JP2750433B2 - Inkjet recording paper - Google Patents
Inkjet recording paperInfo
- Publication number
- JP2750433B2 JP2750433B2 JP63031575A JP3157588A JP2750433B2 JP 2750433 B2 JP2750433 B2 JP 2750433B2 JP 63031575 A JP63031575 A JP 63031575A JP 3157588 A JP3157588 A JP 3157588A JP 2750433 B2 JP2750433 B2 JP 2750433B2
- Authority
- JP
- Japan
- Prior art keywords
- recording paper
- acid
- pva
- mol
- group
- 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
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
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記録用紙に関し、インク吸収
能にすぐれ解像度が高く、鮮明な記録画像を形成するイ
ンクジェット記録用紙に関する。Description: FIELD OF THE INVENTION The present invention relates to an ink jet recording sheet, and more particularly, to an ink jet recording sheet which is excellent in ink absorption capacity, has a high resolution, and forms a clear recorded image.
［従来の技術］ インクジェット記録方式は、ファクシミリ、各種プリ
ンター等への応用が進められている。インクジェット記
録方式に使用される被記録材に要求される性質として
は、インクの吸収速度が大きいこと、インクドットの径
が必要以上に大きくならないこと等である。[Prior Art] The inkjet recording method is being applied to facsimile machines, various printers, and the like. Properties required for the recording material used in the ink jet recording method include a high ink absorption speed and a requirement that the diameter of the ink dot does not become larger than necessary.
かかる欠点を改善する方法として、例えば特開昭61−
134291号公報に示される如く、各種ポリビニルアルコー
ル（以下PVAと略記する）系樹脂を紙中及び／又は塗工
層中に存在させることが提案されている。As a method for improving such a defect, for example, Japanese Patent Application Laid-Open
As disclosed in JP 134291, it has been proposed that various polyvinyl alcohol (hereinafter abbreviated as PVA) resins be present in paper and / or in a coating layer.
［本発明が解決しようとする問題点］ しかし、本発明者の検討では近時の高品質の要求に必
ずしも対応が出来ないため、更にインク吸収能にすぐ
れ、解像度が高くかつ鮮明な記録画面を形成出来るイン
クジェット記録紙を提供することが要請されることが明
らかとなった。[Problems to be Solved by the Present Invention] However, since the present inventors cannot always respond to the recent demand for high quality, it has been found that a higher-resolution and higher-resolution recording screen with higher ink absorption capacity can be obtained. It has become clear that there is a need to provide an inkjet recording paper that can be formed.
［問題点を解決するための手段］ 本発明者は、更に研究した結果、４％水溶液の20℃に
おける粘度が、２〜60cpsのアニオン性基を有するPVA系
樹脂を紙中及び／又は塗工層中に存在させたインクジェ
ット記録紙が目的を達成出来ることを見出し、本発明を
完成した。[Means for Solving the Problems] As a result of further studies, the present inventor has reported that a 4% aqueous solution of a PVA resin having an anionic group having a viscosity at 20 ° C. of 2 to 60 cps is applied to paper and / or coated. It has been found that the ink jet recording paper present in the layer can achieve the object, and the present invention has been completed.
本発明でいうアニオン性基としては、代表的にはスル
ホン酸基やカルボキシル基である。The anionic group referred to in the present invention is typically a sulfonic acid group or a carboxyl group.
以下、具体的に説明する。 Hereinafter, a specific description will be given.
スルホン酸基含有PVAは次の様にして製造される。 The sulfonic acid group-containing PVA is produced as follows.
エチレンスルホン酸、アリルスルホン酸、メタアリ
ルスルホン酸等のオレフィンスルホン酸又はその塩と酢
酸ビニル等のビニルエステルとをアルコールあるいはア
ルコール／水混合溶媒中で重合し得られる重合体を更に
ケン化する方法。A method for further saponifying a polymer obtained by polymerizing an olefin sulfonic acid such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid or a salt thereof with a vinyl ester such as vinyl acetate in an alcohol or an alcohol / water mixed solvent. .
［Ｒはアルキル基、Ｒ′はアルキレン基、Ｍは水素又は
アルカリ金属、アンモニウムイオン］で示されるスルホ
アルキルマレートと酢酸ビニル等のビニルエステルとを
共重合させ、得られる共重合体を更にケン化する方法。
上記スルホアルキルマレートにはナトリウムスルホプロ
ピル２−エチルヘキシルマレート、ナトリウムスルホプ
ロピルトリデシルマレート、ナトリウムスルホプロピル
エイコシルマレート等が挙げられる。 [R is an alkyl group, R 'is an alkylene group, M is hydrogen or an alkali metal, ammonium ion] and a vinyl ester such as vinyl acetate is copolymerized. How to
Examples of the sulfoalkyl malate include sodium sulfopropyl 2-ethylhexyl malate, sodium sulfopropyl tridecyl malate, and sodium sulfopropyl eicosyl malate.
