JP2006281474A - Method for manufacturing inkjet recording medium - Google Patents

Method for manufacturing inkjet recording medium Download PDF

Info

Publication number
JP2006281474A
JP2006281474A JP2005101090A JP2005101090A JP2006281474A JP 2006281474 A JP2006281474 A JP 2006281474A JP 2005101090 A JP2005101090 A JP 2005101090A JP 2005101090 A JP2005101090 A JP 2005101090A JP 2006281474 A JP2006281474 A JP 2006281474A
Authority
JP
Japan
Prior art keywords
coating composition
hydrazine
recording medium
polyvinyl alcohol
coating
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.)
Pending
Application number
JP2005101090A
Other languages
Japanese (ja)
Inventor
Kenichi Hosaka
健一 保坂
Makoto Kato
真 加藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Priority to JP2005101090A priority Critical patent/JP2006281474A/en
Publication of JP2006281474A publication Critical patent/JP2006281474A/en
Pending legal-status Critical Current

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
    • 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
    • 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
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an inkjet recording medium which does not contain boric acid and its salt subjected to water drainage restrictions on account of their harmfulness and can hardly cause a yellowing phenomenon and can be manufactured with high productivity. <P>SOLUTION: In this method, a coating composition contains (1) a submicron pigment, (2) a diacetoneacrylamide-modified polyvinyl alcohol and (3) a minimum 50 to 95% of a hydrazine-series crosslinking agent which gels the coating composition, In addition, right before the coating process, the hydrazine-series crosslinking agent is applied with its additional dose to the coating composition 50% or higher through with a chemical reaction between the diacetoneacrylamide-modified polyvinyl alcohol and the applied hydrazine-series crosslinking agent. Alternatively, the coating composition is applied to the surface of a base material previously coated with an undercoat layer containing the hydrazine-series crosslinking agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、毒性を有するホウ酸およびその塩を使用せず、乾燥を高速に行うことができ、かつ製造されたインクジェット記録媒体が経時で黄変しないインクジェット記録媒体の製造方法に関する。   The present invention relates to a method for producing an inkjet recording medium that can be dried at high speed without using toxic boric acid and its salt, and that the produced inkjet recording medium does not yellow over time.

近年、インクジェットプリンタの技術が急速に進歩し、一般的な銀塩写真法によるものと同等以上の画像品質を有する記録物が得られるようになってきた。これに伴い、インクジェット用の記録媒体にも、銀塩写真法に用いられるものと同等の質感、すなわち光沢感や表面の透明感を有するものが求められている。このような要求を満たすインクジェット記録媒体として、紙やプラスチックフィルム等の基材上に、多孔質のインク吸収層を設けた記録媒体が用いられている。   In recent years, the technology of inkjet printers has advanced rapidly, and it has become possible to obtain recorded matter having image quality equivalent to or higher than that obtained by a general silver salt photography method. Along with this, there is a demand for ink jet recording media having a texture equivalent to that used in silver salt photography, that is, having gloss and surface transparency. As an inkjet recording medium that satisfies such requirements, a recording medium in which a porous ink absorbing layer is provided on a substrate such as paper or a plastic film is used.

基材上に多孔質のインク吸収層を設けるためには、無機顔料とバインダーを適宜混合した組成物を塗工し、該組成物の溶媒を乾燥除去して無機顔料とバインダーからなる塗工層を形成させることが行われている。しかし、このような方法で塗工層を形成させる場合、乾燥時の体積収縮に起因する内部応力のため乾燥後の塗工層に亀裂が生じてしまう。これを避ける方法として、塗工組成物を基材上に塗工した後、該組成物に含まれるバインダーを架橋することで亀裂を抑制することが提案されており、その一例として、特許文献１で提案されている、アルミナ水和物、ポリビニルアルコールとホウ酸またはホウ酸塩を含有したインクジェット記録媒体用の塗工組成物が提案されている。しかし、ホウ酸およびその塩は摂取量がある程度を超えると人体に悪影響を及ぼす可能性があり、水質汚濁防止法施行令（昭和四十六年六月十七日政令第百八十八号）でもその排出が規制されている。   In order to provide a porous ink absorption layer on a substrate, a composition in which an inorganic pigment and a binder are appropriately mixed is applied, and the solvent of the composition is removed by drying to form a coating layer comprising an inorganic pigment and a binder. Has been made to form. However, when the coating layer is formed by such a method, the coating layer after drying is cracked due to internal stress caused by volume shrinkage during drying. As a method for avoiding this, it has been proposed to suppress cracking by coating a coating composition on a substrate and then crosslinking the binder contained in the composition. A coating composition for an ink jet recording medium containing alumina hydrate, polyvinyl alcohol and boric acid or borate has been proposed. However, boric acid and its salts may adversely affect the human body if the intake exceeds a certain level, and the Water Pollution Control Law Enforcement Order (Decree No. 188 of June 17, 1969) But its emissions are regulated.

このような問題を有さない塗工組成物として、特許文献２では、アセトアセチル基を有するポリビニルアルコールとヒドラジン系架橋剤を含むインクジェット記録媒体が提案されている。しかし、本発明の発明者が試験したところによれば、特許文献２の技術によりインクジェット記録媒体を製造した場合、製造されたインクジェット記録媒体が大気中に暴露された場合、経時により黄変しやすいという問題があった。   As a coating composition not having such a problem, Patent Document 2 proposes an ink jet recording medium containing polyvinyl alcohol having an acetoacetyl group and a hydrazine-based crosslinking agent. However, according to the test of the inventor of the present invention, when an ink jet recording medium is manufactured by the technique of Patent Document 2, when the manufactured ink jet recording medium is exposed to the atmosphere, it tends to yellow over time. There was a problem.

これに対し、特許文献３で提案されているような、アセトアセチル基を含有するポリビニルアルコールに代え、ジアセトンアクリルアミド変性ポリビニルアルコールを用いた記録媒体では、経時による黄変を生じることはない。しかし、この技術を用いた場合、乾燥時のひび割れが生じやすく、これを防ぐためにかなりの長時間をかけて塗工組成物を乾燥させる必要があった。具体的には、特許文献３の実施例では、常温すなわち２０℃で４８時間かけて、基材上に塗工された塗工組成物を乾燥させている。記録媒体の製造において、塗工組成物の乾燥は通常、長くとも５分以内に完了することが望まれ、言いかえれば乾燥に４８時間というような長時間を要する技術は到底実用的とは言えないものであった。
特開平７−７６１６１号公報 特開２００５−３５００７号公報 特開平１１−３４８４１７号公報 In contrast, a recording medium using diacetone acrylamide-modified polyvinyl alcohol instead of polyvinyl alcohol containing an acetoacetyl group as proposed in Patent Document 3 does not cause yellowing over time. However, when this technique is used, cracks at the time of drying tend to occur, and in order to prevent this, it was necessary to dry the coating composition over a considerable period of time. Specifically, in the Example of Patent Document 3, the coating composition coated on the substrate is dried at room temperature, that is, 20 ° C. for 48 hours. In the production of a recording medium, it is usually desired that drying of the coating composition be completed within 5 minutes at the most. In other words, a technique that requires a long time, such as 48 hours, is extremely practical. It was not.
JP-A-7-76161 JP 2005-35007 A JP-A-11-348417

