JPS61134291A - Ink jet recording paper - Google Patents
Ink jet recording paperInfo
- Publication number
- JPS61134291A JPS61134291A JP59255970A JP25597084A JPS61134291A JP S61134291 A JPS61134291 A JP S61134291A JP 59255970 A JP59255970 A JP 59255970A JP 25597084 A JP25597084 A JP 25597084A JP S61134291 A JPS61134291 A JP S61134291A
- Authority
- JP
- Japan
- Prior art keywords
- recording paper
- cationic group
- pva
- paper
- cationic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Duplication Or Marking (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、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、特に解像度が
高く、高度に耐水性のある記録画像を形成するインクジ
ェット記録用紙に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to an inkjet recording paper, and more particularly to an inkjet recording paper that forms recorded images with high resolution and high water resistance.
Ｂ、従来の技術
インクジェット記録方式は騒音が少いこと、カラー化が
容易であること、高速記録が可能であること等の理由か
ら、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。従来、インクジェット記録方式に使用される
被記録材としては通常の紙が使用されてきた。しかし、
記録の高速化あるいは多色化などインクジェット記録機
の性能向上に伴いインクジェット記録用紙に対してもよ
シ高度な特性が要求されてきている。すなわち第１にイ
ンクの吸収速度が大きいこと、第２にインクドツトの径
が必要以上に大きくならないこと、第３にインクジェッ
ト記録方式に用いられるインクが水溶性であるため記録
画像の耐水性が低いという欠点を改良すること等である
。B. Conventional technology The inkjet recording method is being applied to facsimiles, various printers, etc. because of its low noise, ease of colorization, and high-speed recording. Conventionally, ordinary paper has been used as a recording material used in inkjet recording methods. but,
As the performance of inkjet recording machines improves, such as faster recording and multicolor recording, inkjet recording paper is also required to have more sophisticated properties. First, the absorption speed of the ink is high; second, the diameter of the ink dots must not become larger than necessary; and third, because the ink used in the inkjet recording method is water-soluble, the water resistance of the recorded image is low. This includes improving deficiencies.
これらの要求を満たすため、種々の検討がなされている
が、一般にインク吸収性のよいものはインクドツトが広
が９やすいという傾向にあり、また記録画像の耐水性も
未だ実用レベルの要求に遠くおよばないというのが現状
である。Various studies have been conducted to meet these requirements, but in general, ink dots with good ink absorption tend to spread easily, and the water resistance of recorded images is still far from meeting the requirements for practical use. The current situation is that there is no such thing.
Ｃ１本発明が解決しようとす 問題点
本発明の目的は、前記のような諸要求を満足させ、特に
解像度が高くかつ耐水性にすぐれた記録画像を形成する
インクジェット記録用紙を提供することＫある。C1 Problems to be Solved by the Present Invention An object of the present invention is to provide an inkjet recording paper that satisfies the above-mentioned requirements and forms recorded images with particularly high resolution and excellent water resistance. .
Ｄ１問題点を解決する為の手段
本発明者は上記の問題点を解決すべく鋭意検討の結果、
紙基材中及び／又は塗工層中に、カチオンｔｉ基ｔ−有
するポリビニルアルコール系樹脂（以下ポリビニルアル
コールをＰＶＡと略記する）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が、特に解像度が高く、
かつ高度に耐水性のある記録画像を形成するインクジェ
ット記録用紙であることを見出し、本発明を完成するに
到ったものである。Means for Solving Problem D1 As a result of intensive studies to solve the above problems, the inventor of the present invention found that
An inkjet recording paper is characterized in that it contains a polyvinyl alcohol-based resin (hereinafter polyvinyl alcohol is abbreviated as PVA) having cationic Ti groups (t-) in the paper base material and/or the coating layer, especially in terms of resolution. is high;
The present inventors have discovered that the present invention is an inkjet recording paper that forms recorded images that are highly water resistant, and have completed the present invention.