［R1水素又はメチル基、R2は水素又はアルキル基、
Ｒ′,Mはと同様］で示されるスルホアルキル（メタ）
アクリルアミド例えばＮ−スルホイソブチレンアクリル
アミドナトリウム塩と酢酸ビニル等のビニルエステルと
を共重合させ、得られる共重合体をケン化する方法。更
に一般式 で示されるスルホアルキル（メタ）アクリレート、例え
ばナトリウム２−スルホエチルアクリレートと酢酸ビニ
ル等のビニルエステルとを共重合させ、得られる共重合
体をケン化する方法。 [R 1 hydrogen or a methyl group, R 2 is a hydrogen or an alkyl group,
R 'and M are the same as defined above]
A method of copolymerizing acrylamide, for example, sodium salt of N-sulfoisobutyleneacrylamide with a vinyl ester such as vinyl acetate, and saponifying the resulting copolymer. More general formula A method of copolymerizing a sulfoalkyl (meth) acrylate, for example, sodium 2-sulfoethyl acrylate, with a vinyl ester such as vinyl acetate, and saponifying the resulting copolymer.
これら共重合の際には、エチレン性不飽和カルボン酸
アルキルエステル、α−オレフィン、アルキルビニルエ
ーテル等、任意の第３成分を導入させることが可能であ
る。In the case of these copolymerizations, it is possible to introduce an optional third component such as an ethylenically unsaturated carboxylic acid alkyl ester, α-olefin, or alkyl vinyl ether.
PVAを臭素、ヨウで処理した後、酸性亜硫酸ソーダ
水溶液中で加熱する方法。A method in which PVA is treated with bromine and iodine and then heated in an aqueous sodium acid sulfite solution.
PVAを濃厚な硫酸水溶液中で加熱する方法。 A method of heating PVA in a concentrated aqueous sulfuric acid solution.
PVAをスルホン酸基を含有するアルデヒド化合物で
アセタール化する方法。A method of acetalizing PVA with an aldehyde compound containing a sulfonic acid group.
等である。And so on.
スルホン酸基は遊離の酸の形であっても、あるいはナ
トリウム塩、カリウム塩、アンモニウム塩等の形であっ
ても良い。The sulfonic acid group may be in the form of a free acid or in the form of a sodium salt, a potassium salt, an ammonium salt or the like.
スルホン酸基含有PVA系樹脂中におけるスルホン酸基
の含有量は、0.1〜20モル％、好ましくは１〜10モル％
が本発明の目的には好適である。The content of the sulfonic acid group in the sulfonic acid group-containing PVA resin is 0.1 to 20 mol%, preferably 1 to 10 mol%.
Are suitable for the purpose of the present invention.
ケン化度は40〜100モル％、好ましくは60〜100モル％
が実用的であり、更に４％水溶液の20℃における粘度が
２〜60cpsであることが必要であり、好ましくは３〜40c
ps程度のものが有用である。The degree of saponification is 40 to 100 mol%, preferably 60 to 100 mol%.
Is practical, and the viscosity of the 4% aqueous solution at 20 ° C. needs to be 2 to 60 cps, preferably 3 to 40 cps.
Those of the order of ps are useful.
一方、PVAにカルボキシル基を導入する方法としては ビニルエステルと共重合しうるモノマーと共重合さ
せてケン化する方法 PVAにグラフト重合するか、又はポリビニルエステ
ルにグラフト重合してケン化する方法 PVAの化学反応による方法などがあげられる。On the other hand, as a method of introducing a carboxyl group into PVA, a method of copolymerizing with a monomer copolymerizable with a vinyl ester and saponifying a method of grafting PVA, or a method of graft-polymerizing a polyvinyl ester and saponifying a method of PVA Examples include a method by a chemical reaction.