本発明の目的は、ホウ酸およびその塩を含まず、かつ乾燥を高速で行っても塗工層にひび割れを生じず、かつこれにより製造されたインクジェット記録媒体に黄変を生じさせない塗工組成物を用いたインクジェット記録媒体の製造方法を提供することにある。   An object of the present invention is a coating composition that does not contain boric acid and its salt, does not cause cracks in the coating layer even when drying is performed at high speed, and does not cause yellowing in the inkjet recording medium produced thereby An object of the present invention is to provide a method for manufacturing an ink jet recording medium using a product.

以上の課題に対し、（１）サブミクロン顔料、（２）ジアセトンアクリルアミド変性ポリビニルアルコール、（３）塗工組成物をゲル化させる最低量の５０〜９５％のヒドラジン系架橋剤を含み、ジアセトンアクリルアミド変性ポリビニルアルコールと添加されたヒドラジン系架橋剤間の反応が５０％以上進行した塗工組成物に、塗工直前にヒドラジン系架橋剤を追加し、基材上に塗工して乾燥する製造方法を用いることで解決が可能となった。   In order to solve the above problems, (1) a submicron pigment, (2) diacetone acrylamide-modified polyvinyl alcohol, (3) a minimum amount of 50-95% hydrazine-based crosslinking agent that gels the coating composition, A coating composition in which the reaction between acetone acrylamide-modified polyvinyl alcohol and the added hydrazine-based crosslinking agent has progressed by 50% or more is added with a hydrazine-based crosslinking agent immediately before coating, and is coated on a substrate and dried. The solution was made possible by using the manufacturing method.

さらに、（１）サブミクロン顔料、（２）ジアセトンアクリルアミド変性ポリビニルアルコール、（３）塗工組成物をゲル化させる最低量の５０〜９５％のヒドラジン系架橋剤 を含み、ジアジアセトンアクリルアミド変性ポリビニルアルコールと添加されたヒドラジン系架橋剤間の反応が５０％以上進行した塗工組成物を、あらかじめヒドラジン系架橋剤を含む下引き層を塗工した基材上に塗工し、乾燥する製造方法を用いることで解決することが可能になった。   Further, it contains (1) a submicron pigment, (2) diacetone acrylamide modified polyvinyl alcohol, and (3) a minimum amount of 50-95% hydrazine-based cross-linking agent that gels the coating composition. Manufacturing in which a coating composition in which the reaction between polyvinyl alcohol and the added hydrazine-based crosslinking agent has progressed by 50% or more is coated on a substrate on which an undercoat layer containing a hydrazine-based crosslinking agent has been applied in advance and dried. It became possible to solve it by using the method.

本発明により、その有害性から排水規制の対象となるホウ酸およびその塩を含まず、黄変を生じにくく、かつ高い生産性でインクジェット記録媒体を製造できる。   According to the present invention, it is possible to produce an inkjet recording medium with high productivity without containing boric acid and its salt, which are subject to wastewater regulation due to its harmfulness, hardly causing yellowing.

本発明において、サブミクロン顔料とは、その分散液をガラス等の適切な基板上に散布し、走査型電子顕微鏡で観察したときに、観察される粒子の個数の９０％以上が長辺１μｍ以下である顔料を指す。その種類は特に制限されないが、いくつかの例を挙げると、ゲル法シリカ、沈降法シリカ、気相法シリカ、コロイダルシリカ、擬ベーマイト、気相法アルミナ等を用いることができる。   In the present invention, the submicron pigment means that when the dispersion liquid is dispersed on a suitable substrate such as glass and observed with a scanning electron microscope, 90% or more of the number of particles observed is 1 μm or less on the long side. Refers to the pigment. The type is not particularly limited, but some examples include gel method silica, precipitation method silica, gas phase method silica, colloidal silica, pseudoboehmite, and gas phase method alumina.

また、該サブミクロン顔料のＢＥＴ法による比表面積がある程度以上あると、インクジェットインクに含まれる染料がより強固に定着し、印刷画像の高い耐水性が得られることから好ましい。一方該比表面積が大きすぎると、インクの吸収性が低下することがあるから好ましくない。具体的には、該サブミクロン顔料のＢＥＴ法による比表面積は８０〜６００ｍ２／ｇ以上であることが好ましく、１２０〜４００ｍ２／ｇであることがより好ましい。このような顔料は、通常、粒径５〜５０ｎｍ程度の一次粒子が長辺１μｍ以下の高次構造を形成してなる顔料である。 Further, it is preferable that the submicron pigment has a specific surface area by the BET method of a certain level or more because the dye contained in the inkjet ink is more firmly fixed and high water resistance of the printed image can be obtained. On the other hand, if the specific surface area is too large, the ink absorbability may be lowered, which is not preferable. Specifically, the specific surface area according to the BET method of the submicron pigment is preferably 80 to 600 m 2 / g or more, and more preferably 120 to 400 m 2 / g. Such a pigment is usually a pigment in which primary particles having a particle size of about 5 to 50 nm form a higher order structure having a long side of 1 μm or less.

さらに、該サブミクロン顔料の粒子径が１００ｎｍ以上であると、より高速で乾燥しても塗工層に亀裂が生じにくくなることから好ましい。なお、ここで粒子径が１００ｎｍ以上とは、その分散液をガラス等の適切な基板上に散布し、走査型電子顕微鏡で観察したときに、観察野において粒子が占める面積の８０％以上を、長辺１００ｎｍ以上の粒子が占める状態を指す。   Furthermore, it is preferable that the particle diameter of the submicron pigment is 100 nm or more because cracks are less likely to occur in the coating layer even when dried at a higher speed. Here, when the particle diameter is 100 nm or more, when the dispersion is dispersed on a suitable substrate such as glass and observed with a scanning electron microscope, 80% or more of the area occupied by the particles in the observation field, This refers to the state occupied by particles having a long side of 100 nm or more.