本発明に用いられるカチオン性基を有するＰＶＡ系樹脂
としてはカチオン性基としてアミンあるいはアンモニウ
ム基（環状、非環状および芳香族を含む）を有している
ものであればよく、具体的には、例えば以下のような一
般式（■）〜（Ｖ）で表わされるカチオン性の単位を有
するＰＶＡ系樹脂が用いられる。The PVA-based resin having a cationic group used in the present invention may be one having an amine or ammonium group (including cyclic, acyclic, and aromatic) as a cationic group, and specifically, For example, PVA-based resins having cationic units represented by the following general formulas (■) to (V) are used.
〔ここでｎは０〜３、ｍは］ −ｙ ｉ Ｏ、Ｒ’ 、
Ｒ” ｓＲ’、Ｒ’、Ｒ８は水素原子またはメチル基、
ｔ、Ｗは低級アルキル基（置換基を含んでもよい）、Ｘ
はアンモニウム窒素と塩を形成する陰性の基、Ａはアミ
ンあるいはアンモニウム窒素原子と、（Ｉ）式中のアミ
ド基の一窒素原子あるいは（Ｉｌｌ）式中の酸素原子と
を連結する基をそれぞれ示＋。〕上述のカチオン性基を
有するＰＶＡ系樹脂の製造法としては、ビニルエステル
と以下のような一般式（ＶＤ〜（Ｘ）、
ρ
Ｒ３
ＣＨ２＝Ｃ−（ＣＨｚ）ｎ ＯＡ Ｎ＜Ｒａおよびこの
四級化物 （■）
Ｒ３−
ＣＨ２＝Ｃ（ＣＨｚ）ｍ−Ｎ＜Ｒ４およびこの四級化物
（ＩＸ）〔ここでｎは０〜３、ｍは１−ｗ １０ 、
Ｒ’ 、Ｒ２、Ｒ６、Ｒ７、♂は水素原子またはメチ
ル基、Ｒ’、Ｒ’は低級アルキル基（置換基を含んでも
よい）、Ｘはアンモニウム窒素と塩を形成する陰性の基
、人はアミンあるいはアンモニウム窒素原子と、（ＶＩ
）式中のアミド基の窒素原子あるいは（■）式中の酸素
原子とを連結する基をそれぞれ示すっ〕で示される重合
性単量体とをラジカル重合開始剤の存在下に共重合させ
、しかる後に該共重合体中のビニルエステル単位を部分
的にあるいは高度にケン化せしめる方法か挙げられる。[Here, n is 0 to 3, m is] -y i O, R',
R''sR', R', R8 are hydrogen atoms or methyl groups,
t, W are lower alkyl groups (may contain substituents), X
is a negative group that forms a salt with ammonium nitrogen, and A is a group that connects an amine or ammonium nitrogen atom with the mononitrogen atom of the amide group in formula (I) or the oxygen atom in formula (Ill), respectively. +. ] As a method for producing the above-mentioned PVA-based resin having a cationic group, vinyl ester and the following general formula (VD~(X), ρ R3 CH2=C-(CHz)n OA N<Ra, and these four (■) R3- CH2=C(CHz)m-N<R4 and its quaternized product (IX) [where n is 0 to 3, m is 1-w 10 ,
R', R2, R6, R7, ♂ are hydrogen atoms or methyl groups, R', R' are lower alkyl groups (which may contain substituents), X is a negative group that forms a salt with ammonium nitrogen, amine or ammonium nitrogen atom and (VI
) is copolymerized with a polymerizable monomer represented by the nitrogen atom of the amide group in the formula or (■) representing the group connecting the oxygen atom in the formula in the presence of a radical polymerization initiator, There is a method in which the vinyl ester units in the copolymer are then partially or highly saponified.
本方法において使用されるビニルエステルとしては、酢
酸ビニル、プロピオン酸ビニル、ギ酸ビニルが挙げられ
るが経済的にみて酢酸ビニルが好ましい。Vinyl esters used in this method include vinyl acetate, vinyl propionate, and vinyl formate, but vinyl acetate is preferred from an economic standpoint.