の方法としては、ギ酸ビニル、酢酸ビニルまたはプ
ロピオン酸ビニルなどの有機酸ビニルエステルと共重合
しうる不飽和塩基性酸、不飽和二塩基性酸、これらの無
水物、またはこれらのエステル、例えばアクリル酸、メ
タクリル酸、クロトン酸、マレイン酸、フマル酸、イタ
コン酸、無水マレイン酸、無水イタコン酸などの共重合
体をケン化することにより、あるいは上記ビニルエステ
ル類とアクリルニトリル、メタクリルニトリル、アクリ
ルアミド、メタクリルアミドとの共重合体をケン化する
ことによって目的とする分子中にカルボキシル基を有す
るポリビニルアルコール誘導体を製造することが出来
る。Examples of the method include an unsaturated basic acid, an unsaturated dibasic acid, an anhydride thereof, or an ester thereof, such as an acrylic acid, which can be copolymerized with an organic acid vinyl ester such as vinyl formate, vinyl acetate, or vinyl propionate. Acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, by saponifying a copolymer such as itaconic anhydride, or the above vinyl esters and acrylonitrile, methacrylonitrile, acrylamide, By saponifying a copolymer with methacrylamide, a target polyvinyl alcohol derivative having a carboxyl group in the molecule can be produced.
の方法としては、PVAあるいはポリ酢酸ビニルなど
のようなポリビニルエステル、アクリルニトリル、アク
リルアマイドなどをグラフト重合してケン化する方法な
どがある。Examples of the method include a method in which polyvinyl ester such as PVA or polyvinyl acetate, acrylonitrile, acrylamide, or the like is graft-polymerized and saponified.
の方法としては、PVAに二塩基性酸、たとえばマレ
イン酸、フマル酸、フタル酸、蓚酸、マロン酸、コハク
酸、アジピン酸あるいはこれらの無水物を反応させて片
エステル化反応によってカルボキシル基を導入させるこ
とができる。As a method, a dibasic acid such as maleic acid, fumaric acid, phthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid or an anhydride thereof is reacted with PVA to introduce a carboxyl group by a single esterification reaction. Can be done.
カルボキシル基含有PVA系樹脂中におけるカルボキシ
ル基の含有量は、0.1〜20モル％、好ましくは１〜10％
モルが本発明の目的には好適である。The content of the carboxyl group in the carboxyl group-containing PVA resin is 0.1 to 20 mol%, preferably 1 to 10%.
Mole is preferred for the purposes of the present invention.
ケン化度は40〜100モル％、好ましくは60〜100モル％
が実用的であり、更に４％水溶液の20℃における粘度が
２〜60cpsであることが必要であり、好ましくは３〜40c
ps程度のものが有用である。The degree of saponification is 40 to 100 mol%, preferably 60 to 100 mol%.
Is practical, and the viscosity of the 4% aqueous solution at 20 ° C. needs to be 2 to 60 cps, preferably 3 to 40 cps.
Those of the order of ps are useful.
本発明においてアニオン性基を有するPVA系樹脂をイ
ンクジェット記録用紙中に含有せしめる方法としては、
公知の方法によって抄紙したインクジェット記録用紙に
スプレーあるいはサイドプレスにより表面に塗布あるい
は含浸せしめる方法、あるいは公知のコート紙タイプの
インクジェット記録用紙を製造する際、該コーティング
塗料中に混合し、ブレード、エアナイフ、ロールコータ
ー等の塗工機により塗布する方法、またはインクジェッ
ト記録用紙の抄紙時に内添する方法等が挙げられる。In the present invention, as a method of incorporating a PVA-based resin having an anionic group in the inkjet recording paper,
A method of applying or impregnating the surface by spraying or side-pressing the ink jet recording paper made by a known method, or when manufacturing a known coated paper type ink jet recording paper, mixing in the coating paint, blade, air knife, Examples thereof include a method of applying with a coating machine such as a roll coater, and a method of internally adding at the time of making ink jet recording paper.
インクジェット記録用紙中への該アニオン性基含有PV
A系樹脂の添加量としては通常0.01〜10g/m2好ましくは
0.05〜5g/m2が用いられる。0.01g/m2未満の場合にはイ
ンク吸収能、解像度の改善効果がなく、10g/m2を越える
場合には耐水性が低下する傾向があるため好ましくな
い。The anionic group-containing PV in an ink jet recording paper
The addition amount of the A resin usually 0.01 to 10 g / m 2 is preferably
0.05-5 g / m 2 is used. If it is less than 0.01 g / m 2 , there is no effect of improving the ink absorption capacity and resolution, and if it is more than 10 g / m 2 , the water resistance tends to decrease.