本発明に用いるジアセトンアクリルアミド変性ポリビニルアルコールの製造法は特に制限されないが、一例を挙げれば、メタノール中に酢酸ビニルとジアセトンアクリルアミドを溶解し、窒素を通じながら４０℃ないし６０℃に加熱し、アゾビス−２−イソブチロニトリル等のアゾ開始剤または過酸化ベンゾイル等の過酸化物開始剤等を添加して重合し、重合が終了した後に、水酸化ナトリウムなどの触媒を添加し、酢酸メチルを留出させることで製造することができる。   The production method of diacetone acrylamide-modified polyvinyl alcohol used in the present invention is not particularly limited. For example, vinyl acetate and diacetone acrylamide are dissolved in methanol and heated to 40 ° C. to 60 ° C. while passing through nitrogen. Polymerization is performed by adding an azo initiator such as -2-isobutyronitrile or a peroxide initiator such as benzoyl peroxide. After the polymerization is completed, a catalyst such as sodium hydroxide is added, and methyl acetate is added. It can be produced by distilling.

本発明に用いるジアセトンアクリルアミド変性ポリビニルアルコールのジアセトンアクリルアミド単位の含有量は、低すぎると塗工組成物を高速に乾燥させた場合に乾燥後の塗工層に亀裂が生じやすくなり、高すぎると塗工組成物の粘度が高くなりすぎて塗工操作が困難になることから、０．１〜１５ｍｏｌ％であることが好ましく、０．５〜１０ｍｏｌ％であることがより好ましい。また、本発明に用いるジアセトンアクリルアミド変性ポリビニルアルコールの重合度は、低すぎると塗工組成物を高速に乾燥させた場合に乾燥後の塗工層に亀裂が生じやすくなり、高すぎると塗工組成物の粘度が高くなりすぎて塗工操作が困難になることから、その濃度４質量％の水溶液の２０℃における粘度が５〜２００ｍＰａ・秒であることが好ましく、１０〜１００ｍＰａ・秒であることがより好ましい。さらに、本発明に用いるジアセトンアクリルアミド変性ポリビニルアルコールのけん化度は、低すぎると塗工組成物の粘度が高くなりすぎて塗工操作が困難になることから、７０〜１００ｍｏｌ％であることが好ましく、８５〜１００ｍｏｌ％であることがより好ましい。   If the content of the diacetone acrylamide unit in the diacetone acrylamide modified polyvinyl alcohol used in the present invention is too low, the coating layer after drying tends to crack when the coating composition is dried at high speed, and is too high. Since the viscosity of the coating composition becomes too high and the coating operation becomes difficult, it is preferably 0.1 to 15 mol%, more preferably 0.5 to 10 mol%. In addition, if the polymerization degree of diacetone acrylamide-modified polyvinyl alcohol used in the present invention is too low, the coating layer after drying tends to crack when the coating composition is dried at high speed, and if too high, the coating degree is too high. Since the viscosity of the composition becomes too high and the coating operation becomes difficult, the viscosity at 20 ° C. of an aqueous solution having a concentration of 4% by mass is preferably 5 to 200 mPa · sec, and 10 to 100 mPa · sec. It is more preferable. Furthermore, the degree of saponification of the diacetone acrylamide-modified polyvinyl alcohol used in the present invention is preferably 70 to 100 mol% because if the viscosity is too low, the viscosity of the coating composition becomes too high and the coating operation becomes difficult. More preferably, it is 85-100 mol%.

本発明の塗工組成物には、ジアセトンアクリルアミド変性ポリビニルアルコール以外のポリビニルアルコール、例えば部分鹸化ポリビニルアルコール、完全鹸化ポリビニルアルコール、シリル基、カルボキシル基、アミノ基、アセトアセチル基等種々の官能基を導入したポリビニルアルコール等を併用することもできる。また、本発明で用いるジアセトンアクリルアミド変性ポリビニルアルコールに、シリル基、カルボキシル基、アミノ基、アセトアセチル基等種々の官能基を導入することもできる。   The coating composition of the present invention has various functional groups such as polyvinyl alcohol other than diacetone acrylamide-modified polyvinyl alcohol, such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, silyl group, carboxyl group, amino group, and acetoacetyl group. The introduced polyvinyl alcohol can also be used in combination. Various functional groups such as a silyl group, a carboxyl group, an amino group, and an acetoacetyl group can also be introduced into the diacetone acrylamide-modified polyvinyl alcohol used in the present invention.

本発明におけるジアセトンアクリルアミド変性ポリビニルアルコールの添加量は、少なすぎると乾燥時に亀裂が生じたり、形成されるインクジェット記録媒体の表面強度が不足することがある。一方、ポリビニルアルコールの添加量が多すぎるとインク吸収性が低下することがある。具体的には、ポリビニルアルコールの添加量はサブミクロン顔料の２〜６０質量％であることが好ましく、４〜３０質量％であることがより好ましい。   If the amount of diacetone acrylamide-modified polyvinyl alcohol added in the present invention is too small, cracks may occur during drying, or the surface strength of the formed inkjet recording medium may be insufficient. On the other hand, if the added amount of polyvinyl alcohol is too large, the ink absorbability may decrease. Specifically, the addition amount of polyvinyl alcohol is preferably 2 to 60% by mass of the submicron pigment, and more preferably 4 to 30% by mass.

本発明に使用するヒドラジン系架橋剤としては、ヒドラジン、ヒドラジンの塩、フェニルヒドラジンなどのアリールヒドラジン、メチルヒドラジン、エチルヒドラジンなどのアルキルヒドラジン、エチレンジヒドラジン、プロピレンジヒドラジンなどのアルケンジヒドラジン、ギ酸ヒドラジド、酢酸ヒドラジド、安息香酸ヒドラジドなどのモノカルボン酸ヒドラジド等を用いることもできるが、蓚酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジドなどのジカルボン酸ジヒドラジドが、ジアセトンアクリルアミド変性ポリビニルアルコールとの反応性が高く、温度などの環境要因による影響を受け難い安定した製造を可能ならしめることから特に好ましく使用される。   Examples of the hydrazine-based crosslinking agent used in the present invention include hydrazine, hydrazine salts, aryl hydrazines such as phenyl hydrazine, alkyl hydrazines such as methyl hydrazine and ethyl hydrazine, alkene dihydrazines such as ethylene dihydrazine and propylene dihydrazine, and formic hydrazide. Monocarboxylic acid hydrazides such as acetic acid hydrazide and benzoic acid hydrazide can also be used. Dicarboxylic acid dihydrazides such as dihydrazide are highly reactive with diacetone acrylamide-modified polyvinyl alcohol and are affected by environmental factors such as temperature. Particularly preferably used since it makes it possible to have stable production.