また、本方法において用いられるカチオン性基を有する
重合性単量体のうち（ＶＩ式で表わされる単量体の具体
例としては、例えばＮ −（ｉ、１−ジメチル−３−ジ
メチルアミノプロピ／Ｌ／）（メタ）アクリルアミド、
Ｎ−（１，１−ジメチル−３−ジメチルアミノブチル）
（メタ）アクリルアミド、Ｎ−（１−メチル−１，３−
ジフェニル−３−ジエチルアミノプロｌｌ：”Ａ／ｌ（
メタ）アクリルアミド、Ｎ−（３−ジメチルアミノプロ
ピ／Ｌ／）（メタ）アクリルアミド、Ｎ−（２−ジエチ
ルアミノプロ／Ｌ／）（メタ）アクリルアミド、Ｎ−（
４−ジメチルアミノブチル）（メタ）アクリルアミド、
およびこれラヲハロゲン化アルキルとシわけ塩化メチル
あるいは塩化エチル、またはジメチル硫酸、ｐ−トルエ
ンスルホン酸メチル等の四級化剤で四級化した単量体が
挙げられる。Furthermore, among the polymerizable monomers having a cationic group used in this method, examples of monomers represented by formula VI include, for example, N-(i, 1-dimethyl-3-dimethylaminopropy/ L/) (meth)acrylamide,
N-(1,1-dimethyl-3-dimethylaminobutyl)
(meth)acrylamide, N-(1-methyl-1,3-
Diphenyl-3-diethylaminoproll:”A/l(
meth)acrylamide, N-(3-dimethylaminopropy/L/)(meth)acrylamide, N-(2-diethylaminopro/L/)(meth)acrylamide, N-(
4-dimethylaminobutyl)(meth)acrylamide,
Examples include monomers obtained by separating these raw alkyl halides with methyl chloride or ethyl chloride, or quaternizing them with a quaternizing agent such as dimethyl sulfuric acid or methyl p-toluenesulfonate.
また（■）式で表わされる単量体の具体例としてハ、例
えば、Ｎ−ビニルイミダゾール、２−メチル−Ｎ−ビニ
ルイミダゾールおよびそれらを上述の四級化剤によって
四級化した単量体が挙げられる。Specific examples of the monomer represented by formula (■) include N-vinylimidazole, 2-methyl-N-vinylimidazole, and monomers obtained by quaternizing these with the above-mentioned quaternizing agent. Can be mentioned.
また（■）式で表わされる単量体の具体例としては、例
えば、ビニ／ｌ／−３−ジメチルアミノプロピルエーテ
ル、ビニ／ｌ／−２−ジメチルアミノエチルエーテル、
ビニＡ／−４−ジメチルアミノブチルエーテル、インプ
ロペニル−３−ジメチルアミノプロピルエーテル、イソ
プロペニル−２−ジメチルアミノエチルエーテル、アリ
フレー３−ジメｆＡ／アミノグロビルエーテル、アリル
−２−ジメチルアミノエチルエーテル、アリル−４−ジ
メチルアミノブチルエーテルおよびそれらを上述の四級
化剤によって四級化した単量体が挙げられる。Specific examples of the monomer represented by formula (■) include vinyl/l/-3-dimethylaminopropyl ether, vinyl/l/-2-dimethylaminoethyl ether,
vinyl A/-4-dimethylaminobutyl ether, impropenyl-3-dimethylaminopropyl ether, isopropenyl-2-dimethylaminoethyl ether, Arifre 3-dimefA/aminoglobil ether, allyl-2-dimethylaminoethyl ether, Examples include allyl-4-dimethylaminobutyl ether and monomers obtained by quaternizing them with the above-mentioned quaternizing agent.