かかる記録紙の製造時にタルク、カオリン、炭酸カル
シウム、非膠質シリカ粉末、微粉末状尿素ホルマリン樹
脂填料等の各種填料を有する記録用紙、あるいは非膠質
シリカ粉末、酸性白土、クレー、タルク、炭酸カルシウ
ム、けいそう土、酸化チタン、硫酸バリウム等の白色顔
料を塗工層として有する記録用紙等にアニオン性基含有
PVAを適用することによって、インク吸収能、解像度が
高く、かつ鮮明な記録画像を形成しうるインクジェット
記録用紙を得ることができる。During the production of such recording paper, talc, kaolin, calcium carbonate, non-colloidal silica powder, recording paper having various fillers such as fine powder urea formalin resin filler, or non-colloidal silica powder, acid clay, clay, talc, calcium carbonate, Contains anionic group in recording paper etc. which have white pigment such as diatomaceous earth, titanium oxide, barium sulfate etc. as coating layer
By applying PVA, it is possible to obtain an ink jet recording paper having a high ink absorption capacity and a high resolution and capable of forming a clear recorded image.
記録用紙製造に際してポリアクリルアミド、デンプ
ン、カゼイン、アラビアゴム、カルボキシメチルセルロ
ース、メチルセルロース、通常のPVA、ポリアクリル酸
ソーダ等の水溶液樹脂、合成ゴムラテックス等の合成樹
脂ラテックス、分散蛍光染料、PH調節材、消泡剤、潤滑
剤、防腐剤、界面活性剤等各種添加剤を併用して使用す
ることもできる。In the production of recording paper, polyacrylamide, starch, casein, gum arabic, carboxymethylcellulose, methylcellulose, ordinary PVA, aqueous resin such as sodium polyacrylate, synthetic resin latex such as synthetic rubber latex, dispersed fluorescent dye, pH control material, Various additives such as a foaming agent, a lubricant, a preservative, and a surfactant can be used in combination.
［作用及び効果］ 本発明のインクジェット記録用紙はインク吸収能、解
像度が高く、かつ鮮明な記録画像を与える。[Operation and Effect] The ink jet recording paper of the present invention has a high ink absorption capacity, a high resolution and gives a clear recorded image.
［実施例］ 次に実例を挙げて本発明を更に詳しく説明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
実施例１ アリルスルホン酸ナトリウムと酢酸ビニルとの共重合
体をケン化して得られるスルホン酸ナトリウムの含有量
が５モル％、酢酸ビニル成分のケン化度が88モル％、４
％水溶液粘度（20℃）が、5cpsのスルホン酸ナトリウム
変性PVAを使用して下記の塗工液を調製した。Example 1 The content of sodium sulfonate obtained by saponifying a copolymer of sodium allyl sulfonate and vinyl acetate was 5 mol%, and the saponification degree of the vinyl acetate component was 88 mol%.
The following coating solution was prepared using sodium sulfonate-modified PVA having a 5% aqueous solution viscosity (20 ° C.).
非膠質シリカ粉末 100部 アニオン性基含有PVA系樹脂 50部 水 600部 一方、原紙としては、JIS P8122に基づくサイズ度が
20秒の一般上質紙（坪量65g/m2）を使用し、この原紙上
に上記塗工用組成物を乾燥塗工量で10g/m2となるように
ブレードコーターで塗布し、乾燥してインクジェット記
録用紙を得た。この記録用紙に対して下記２色のインク
を用いてカラーインクジェット記録を行い、記録特性の
評価を行った。Non-colloidal silica powder 100 parts Anionic group-containing PVA resin 50 parts Water 600 parts On the other hand, the sizing degree based on JIS P8122
Using a general high-quality paper (basis weight 65 g / m 2 ) of 20 seconds, apply the above coating composition on this base paper with a blade coater to a dry coating amount of 10 g / m 2 and dry. Thus, an ink jet recording paper was obtained. Color ink jet recording was performed on this recording paper using the following two color inks, and recording characteristics were evaluated.
シアンインク （組成）C.I.ダイレクトブルー86 ２部 ジエチレングリコール 30部 水 70部 ブラックインク（組成） C.I.ダイレクトブラック19 ２部 ジエチレングリコール 30部 水 70部 記録用紙の評価結果を第１表に示す。 Cyan ink (composition) C.I. Direct Blue 86 2 parts Diethylene glycol 30 parts Water 70 parts Black ink (composition) C.I. Direct Black 19 2 parts Diethylene glycol 30 parts Water 70 parts The evaluation results of the recording paper are shown in Table 1.
但し、ドット濃度はJISK7505を印字マイクロドットに
応用してサクラマイクロデンシドメーターPDM−５（小
西六写真工業製）を用いて、被記録材の表に形成された
ドットのうち黒ドットにつき測定した。However, the dot density was measured for black dots among the dots formed on the surface of the recording material using a Sakura Micro Densidometer PDM-5 (manufactured by Konishi Roku Kogyo Kogyo) by applying JISK7505 to printing microdots. .