本発明において、塗工組成物をゲル化させる最低量とは、該ヒドラジン系架橋剤を添加後、２５℃において２４時間経過したときに、塗工組成物がゲル化する最低の添加量を指す。また本発明において、ジアセトンアクリルアミド変性ポリビニルアルコールとヒドラジン系架橋剤間の反応が５０％以上進行するに要する時間は、塗工組成物をゲル化させる最低量の２倍量のヒドラジン系架橋剤を添加したときに、塗工組成物がゲル化するまでの時間として概算することができる。   In the present invention, the minimum amount of gelling of the coating composition refers to the minimum amount of gelation of the coating composition after 24 hours at 25 ° C. after the addition of the hydrazine-based crosslinking agent. . In the present invention, the time required for the reaction between the diacetone acrylamide-modified polyvinyl alcohol and the hydrazine crosslinking agent to proceed by 50% or more is the amount of hydrazine crosslinking agent that is twice the minimum amount for gelling the coating composition. When added, it can be estimated as the time until the coating composition gels.

本発明において、塗工直前に追加して添加するヒドラジン系架橋剤の量は、少なくとも塗工組成物を速やかにゲル化させるに十分な量であることが必要であるが、その量が多すぎても副反応の発生による黄変などの問題を引き起こすことから好ましくない。その具体的な量は、使用するジアセトンアクリルアミド変性ポリビニルアルコールの重合度や、塗工組成物中への各成分の配合量によっても異なってくるが、通常サブミクロン顔料の０．５〜１０質量％とすることが好ましい。また、本発明において、塗工直前に塗工組成物にヒドラジン系架橋剤を追加して添加する方法としては、流路系内において、液状のヒドラジン系架橋剤ないしヒドラジン系架橋剤の溶液を塗工組成物と混合する、いわゆるインラインミキサーを用い、直ちに塗工装置にて塗工する等の方法がある。   In the present invention, the amount of the hydrazine-based cross-linking agent to be added immediately before the coating needs to be at least a sufficient amount to quickly gel the coating composition, but the amount is too large. However, it is not preferable because it causes problems such as yellowing due to the occurrence of side reactions. The specific amount varies depending on the degree of polymerization of the diacetone acrylamide-modified polyvinyl alcohol used and the blending amount of each component in the coating composition, but usually 0.5 to 10 mass of the submicron pigment. % Is preferable. In the present invention, as a method of adding a hydrazine-based crosslinking agent to the coating composition immediately before coating, a liquid hydrazine-based crosslinking agent or hydrazine-based crosslinking agent solution is applied in the flow path system. There is a method of using a so-called in-line mixer, which is mixed with a working composition, and immediately applying with a coating apparatus.

本発明において、基材にあらかじめ塗工する下引き層に含まれるヒドラジン系架橋剤の量は、少なくとも塗工組成物を速やかにゲル化させるに十分な量であることが必要であるが、その量が多すぎても副反応の発生による黄変などの問題を引き起こすことから好ましくない。その具体的な量は、使用するジアセトンアクリルアミド変性ポリビニルアルコールの重合度や、塗工組成物中への各成分の配合量によっても異なってくるが、通常この上に塗工される塗工組成物に含まれるサブミクロン顔料の０．５〜１０質量％とすることが好ましい。また、下引き層を一旦乾燥させてから塗工組成物を塗工しても良いし、下引き層を乾燥させずにそのまま塗工組成物を塗工しても構わない。   In the present invention, the amount of the hydrazine-based cross-linking agent contained in the undercoat layer that is previously applied to the substrate needs to be at least an amount sufficient to quickly gel the coating composition. An excessive amount is not preferred because it causes problems such as yellowing due to the occurrence of side reactions. The specific amount varies depending on the polymerization degree of diacetone acrylamide-modified polyvinyl alcohol to be used and the blending amount of each component in the coating composition. It is preferable to set it as 0.5-10 mass% of the submicron pigment contained in a thing. Alternatively, the coating composition may be applied after the undercoat layer is once dried, or the coating composition may be applied as it is without drying the undercoat layer.

本発明の塗工組成物には、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合樹脂、スチレン−ブタジエン共重合樹脂、スチレン−アクリル共重合樹脂、アクリル樹脂、ウレタン樹脂等、ポリビニルアルコール以外のバインダーを併用することもできる。   In the coating composition of the present invention, a vinyl acetate resin, an ethylene-vinyl acetate copolymer resin, a styrene-butadiene copolymer resin, a styrene-acryl copolymer resin, an acrylic resin, a urethane resin, or the like is used in combination with a binder other than polyvinyl alcohol. You can also

本発明の塗工組成物は、通常、各成分を水中に分散ないし溶解させた水性塗工物の形態で用いられる。また本発明の塗工組成物には、必要に応じて、界面活性剤、消泡剤、増粘剤、色味調整剤、酸化防止剤、紫外線吸収剤など各種の添加剤を添加することもできる。   The coating composition of the present invention is usually used in the form of an aqueous coating product in which each component is dispersed or dissolved in water. In addition, various additives such as a surfactant, an antifoaming agent, a thickening agent, a color adjusting agent, an antioxidant, and an ultraviolet absorber may be added to the coating composition of the present invention as necessary. it can.

本発明の塗工組成物を塗工する基材に特に制限は無く、非塗工紙、塗工紙、樹脂被覆紙、プラスチックフィルムなどを用いることができる。これらのうち、緻密な塗工層を有する塗工紙、樹脂被覆紙、プラスチックフィルムなど塗工組成物中の溶媒を吸収し難いものが、塗工組成物中の成分を不均等に吸収してその組成を変化させることがなく、より高品質の塗工層を形成させることから特に好ましく使用される。ただし、本発明の塗工組成物を塗工した基材を、キャスト装置により処理する場合には、透気性を有する支持体がむしろ好ましく使用される。   There is no restriction | limiting in particular in the base material which coats the coating composition of this invention, A non-coating paper, a coating paper, resin-coated paper, a plastic film etc. can be used. Of these, those that are difficult to absorb the solvent in the coating composition, such as coated paper, resin-coated paper, and plastic film having a dense coating layer, absorb the components in the coating composition unevenly. It is particularly preferably used because a higher quality coating layer can be formed without changing its composition. However, when the substrate coated with the coating composition of the present invention is processed by a casting apparatus, a support having air permeability is preferably used.