また（ＩＸ）式で表わされる単量体の具体例としてはア
リルジメチルアミン、メタアリルジメチルアミン、３−
ブテンジメチルアミンおよびそれらを上述の四級化剤に
よって四級化した単量体が挙げられる。Specific examples of the monomer represented by formula (IX) include allyldimethylamine, metaallyldimethylamine, 3-
Examples include butene dimethylamine and monomers obtained by quaternizing them with the above-mentioned quaternizing agents.
更に（Ｘ）式で表わされる単量体の具体例としては、例
えば、ジメチルジアリルアンモニウムクロリド、ジエチ
ルジアリルアンモニウムクロリドなどが挙げられろう
上述の（ＶＩ）〜（Ｘ）式で表わされるカチオン性基を
有する単量体において工業的製造の容易性あるいはイン
クジェット記録用紙中に含有せしめた場合の耐水性の高
度性の点で（ＶＩ）、（■）または（■）式で表わされ
る単量体とシわけ（ＶＩ）式または（■）式で表わされ
る単量体が好ましく用いられる。Furthermore, specific examples of the monomer represented by formula (X) include dimethyldiallylammonium chloride, diethyldiallylammonium chloride, etc. Monomers represented by formulas (VI), (■), or (■) are suitable for ease of industrial production or high water resistance when incorporated into inkjet recording paper. A monomer represented by formula (VI) or formula (■) is preferably used.
また上述のカチオン性基を有する単量体とビニルエステ
ルとの共重合を実施する際には、これらの他に他の共重
合性単量体、例えば、エチレン、プロピレン、スチレン
、アルキルビニルエーテル、バーサチック酸ビニル、（
メタ）アクリｌレアミド、（メタ）アクリル酸、無水マ
レイン酸、クロトン酸、イタコン酸、フマル酸等の不飽
和酸およびそのアルキルエステル、アルカリ塩等を少量
併用使用することもできる。In addition, when carrying out copolymerization of the above-mentioned cationic group-containing monomer and vinyl ester, other copolymerizable monomers such as ethylene, propylene, styrene, alkyl vinyl ether, versatic Vinyl acid, (
Unsaturated acids such as meth)acrylic reamide, (meth)acrylic acid, maleic anhydride, crotonic acid, itaconic acid, and fumaric acid, and their alkyl esters and alkali salts can also be used in combination in small amounts.
本発明において用いられるカチオン性基を有するＰＶＡ
系樹脂中のカチオン性基の含有量としてはカチオン性基
を有する単量体単位として０．０１〜１０モル％、好ま
しくは０．０５〜５モル％の範囲から選ばれることが好
ましい。またビニルエステル単位のケン化度としては水
溶性の範囲であればよく、カチオン性基を有する単量体
単位の含有量によっても異なるが通常５０〜】００モル
％、好ましくは６０〜１００モル％の範囲から選ばれる
。更に該変性ＰＶＡの重合度としては特に制限はないが
通常５０〜３０００好ましくは１００〜２５００の範囲
から選ばれる。PVA having a cationic group used in the present invention
The content of cationic groups in the resin system is preferably selected from the range of 0.01 to 10 mol%, preferably 0.05 to 5 mol%, based on monomer units having cationic groups. The degree of saponification of the vinyl ester unit may be within a water-soluble range, and although it varies depending on the content of monomer units having cationic groups, it is usually from 50 to 100 mol%, preferably from 60 to 100 mol%. selected from the range. Further, the degree of polymerization of the modified PVA is not particularly limited, but is usually selected from the range of 50 to 3,000, preferably 100 to 2,500.
本発明においてカチオン性基を有する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、
例えば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シ表面に塗布
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、グレード、エアナイフ、ロール
コータ−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, the method for incorporating the PVA resin having a cationic group into the inkjet recording paper is as follows:
For example, the surface of inkjet recording paper made by a known method is coated or impregnated by spraying or side press, or when producing a known coated paper type inkjet recording paper, it is mixed into the coating paint and graded. , a method of applying with a coating machine such as an air knife or a roll coater, or a method of adding it internally at the time of paper making of inkjet recording paper.
