to a substrate together with an ink absorber.
て酸化防止剤と該ゾルの合計量に対し、５〜90重量％で
ある請求の範囲（１）の製造方法。2. The method according to claim 1, wherein the amount of the alumina sol used is 5 to 90% by weight based on the total amount of the antioxidant and the sol in terms of Al 2 O 3 .
止剤、有機硫黄系酸化防止剤、ホスファイト系酸化防止
剤である請求の範囲（１）の製造方法。3. The method according to claim 1, wherein the antioxidant of the ink is a phenol-based antioxidant, an organic sulfur-based antioxidant, and a phosphite-based antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62252513A JPH0813570B2 (en) | 1987-10-08 | 1987-10-08 | Method for manufacturing inkjet recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62252513A JPH0813570B2 (en) | 1987-10-08 | 1987-10-08 | Method for manufacturing inkjet recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0195091A JPH0195091A (en) | 1989-04-13 |
| JPH0813570B2 true JPH0813570B2 (en) | 1996-02-14 |
Family
ID=17238415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62252513A Expired - Lifetime JPH0813570B2 (en) | 1987-10-08 | 1987-10-08 | Method for manufacturing inkjet recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813570B2 (en) |
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Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787989A (en) * | 1980-11-21 | 1982-06-01 | Matsushita Electric Ind Co Ltd | Ink jet recording paper |
| JPS6056587A (en) * | 1983-09-09 | 1985-04-02 | Teijin Ltd | Recording sheet |
| JPS60171190A (en) * | 1984-02-16 | 1985-09-04 | Mishima Seishi Kk | Ink jet recording paper |
| JPS60232990A (en) * | 1984-05-02 | 1985-11-19 | Mitsubishi Paper Mills Ltd | Ink jet recording medium |
| JPS6226319A (en) * | 1985-07-26 | 1987-02-04 | Mazda Motor Corp | Ceramic auxiliary chamber for internal-combustion engine |
| JPS62111782A (en) * | 1985-11-11 | 1987-05-22 | Asahi Glass Co Ltd | Recording paper |
| JPS62170381A (en) * | 1986-01-24 | 1987-07-27 | Canon Inc | Recorded material |
| JPS62174183A (en) * | 1986-01-29 | 1987-07-30 | Canon Inc | Recording material |
-
1987
- 1987-10-08 JP JP62252513A patent/JPH0813570B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0195091A (en) | 1989-04-13 |
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