本発明の塗工組成物および下引き層を塗工する方法に特に制限は無く、エアナイフコーター、リバースロールコーター、コンマコーター、グラビアコーター等の塗工方式を用いることもできるが、リップコーター、ダイコーター、カーテンコーターなどの前計量コーターが、得られる塗工層の均一性の点から好ましく使用される。本発明の塗工組成物を基材上に塗工する量に特に制限は無いが、インク吸収性と経済性を両立させるためには通常、固形分として１０〜４０ｇ／ｍ２が塗工される。 The coating composition of the present invention and the method for coating the undercoat layer are not particularly limited, and coating methods such as an air knife coater, reverse roll coater, comma coater, and gravure coater can be used. A pre-weighing coater such as a coater or a curtain coater is preferably used from the viewpoint of the uniformity of the obtained coating layer. Although there is no restriction | limiting in particular in the quantity which coats the coating composition of this invention on a base material, Usually, 10-40 g / m < 2 > is applied as solid content in order to make ink absorptivity and economical efficiency compatible. The

本発明の塗工組成物を塗工した後、組成物中の揮発分を揮発させる方法に特に制限は無く、熱風乾燥機、赤外線乾燥機、シリンダー乾燥機等の種々の乾燥装置を用いることができる。また、基材上の塗工組成物が湿潤状態にある間に加熱された鏡面に圧着し、鏡面を塗工層に転写することで光沢面を得ると同時に行う、いわゆるキャスト装置を用いることもできる。   There is no particular limitation on the method for volatilizing the volatile components in the composition after coating the coating composition of the present invention, and various drying devices such as a hot air dryer, an infrared dryer, and a cylinder dryer can be used. it can. In addition, it is also possible to use a so-called casting apparatus that performs pressure bonding to a heated mirror surface while the coating composition on the substrate is in a wet state and transfers the mirror surface to the coating layer to obtain a glossy surface at the same time it can.

本発明の塗工組成物を塗工し、組成物中の揮発分を乾燥させてインクジェット記録媒体を製造した後、さらに、カレンダー装置、キャスト装置などを用いて表面光沢を向上させることもできる。また、これらの装置を用いた処理に先立って、あらかじめ塗工層に水分を付与することで、これら装置による処理の効果を高めることもできる。なお、これらの装置で表面光沢を向上させる場合には、本発明の塗工組成物に、ジメチルオクチルアミン、ジメチルオクタデシルアミン、トリメチルオクチルアンモニウムクロリド、トリメチルオクタデシルアンモニウムクロリド、ステアリン酸、オクチルアルコール、オクタデシルアルコール、カプリル酸、ステアリン酸、流動パラフィン、シリコーン油等の油性物質、およびこれらの分散体等を、離型剤として少量添加することで、より面質が良好な記録媒体が得られるので好ましい。   After the coating composition of the present invention is applied and the volatile components in the composition are dried to produce an ink jet recording medium, the surface gloss can be further improved using a calendar device, a casting device, or the like. Moreover, prior to the treatment using these apparatuses, the effect of the treatment by these apparatuses can be enhanced by applying moisture to the coating layer in advance. In the case of improving the surface gloss with these apparatuses, the coating composition of the present invention includes dimethyloctylamine, dimethyloctadecylamine, trimethyloctylammonium chloride, trimethyloctadecylammonium chloride, stearic acid, octyl alcohol, octadecyl alcohol. It is preferable to add a small amount of oily substances such as caprylic acid, stearic acid, liquid paraffin, silicone oil, and dispersions thereof as a release agent, since a recording medium with better surface quality can be obtained.

以下本発明の実施例を示す。なお、本実施例中において濃度を％で表示してある場合には、特に明記しない限り質量％で表示されているものとする。   Examples of the present invention will be described below. In addition, when the concentration is displayed in% in this example, it is displayed in mass% unless otherwise specified.

［アルミナ水和物の分散液の調製］
水２９９．００ｇを攪拌しながら、酢酸１．００ｇ、アルミナ水和物（強熱残量８０．３％、比表面積１４６ｍ２／ｇ、結晶型擬ベーマイト）の粉体１００．００ｇを添加し、そのまま２時間攪拌して分散・解膠し、アルミナ水和物の分散液を得た。この分散物を水で１００倍に希釈し、ガラス基板上に散布して走査型電子顕微鏡で観察したところ、個数で９０％以上の粒子の長辺が４００ｎｍ以下であり、また長辺１００ｎｍ以上の粒子が観察野中で全粒子が占める面積の８０％以上を占めていた。 [Preparation of Alumina Hydrate Dispersion]
While stirring 299.00 g of water, 1.00 g of acetic acid, 100.00 g of powder of alumina hydrate (remaining ignition temperature 80.3%, specific surface area 146 m 2 / g, crystalline pseudoboehmite) were added, The mixture was stirred as it was for 2 hours for dispersion and peptization to obtain a dispersion of alumina hydrate. When this dispersion was diluted 100 times with water, dispersed on a glass substrate and observed with a scanning electron microscope, the long side of 90% or more of the particles was 400 nm or less, and the long side was 100 nm or more. The particles accounted for 80% or more of the area occupied by all particles in the observation field.

［塗工組成物をゲル化させるヒドラジン系架橋剤の最低量を求める試験］
上のアルミナ水和物の分散液を１０バッチ調製し、それぞれに濃度１０％のジアセトンアクリルアミド変性ポリビニルアルコール（日本酢ビ・ポバール社製ＤＦ−１７）水溶液８０．００ｇ（ジアセトンアクリルアミド変性ポリビニルアルコール８．００ｇ）を添加・混合し、ついで濃度１０％のアジピン酸ジヒドラジド水溶液を０．１０ｇから１．００ｇまで０．１０ｇきざみで添加し、２５℃で２４時間放置したところ、アジピン酸ジヒドラジド水溶液を０．８０ｇ（アジピン酸ジヒドラジド０．０８ｇ）以上添加したものはゲル化し、添加量がこれ未満であるものはゲル化しなかった。 [Test for determining minimum amount of hydrazine-based cross-linking agent that gels coating composition]
10 batches of the above dispersion of alumina hydrate were prepared, and 80.00 g of diacetone acrylamide-modified polyvinyl alcohol (DF-17, manufactured by Nihon Virgin-Poval) with a concentration of 10% each (diacetone acrylamide-modified polyvinyl alcohol). 8.00 g) was added and mixed, then 10% strength adipic acid dihydrazide aqueous solution was added in increments of 0.10 g from 0.10 g to 1.00 g and allowed to stand at 25 ° C. for 24 hours. What added 0.80g (adipic acid dihydrazide 0.08g) or more gelatinized, and what added less than this did not gelatinize.

［ジアセトンアクリルアミド変性ポリビニルアルコールとヒドラジン系架橋剤間の反応が５０％以上進行するに要する時間を求める試験］
上のアルミナ水和物の分散液に、濃度１０％のジアセトンアクリルアミド変性ポリビニルアルコール（日本酢ビ・ポバール社製ＤＦ−１７）水溶液８０．００ｇ（ジアセトンアクリルアミド変性ポリビニルアルコール８．００ｇ）を添加・混合し、ついで濃度１０％のアジピン酸ジヒドラジド水溶液を、塗工組成物をゲル化させる最低量の２倍量、すなわち１．６０ｇ（アジピン酸ジヒドラジド０．１６ｇ）添加し放置したところ、アジピン酸ジヒドラジド水溶液の添加後３時間でゲル化していることが観察された。 [Test for obtaining time required for reaction between diacetone acrylamide-modified polyvinyl alcohol and hydrazine-based crosslinking agent to proceed by 50% or more]
Add 80.00 g of diacetone acrylamide-modified polyvinyl alcohol (DF-17, manufactured by Nippon Bibi-Poval Co., Ltd.) with a concentration of 10% to the above dispersion of alumina hydrate (8.00 g of diacetone acrylamide-modified polyvinyl alcohol). Mix, then add 10% strength adipic acid dihydrazide aqueous solution twice the minimum amount to gel the coating composition, that is, 1.60 g (0.16 g adipic acid dihydrazide) and leave it to stand. It was observed that gelation occurred 3 hours after the addition of the aqueous dihydrazide solution.