インクシェツト記録用紙中への該カチオン性基含有ＰＶ
Ａ系樹脂の添加量としては通常０．０１〜１０ ｆ／ｌ
Ａ好ましくは０．０５〜５ｙ／イが用いられる。The cationic group-containing PV in the inksheet recording paper
The amount of A-based resin added is usually 0.01 to 10 f/l.
A: Preferably, 0.05 to 5y/i is used.
０．０１ ｆ／ｍ未満の場合には解像度、耐□水性の向
上効果がなく、１０ ｆ／ｌａ、を超える場合にはイン
ク吸収速度が低下する傾向があるため好ましくない。When it is less than 0.01 f/m, there is no effect of improving resolution and water resistance, and when it exceeds 10 f/la, the ink absorption speed tends to decrease, which is not preferable.
上述の如く、本発明において用いられるカチオン性基含
有Ｐ’ＶＡ系樹脂はあらゆるタイプのインクジェット記
録用紙に適用が可能であシ、特にタルク、カオリン、炭
酸カルシウム、非膠質シリカ粉７ｅ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適用すること
によって、解像度が高く、高度に耐水性の記録画像を形
成しうるインクジェット記録用紙を得ることができる。As mentioned above, the cationic group-containing P'VA resin used in the present invention can be applied to all types of inkjet recording paper, especially talc, kaolin, calcium carbonate, non-colloidal silica powder 7e powdered urea-formalin. Recording paper with various fillers such as resin fillers, or recording paper with coating layers of white pigments such as non-colloidal silica powder, acid clay, clay, talc, calcium carbonate, diatomaceous earth, titanium oxide, barium sulfate, etc. By applying this method, it is possible to obtain inkjet recording paper that can form recorded images with high resolution and high water resistance.
尚、カチオン性基含有ＰＶＡ系樹脂をインクジェット記
録用紙中に含有せしめる際、ポリアクリルアミド、デン
プン、カゼイン、アラビアコ゛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性樹脂、合成ゴムラテックス等
の合成樹脂ラテックス、分散螢光染料、ｐＨ調節剤、消
泡剤、潤滑剤、防屑剤、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。When incorporating a cationic group-containing PVA resin into inkjet recording paper, water-soluble resins such as polyacrylamide, starch, casein, arabic comb, carboxymethyl cellulose, methyl cellulose, ordinary PVA, sodium polyacrylate, synthetic rubber, etc. Various additives such as synthetic resin latex such as latex, dispersed fluorescent dye, pH adjuster, antifoaming agent, lubricant, anti-dust agent, and surfactant can also be used in combination.
８０作用及び本発明の効果
本発明のインクジェット記録用紙が、解像度が高くかつ
耐水性の良好な記録画像を形成しうる理由については十
分解明されているわけではないが、次のように推定され
る。80 Actions and Effects of the Present Invention Although the reason why the inkjet recording paper of the present invention is able to form recorded images with high resolution and good water resistance has not been fully elucidated, it is presumed as follows. .
すなわち、インクジェット記録方式において用いられる
水性インク中の染料は一般にアニオン性であり、本発明
の記録用紙中に含有せしめるカチオン性基含有ＰＶＡ系
樹脂はアニオン性化合物と著しく高い反応性を有するた
め、記録用紙にインクが適用されると瞬間的に反応して
、吸収するとともにインクの広がシを抑制し、かつ耐水
性の化学結合体を形成するためであると推定される。That is, the dye in the water-based ink used in the inkjet recording method is generally anionic, and the cationic group-containing PVA resin contained in the recording paper of the present invention has extremely high reactivity with anionic compounds. It is presumed that this is because when ink is applied to paper, it instantly reacts, absorbs it, suppresses the spread of ink, and forms a water-resistant chemical bond.