又、インク吸収性は、IBM3852カラーインクジェット
プリンターで混色２度打ちを行い、この時各インクのニ
ジミがなく１秒後に完全にインク受理層に吸収されてい
る場合を○にて評価した。The ink absorptivity was evaluated by performing a double-color hitting twice using an IBM3852 color inkjet printer, and when each ink was completely absorbed in the ink receiving layer after 1 second without blurring.
実施例２〜４ 実施例１で用いられたアニオン変性PVAに替えて次の
ような変性PVAを用いる以外は実施例１と同様に行っ
た。評価結果を合わせて第１表に示す。Examples 2 to 4 The same procedure was performed as in Example 1 except that the following modified PVA was used instead of the anion-modified PVA used in Example 1. Table 1 also shows the evaluation results.
実施例2; アリルスルホン酸ナトリウム変性PVA アリルスルホン酸ナトリウム:1モル％ 酢酸ビニル成分のケン化度:98モル％ ４％水溶液粘度（20℃）:10cps 実施例3: Ｎ−スルホイソブチレンアクリルアミドナトリウム変性
PVA Ｎ−スルホイソブチレンアクリルアミドナトリウム:1
0モル％ 酢酸ビニル成分のケン化度:88モル％ ４％水溶液粘度（20℃）:20cps 実施例４ マレイン酸モノメチル変性PVA マレイン酸モノメチル:5モル％ 酢酸ビニル成分のケン化度:90モル％ ４％水溶液粘度（20℃）:30cps 比較例１ 実施例１において用いられたアニオン性基含有PVA系
樹脂にかえてPVA（ケン化度98.5、重合度1750）を用い
る以外は実施例１と同様に行った。Example 2; sodium allyl sulfonate-modified PVA sodium allyl sulfonate: 1 mol% Degree of saponification of vinyl acetate component: 98 mol% 4% aqueous solution viscosity (20 ° C.): 10 cps Example 3: sodium N-sulfoisobutylene acrylamide modified
PVA sodium N-sulfoisobutylene acrylamide: 1
0 mol% Saponification degree of vinyl acetate component: 88 mol% 4% Aqueous solution viscosity (20 ° C.): 20 cps Example 4 Monomethyl maleate-modified PVA monomethyl maleate: 5 mol% Degree of saponification of vinyl acetate component: 90 mol% 4% aqueous solution viscosity (20 ° C): 30 cps Comparative Example 1 Same as Example 1 except that PVA (degree of saponification 98.5, degree of polymerization 1750) was used instead of the anionic group-containing PVA resin used in Example 1. I went to.
結果を合わせて第１表に示す。 The results are shown in Table 1.
比較例２ 酢酸ビニルとトリメチル−３−（１−アクリルアミド
プロピル）アンモニウムクロリドとの共重合体をケン化
して得られる、カチオン性基を有する単量体単位の含有
量が３モル％で酢酸ビニル単位のケン化度98.5モル％、
重合度1750のものを使用した以外は、実施例１と同じ実
験を行った。Comparative Example 2 The content of the monomer unit having a cationic group obtained by saponifying a copolymer of vinyl acetate and trimethyl-3- (1-acrylamidopropyl) ammonium chloride was 3 mol%, and the vinyl acetate unit was 98.5 mol% of saponification degree of
The same experiment as in Example 1 was performed, except that the one having a polymerization degree of 1750 was used.
結果を第１表に合わせて示す。 The results are shown in Table 1.
Claims (2)
20℃における粘度が、２〜60cpsのアニオン性基を有す
るポリビニルアルコール系樹脂を含有してなることを特
徴とするインクジェット記録用紙。1. A 4% aqueous solution in paper and / or a coating layer.
An ink jet recording paper comprising a polyvinyl alcohol resin having an anionic group having a viscosity at 20 ° C. of 2 to 60 cps.
ル系樹脂がスルホン酸塩基を含有するポリビニルアルコ
ール系樹脂である特許請求の範囲第１項記載のインクジ
ェット記録用紙。2. The ink jet recording paper according to claim 1, wherein the polyvinyl alcohol-based resin having an anionic group is a polyvinyl alcohol-based resin containing a sulfonate group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63031575A JP2750433B2 (en) | 1988-02-12 | 1988-02-12 | Inkjet recording paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63031575A JP2750433B2 (en) | 1988-02-12 | 1988-02-12 | Inkjet recording paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01206088A JPH01206088A (en) | 1989-08-18 |
| JP2750433B2 true JP2750433B2 (en) | 1998-05-13 |
Family
ID=12334975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63031575A Expired - Lifetime JP2750433B2 (en) | 1988-02-12 | 1988-02-12 | Inkjet recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2750433B2 (en) |
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