［塗工組成物Ａの調製］
上のアルミナ水和物の分散液に、濃度１０％のジアセトンアクリルアミド変性ポリビニルアルコール（日本酢ビ・ポバール社製ＤＦ−１７）水溶液８０．００ｇ（ポリビニルアルコール８．００ｇ）を添加・混合し、ついで濃度１０％のアジピン酸ジヒドラジド水溶液を０．７０ｇ（アジピン酸ジヒドラジド０．０７ｇ）添加し、３時間放置して塗工組成物Ａを調製した。 [Preparation of coating composition A]
To the above dispersion of alumina hydrate, 80.00 g (polyvinyl alcohol 8.00 g) of an aqueous solution of 10% diacetone acrylamide-modified polyvinyl alcohol (DF-17, manufactured by Nihon Acetate / Poval) was added and mixed. Subsequently, 0.70 g (0.07 g of adipic acid dihydrazide) of a 10% concentration adipic acid dihydrazide aqueous solution was added, and the mixture was allowed to stand for 3 hours to prepare a coating composition A.

［インクジェット記録媒体の作製］
塗工組成物Ａに、濃度１０％のアジピン酸ジヒドラジド水溶液の１０．００ｇ（アジピン酸ジヒドラジド１．００ｇ）をさらに添加し、直ちに表面を易接着処理した白色ポリエチレンテレフタレートフィルム上に、乾燥後の塗工量が２５ｇ／ｍ２になるよう、バーコーターを使用して塗工した。これを、１５０℃の熱風乾燥機中で、乾燥までの時間が９０秒となるような風量で乾燥して、インクジェット記録媒体を作製した。 [Preparation of inkjet recording medium]
To the coating composition A, 10.00 g of a 10% concentration of adipic acid dihydrazide aqueous solution (1.00 g of adipic acid dihydrazide) was further added, and immediately after drying, the coating was applied onto a white polyethylene terephthalate film whose surface was subjected to easy adhesion treatment. Coating was performed using a bar coater so that the work amount was 25 g / m 2 . This was dried in a hot air drier at 150 ° C. with an air volume such that the time until drying was 90 seconds, thereby producing an ink jet recording medium.

［塗工組成物Ｂの調製］
濃度１０％のアジピン酸ジヒドラジド水溶液の量を０．４０ｇ（アジピン酸ジヒドラジド０．０４ｇ）にした以外は、塗工組成物Ａと同様にして塗工組成物Ｂを調製した。 [Preparation of coating composition B]
A coating composition B was prepared in the same manner as the coating composition A except that the amount of the 10% adipic acid dihydrazide aqueous solution was changed to 0.40 g (adipic acid dihydrazide 0.04 g).

［インクジェット記録媒体の作製］
塗工組成物Ａの代わりに塗工組成物Ｂを用いた以外には、実施例１と同様にしてインクジェット記録媒体を作製した。 [Preparation of inkjet recording medium]
An ink jet recording medium was prepared in the same manner as in Example 1 except that the coating composition B was used instead of the coating composition A.

表面を易接着処理した白色ポリエチレンテレフタレートフィルム上に、濃度１０％のアジピン酸ジヒドラジド水溶液を、乾燥後の塗工量が０．２３ｇ／ｍ２となるように塗工し、１５０℃の熱風乾燥機中で乾燥した。ここに、塗工組成物Ａを、乾燥後の塗工量が２５ｇ／ｍ２になるよう、バーコーターを使用して塗工した。これを、１５０℃の熱風乾燥機中で、乾燥までの時間が９０秒となるような風量で乾燥して、インクジェット記録媒体を作製した。 On a white polyethylene terephthalate film whose surface has been subjected to easy adhesion treatment, an aqueous solution of adipic acid dihydrazide having a concentration of 10% is applied so that the coating amount after drying is 0.23 g / m 2, and a hot air dryer at 150 ° C. Dried in. The coating composition A was applied using a bar coater so that the coating amount after drying was 25 g / m 2 . This was dried in a hot air drier at 150 ° C. with an air volume such that the time until drying was 90 seconds, thereby producing an ink jet recording medium.

塗工組成物Ａの代わりに塗工組成物Ｂを用いた以外には、実施例３と同様にしてインクジェット記録媒体を作製した。   An ink jet recording medium was produced in the same manner as in Example 3 except that the coating composition B was used instead of the coating composition A.

［比較例１］
［塗工組成物Ｃの調製］
アジピン酸ジヒドラジド水溶液を添加しなかった以外は、塗工組成物Ａと同様にして塗工組成物Ｃを調製した。 [Comparative Example 1]
[Preparation of coating composition C]
A coating composition C was prepared in the same manner as the coating composition A, except that the adipic acid dihydrazide aqueous solution was not added.

［インクジェット記録媒体の作製］
塗工組成物Ａの代わりに塗工組成物Ｃを用いた以外には、実施例１と同様にしてインクジェット記録媒体を作製しようとしたが、乾燥後の塗工層の全面に亀裂が生じてしまい、良好なインクジェット記録媒体を得ることはできなかった。 [Preparation of inkjet recording medium]
An ink jet recording medium was prepared in the same manner as in Example 1 except that the coating composition C was used in place of the coating composition A. However, cracks occurred on the entire surface of the coating layer after drying. As a result, a good ink jet recording medium could not be obtained.

［比較例２］
塗工組成物Ｃに、濃度１０％のアジピン酸ジヒドラジド水溶液の１０．７０ｇ（アジピン酸ジヒドラジド１．０７ｇ）を添加し、直ちに表面を易接着処理した白色ポリエチレンテレフタレートフィルム上に、乾燥後の塗工量が２５ｇ／ｍ２になるよう、バーコーターを使用して塗工した。これを、これを、１５０℃の熱風乾燥機中で、乾燥までの時間が９０秒となるような風量で乾燥して、インクジェット記録媒体を作製しようとしたが、乾燥後の塗工層の全面に亀裂が生じてしまい、良好なインクジェット記録媒体を得ることはできなかった。 [Comparative Example 2]
10.70 g (1.07 g of adipic acid dihydrazide) of a 10% concentration of adipic acid dihydrazide aqueous solution was added to coating composition C, and the coated film after drying was immediately applied onto a white polyethylene terephthalate film whose surface was easily adhered. Coating was performed using a bar coater so that the amount was 25 g / m 2 . This was dried in a hot air drier at 150 ° C. with an air flow so that the time until drying was 90 seconds, and an attempt was made to produce an ink jet recording medium. As a result, cracks occurred, and a good ink jet recording medium could not be obtained.