以下に実施例を挙げて本発明を更に詳しく説明するが、
本発明はこれによって制限されるものではない。なお実
施例中特〈ことわシのないかぎり「％」および「部」は
重量規準を表わす。The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited thereby. In the examples, unless otherwise specified, "%" and "part" represent weight standards.
実施例１
カチオン性基含有ＰＶＡ系樹脂として酢酸ビニルとトリ
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
のものを使用して下記組成に基づき塗工用組成物を作成
した。Example 1 Content of monomer units having a cationic group obtained by saponifying a copolymer of vinyl acetate and trimethyl-3-(1-acrylamidopropyl)ammonium chloride as a cationic group-containing PVA resin is 3 mol%, the degree of saponification of vinyl acetate unit is 98.5 mol%, and the degree of polymerization is 1750.
A coating composition was prepared using the following composition.
非膠質シリカ粉末 １００部カチオン性
基含有ＰＶＡ系樹脂 ２５部水
５００部一方原紙としては
ＪＩＳｐ８１２２に基づくサイズ度が３０秒の一般上質
紙（坪量６ ｓ ｙ／ｄ ）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２０１／ｒＡ、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４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 PVA resin containing cationic group 25 parts Water
500 copies On the other hand, general high-quality paper (basis weight 6 sy/d) with a sizing degree of 30 seconds based on JIS Sp8122 was used as the base paper, and the above coating composition was applied on this base paper in a dry coating amount of 201/rA. , and dried to obtain inkjet recording paper. Color inkjet recording was performed on this recording paper using the following four color inks, and the recording characteristics were evaluated.
イエローインク（組成）
Ｃ，Ｘ、アシッドイエロー２３ ２部ジエチレン
グリコール ３０部水
７０部マゼンタインク（組成）
ｃ、 ｒ、アシッドレッド３２ ２部ジエチレ
ングリコ−７し ３０部水
７０部シアンインク（組
成）
Ｃ，１，ダイレクトブルー８６ ２部ジエチレン
グリコ−／Ｌ／ ３０部水
７０部ブラックインク（
組成）
ＣｏＬ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部記録用紙の記録特性の評価
結果を第１表に示す。Yellow ink (composition) C, X, acid yellow 23 2 parts diethylene glycol 30 parts water
70 parts magenta ink (composition) c, r, acid red 32 2 parts diethylene glycol-7 30 parts water
70 parts Cyan ink (composition) C, 1, Direct Blue 86 2 parts diethylene glycol/L/ 30 parts water
70 copies black ink (
Composition) CoL Direct Black 19 2 parts diethylene glycol 30 parts water
Table 1 shows the evaluation results of the recording characteristics of the 70-copy recording paper.
にじみ度は印字ドツトの直径を実体顕微鏡で測定し、イ
ンク滴径の何倍になったかを示した。謝水性は、被記録
紙を流水中に３時間浸漬し、浸漬後、マクベス濃度計を
用いて測定した光学密度（９Ｄ）を浸漬前の！Ｄ値と比
較して示した。The degree of bleeding was determined by measuring the diameter of the printed dot using a stereomicroscope and indicating how many times larger it was than the diameter of the ink droplet. Water resistance is determined by immersing the recording paper in running water for 3 hours, and measuring the optical density (9D) using a Macbeth densitometer after immersion. It is shown in comparison with the D value.
実施例２〜４
実施例１で用いられたカチオン変性ｆｆＡ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。評価結果を合せて第１表に示す。Examples 2 to 4 The same procedure as in Example 1 was carried out except that the following modified PVA was used in place of the cation-modified ffA used in Example 1. The evaluation results are also shown in Table 1.
実施例２で用いたカチオン性基含有ＰＶＡ系樹脂二酢酸
ビニルとトリメチル−３−（１−メタアクリルアミドプ
ロピ／Ｌ／）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５５０のＰＶＡ系樹脂。A monomer having a cationic group obtained by saponifying the copolymer of cationic group-containing PVA resin vinyl diacetate and trimethyl-3-(1-methacrylamidopropyl/L/)ammonium chloride used in Example 2. A PVA resin with a content of mer units of 3 mol%, a degree of saponification of vinyl acetate units of 98.5 mol%, and a degree of polymerization of 550.
実施例３で用いたカチオン性基含有ＰｖＡ系樹脂：酢酸
ビニルとトリメチル−３−（１−アクリｌレアミド−１
，１−ジメチルプロピル）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０．２モｌし％で酢酸ビニル単位のケ
ン化度９８．５モル％、重合度２０００のＰＶＡ系樹脂
。Cationic group-containing PvA resin used in Example 3: Vinyl acetate and trimethyl-3-(1-acrylic reamide-1)
, 1-dimethylpropyl) ammonium chloride, and the content of the monomer unit having a cationic group obtained by saponifying the copolymer with cationic group is 0.2 mol%, and the degree of saponification of the vinyl acetate unit is 98.5. PVA resin with mol% and degree of polymerization of 2000.
実施例４で用いたカチオン性基含有ＰＶＡ系樹脂：酢酸
ビニルとトリメチル−２−アリルオキシエチルアンモニ
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４モル％で酢酸ビ
ニル単位のケン化度８８モル％、重合度５５０のＰＶＡ
系樹脂。Cationic group-containing PVA resin used in Example 4: Content of monomer units having cationic groups obtained by saponifying a copolymer of vinyl acetate and trimethyl-2-allyloxyethylammonium chloride. PVA with a degree of saponification of vinyl acetate units of 88 mol% and a degree of polymerization of 550 at 4 mol%
system resin.
実施例５
実施例１で用いられたカチオン変性ＰＶＡ ２５部に替
えてカチオン変性基含有ＰＶＡ系樹脂として酢酸ビニル
とＮ−ビニル−２，３−ジメチルイミダゾリニウムクロ
リドとの共重合体をケン化して得られるイミダゾリニウ
ム基の含有量が４モル％で酢酸ビニル単位のケン化度９
８．５（ニル％、重合度］７５０のＰＶＡ系樹脂の２０
部と通常のＰＶＡ（ケン化度９８．５モル％、重合度１
７５０ ）２０部とを併用して用いる以外は実施例１と
同様に行った。結果を合せて第１表に示すっ
実施例６
実施例１で用いたカチオン性基含有ＰＶＡ系樹脂の６％
水溶液をサイズプレスを用いてサイズ度１０秒の一般紙
（坪量６５ ｆ／ａ ）に乾燥重量として２ ｆ／ｒＡ
となるように塗布し記録用紙を得た。この記録用紙を実
施例】と同様にして評価した。結果を合せて第１表に示
す。Example 5 In place of 25 parts of the cation-modified PVA used in Example 1, a copolymer of vinyl acetate and N-vinyl-2,3-dimethylimidazolinium chloride was saponified as a cation-modified group-containing PVA resin. The content of imidazolinium group obtained by
8.5 (Nil%, degree of polymerization) 20 of PVA resin of 750
part and normal PVA (saponification degree 98.5 mol%, polymerization degree 1
Example 1 was carried out in the same manner as in Example 1 except that 20 parts of 750) were used in combination. The results are shown in Table 1. Example 6 6% of the cationic group-containing PVA resin used in Example 1
The aqueous solution was applied to general paper (basis weight 65 f/a) with a size degree of 10 seconds using a size press to give a dry weight of 2 f/rA.
A recording paper was obtained by applying the following coating. This recording paper was evaluated in the same manner as in Example. The results are shown in Table 1.
実施例７〜８
実施例６で用いたカチオン性基含有ＰＶＡ系樹脂にかえ
て以下のＰＶＡ系樹脂を用いる以外は実施例６と同様に
行った。結果を合せて第１表に示す。Examples 7-8 The same procedure as in Example 6 was carried out except that the following PVA-based resin was used in place of the cationic group-containing PVA-based resin used in Example 6. The results are shown in Table 1.