［比較例３］
塗工組成物Ｃに、濃度１０％のアジピン酸ジヒドラジド水溶液の２０．００ｇ（アジピン酸ジヒドラジド２．００ｇ）を添加し、直ちに表面を易接着処理した白色ポリエチレンテレフタレートフィルム上に、乾燥後の塗工量が２５ｇ／ｍ２になるよう、バーコーターを使用して塗工した。これを、これを、１５０℃の熱風乾燥機中で、乾燥までの時間が９０秒となるような風量で乾燥して、インクジェット記録媒体を作製しようとしたが、乾燥後の塗工層の全面に亀裂が生じてしまい、良好なインクジェット記録媒体を得ることはできなかった。 [Comparative Example 3]
To the coating composition C, 20.00 g of an adipic acid dihydrazide aqueous solution with a concentration of 10% (2.00 g of adipic acid dihydrazide) was added, and the coating after drying was immediately applied onto a white polyethylene terephthalate film whose surface was easily adhered. Coating was performed using a bar coater so that the amount was 25 g / m 2 . This was dried in a hot air drier at 150 ° C. with an air flow so that the time until drying was 90 seconds, and an attempt was made to produce an ink jet recording medium. As a result, cracks occurred, and a good ink jet recording medium could not be obtained.

［比較例４］
［塗工組成物Ｄの調製］
濃度１０％のアジピン酸ジヒドラジド水溶液の量を１０．４０ｇ（アジピン酸ジヒドラジド１．０４ｇ）にした以外は、塗工組成物Ａと同様にして塗工組成物Ｄを調製したが、この塗工組成物は３時間放置後にはゲル化しており、インクジェット記録媒体の作製に用いることはできなかった。 [Comparative Example 4]
[Preparation of coating composition D]
A coating composition D was prepared in the same manner as the coating composition A except that the amount of the 10% adipic acid dihydrazide aqueous solution was changed to 10.40 g (1.04 g of adipic acid dihydrazide). The product gelled after being left for 3 hours and could not be used to produce an ink jet recording medium.

［比較例５］
塗工組成物Ａの代わりに塗工組成物Ｃを用いた以外には、実施例３と同様にしてインクジェット記録媒体を作製しようとしたが、乾燥後の塗工層の全面に亀裂が生じてしまい、良好なインクジェット記録媒体を得ることはできなかった。 [Comparative Example 5]
An attempt was made to produce an ink jet recording medium in the same manner as in Example 3 except that the coating composition C was used in place of the coating composition A, but cracks occurred on the entire surface of the coating layer after drying. As a result, a good ink jet recording medium could not be obtained.

［比較例６］
白色ポリエチレンテレフタレートフィルム上に下引きするアジピン酸ジヒドラジドの量を、乾燥後の塗工量が０．４６ｇ／ｍ２となるようにした以外には比較例５と同様にしてインクジェット記録媒体を作製しようとしたが、乾燥後の塗工層の全面に亀裂が生じてしまい、良好なインクジェット記録媒体を得ることはできなかった。 [Comparative Example 6]
An inkjet recording medium is prepared in the same manner as in Comparative Example 5 except that the amount of adipic acid dihydrazide to be subtracted on the white polyethylene terephthalate film is set to 0.46 g / m 2 after drying. However, cracks occurred on the entire surface of the coating layer after drying, and a good ink jet recording medium could not be obtained.

［比較例７］
ジアセトンアクリルアミド変性ポリビニルアルコールに代え、アセトアセチル変性ポリビニルアルコール（日本合成化学工業社製Ｚ−２００）を用いた以外には、実施例１と同様にしてインクジェット記録媒体を作製した。 [Comparative Example 7]
An ink jet recording medium was prepared in the same manner as in Example 1 except that acetoacetyl-modified polyvinyl alcohol (Z-200 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used instead of diacetone acrylamide-modified polyvinyl alcohol.

［比較例８］
ジアセトンアクリルアミド変性ポリビニルアルコールに代え、アセトアセチル変性ポリビニルアルコール（日本合成化学工業社製Ｚ−２００）を用いた以外には、実施例３と同様にしてインクジェット記録媒体を作製した。 [Comparative Example 8]
An ink jet recording medium was prepared in the same manner as in Example 3 except that acetoacetyl-modified polyvinyl alcohol (Z-200 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used instead of diacetone acrylamide-modified polyvinyl alcohol.

［評価］
各実施例および比較例７および８で得られたインクジェット記録媒体は、いずれも良好な表面光沢を有していた。また、これらの記録媒体にインクジェットプリンタで評価画像を印刷したところ、いずれも良好な画像が得られた。 [Evaluation]
The ink jet recording media obtained in each Example and Comparative Examples 7 and 8 all had good surface gloss. Moreover, when an evaluation image was printed on these recording media with an ink jet printer, good images were obtained in all cases.

［黄変性の評価］
各実施例で得られたインクジェット記録媒体を３０日間大気に暴露したが、著しい変色は観察されなかった。いっぽう、比較例７および８で得られたインクジェット記録媒体を同じに大気に暴露したところ、その表面に著しい黄変が観察された。 [Evaluation of yellowing]
The inkjet recording medium obtained in each example was exposed to the atmosphere for 30 days, but no significant discoloration was observed. On the other hand, when the ink jet recording media obtained in Comparative Examples 7 and 8 were exposed to the same atmosphere, significant yellowing was observed on the surface.

実施例１および２、比較例１〜４および７のアジピン酸ジヒドラジドの添加量および塗工直前のアジピン酸ジヒドラジドの添加量、塗工時のひび割れの有無および製造された記録媒体の大気暴露後の黄変をまとめ表１に示す。   The amount of adipic acid dihydrazide added in Examples 1 and 2 and Comparative Examples 1 to 4 and 7 and the amount of adipic acid dihydrazide immediately before coating, the presence or absence of cracks during coating, and the recording medium produced after exposure to the atmosphere The yellowing is summarized and shown in Table 1.

Figure 2006281474
Figure 2006281474

実施例３および４、比較例５、６および８の塗工組成物調製時のアジピン酸ジヒドラジドの添加量および基材上にあらかじめ塗工するアジピン酸ジヒドラジドの量、塗工時のひび割れの有無および製造された記録媒体の大気暴露後の黄変をまとめ表２に示す。   The amount of adipic acid dihydrazide added during preparation of the coating compositions of Examples 3 and 4 and Comparative Examples 5, 6 and 8, and the amount of adipic acid dihydrazide applied beforehand on the substrate, the presence or absence of cracks during coating, and Table 2 shows the yellowing of the manufactured recording medium after exposure to the atmosphere.

Figure 2006281474
Figure 2006281474

各実施例と各比較例を比較すれば明らかであるように、本発明により、その有害性から排水規制の対象となるホウ酸およびその塩を含まず、黄変を生じにくく、かつ高い生産性でインクジェット記録媒体を製造できた。   As is clear from the comparison between each example and each comparative example, the present invention does not include boric acid and its salts that are subject to wastewater regulation due to its harmfulness, is less prone to yellowing, and has high productivity. Thus, an inkjet recording medium could be manufactured.

Claims (2)

（１）サブミクロン顔料、（２）ジアセトンアクリルアミド変性ポリビニルアルコール、（３）塗工組成物をゲル化させる最低量の５０〜９５％のヒドラジン系架橋剤を含み、ジアセトンアクリルアミド変性ポリビニルアルコールと添加されたヒドラジン系架橋剤間の反応が５０％以上進行した塗工組成物に、塗工直前にヒドラジン系架橋剤を追加して塗工することを特徴とするインクジェット記録媒体の製造方法。   (1) a submicron pigment, (2) diacetone acrylamide modified polyvinyl alcohol, (3) a minimum amount of 50-95% hydrazine-based cross-linking agent for gelling the coating composition, A method for producing an ink jet recording medium, comprising adding a hydrazine-based crosslinking agent to a coating composition in which a reaction between the added hydrazine-based crosslinking agents has progressed by 50% or more immediately before coating. （１）サブミクロン顔料、（２）ジアセトンアクリルアミド変性ポリビニルアルコール、（３）塗工組成物をゲル化させる最低量の５０〜９５％のヒドラジン系架橋剤を含み、ジアセトンアクリルアミド変性ポリビニルアルコールと添加されたヒドラジン系架橋剤間の反応が５０％以上進行した塗工組成物を、あらかじめヒドラジン系架橋剤を含む下引き層を塗工した基材上に塗工することを特徴とするインクジェット記録媒体の製造方法。   (1) a submicron pigment, (2) diacetone acrylamide modified polyvinyl alcohol, (3) a minimum amount of 50-95% hydrazine-based cross-linking agent for gelling the coating composition, Inkjet recording characterized in that a coating composition in which a reaction between added hydrazine-based crosslinking agents has progressed by 50% or more is coated on a base material previously coated with an undercoat layer containing a hydrazine-based crosslinking agent. A method for manufacturing a medium.
JP2005101090A 2005-03-31 2005-03-31 Method for manufacturing inkjet recording medium Pending JP2006281474A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005101090A JP2006281474A (en) 2005-03-31 2005-03-31 Method for manufacturing inkjet recording medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005101090A JP2006281474A (en) 2005-03-31 2005-03-31 Method for manufacturing inkjet recording medium

Publications (1)

Publication Number Publication Date
JP2006281474A true JP2006281474A (en) 2006-10-19

Family

ID=37403894

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005101090A Pending JP2006281474A (en) 2005-03-31 2005-03-31 Method for manufacturing inkjet recording medium

Country Status (1)

Country Link
JP (1) JP2006281474A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012070339A1 (en) * 2010-11-24 2012-05-31 日本酢ビ・ポバール株式会社 Method for producing inkjet recording material
JP2013039730A (en) * 2011-08-16 2013-02-28 Japan Vam & Poval Co Ltd Method of producing inkjet recording material
WO2015056505A1 (en) 2013-10-18 2015-04-23 日本酢ビ・ポバール株式会社 Method of producing polyvinyl alcohol resin, and polyvinyl alcohol resin obtained thereby

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012070339A1 (en) * 2010-11-24 2012-05-31 日本酢ビ・ポバール株式会社 Method for producing inkjet recording material
JP5647263B2 (en) * 2010-11-24 2014-12-24 日本酢ビ・ポバール株式会社 Method for producing ink jet recording material
EP2644403A4 (en) * 2010-11-24 2015-11-25 Japan Vam & Poval Co Ltd Method for producing inkjet recording material
JP2013039730A (en) * 2011-08-16 2013-02-28 Japan Vam & Poval Co Ltd Method of producing inkjet recording material
WO2015056505A1 (en) 2013-10-18 2015-04-23 日本酢ビ・ポバール株式会社 Method of producing polyvinyl alcohol resin, and polyvinyl alcohol resin obtained thereby
US10538120B2 (en) 2013-10-18 2020-01-21 Japan Vam & Poval Co., Ltd. Method for producing polyvinyl alcohol resin, and polyvinyl alcohol resin obtained by the method

Similar Documents

Publication Publication Date Title
CN105636996B (en) The manufacturing method of polyvinyl alcohol resin and thus obtained polyvinyl alcohol resin
US7901749B2 (en) Porous inkjet printing substrate containing polymer-grafted mineral oxides
JP4638324B2 (en) Inkjet recording medium
JP2008246984A (en) Inkjet recording medium
JP2006281474A (en) Method for manufacturing inkjet recording medium
JPH1191242A (en) Treatment liquid for material to be recorded
JP2007016208A (en) Micro-particle dispersion and medium to be recorded using the same
JP5210116B2 (en) Inkjet recording medium
JP4418583B2 (en) Resin composition for inkjet recording and recording sheet
JP7348723B2 (en) Method for promoting crosslinking reaction of polyvinyl alcohol resin
JP2007268928A (en) Inkjet recording medium
JP2002120452A (en) Composition for ink jet recording material, and body to be recorded or recording sheet using the same
JP4350673B2 (en) Method for manufacturing ink jet recording medium and ink jet recording medium
JP2001322347A (en) Ink jet printing method
JP2008246949A (en) Manufacturing method of thermal transfer image receiving sheet
JP4499023B2 (en) Resin composition for ink recording medium and ink recording medium
JP2006231595A (en) Coating composition for inkjet recording medium and inkjet recording medium
JP4509939B2 (en) Resin composition for ink recording medium and ink recording medium
JP2006051741A (en) Liquid composition and recording medium
JP2007055166A (en) Method for manufacturing glossy cast paper
JP2002052805A (en) Ink jet recording method and recorded matter obtained by the method
JP2006168045A (en) Image forming method, liquid composition, and recorded article
JP2004001445A (en) Manufacturing method for inkjet recording paper sheet and inkjet recording paper sheet obtained by this manufacturing method
FR2903044A1 (en) MATERIAL FOR FORMING OR EDITING IMAGES AND METHOD FOR MANUFACTURING THE SAME
JP2002137533A (en) Coating agent of ink jet printing sheet and sheet