実施例７で用いたカチオン性基含有ｆｆＡ系樹脂：実施
例３で用いたカチオン性基含有ＰＶＡ系樹脂。Cationic group-containing ffA resin used in Example 7: Cationic group-containing PVA resin used in Example 3.
実施例８で用いたカチオン性基含有ＰＶＡ系樹脂：実施
例５で用いたカチオン性基含有ｆｆＡ系樹脂。Cationic group-containing PVA resin used in Example 8: Cationic group-containing ffA resin used in Example 5.
比較例１
実施例１においてεいられたカチオン性基含有ＰＶＡ系
樹脂にかえてＰＶＡ （ケン化度９８．５、重合度１７
５０ ）を用いる以外は実施例】と同様に行った。Comparative Example 1 PVA (saponification degree 98.5, polymerization degree 17) was used instead of the cationic group-containing PVA resin used in Example 1.
Example 50) was used in the same manner as in Example].
結果を合せて第１表に示す。The results are shown in Table 1.
比較例２
実施例１で用いられたカチオン変性ＰＶＡ ２５部と水
５００部に替えて該変性ＰＶＡ１５０部と水１０００部
を用いる以外は実施例１と同様に行った。（この場合、
カチオン変性ＰＶＡ０紙中への添加量は１２ ｆ／ａと
なる。）得られたインクジェット記録用紙はインク吸収
速度が低いものであった。Comparative Example 2 The same procedure as in Example 1 was carried out except that 150 parts of the modified PVA and 1000 parts of water were used instead of 25 parts of the cationically modified PVA and 500 parts of water used in Example 1. (in this case,
The amount added to the cation-modified PVA0 paper is 12 f/a. ) The obtained inkjet recording paper had a low ink absorption speed.
比較例３
実施例６において用いられた一般紙をそのまま用いる以
外は実施例１と同様に行った。記録特性の評価結果を合
せて第１表に示す。Comparative Example 3 The same procedure as in Example 1 was carried out except that the general paper used in Example 6 was used as it was. The evaluation results of recording characteristics are also shown in Table 1.
Claims (2)
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
徴とするインクジエツト記録用紙。(1) An inkjet recording paper characterized by containing a polyvinyl alcohol resin having a cationic group in the paper and/or the coating layer.
脂が、酢酸ビニルと一般式 ▲数式、化学式、表等があります▼ 〔ここでＲ＾１、Ｒ＾２は水素原子またはメチル基、Ｂ
は▲数式、化学式、表等があります▼または▲数式、化
学式、表等があります▼、Ｘ＾−、Ｒ＾３、Ｒ＾４、Ｒ
＾５は低級アルキル基（置換基を含んでもよい）、Ｘは
アンモニウム窒素と塩を形成する陰性の基、ＡはＢ中の
窒素原子と上式中のアミド基の窒素原子を連結する基を
示す。〕 で示されるカチオン性基を有する単量体との共重合体の
ケン化物である特許請求の範囲第１項に記載のインクジ
エツト記録用紙。(2) Polyvinyl alcohol resin having a cationic group has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [Here, R^1 and R^2 are hydrogen atoms or methyl groups, B
▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼, X^-, R^3, R^4, R
^5 is a lower alkyl group (which may contain a substituent), X is a negative group that forms a salt with ammonium nitrogen, and A is a group that connects the nitrogen atom in B with the nitrogen atom of the amide group in the above formula. show. ] The inkjet recording paper according to claim 1, which is a saponified product of a copolymer with a monomer having a cationic group represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59255970A JPS61134291A (en) | 1984-12-03 | 1984-12-03 | Ink jet recording paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59255970A JPS61134291A (en) | 1984-12-03 | 1984-12-03 | Ink jet recording paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61134291A true JPS61134291A (en) | 1986-06-21 |
| JPH0567432B2 JPH0567432B2 (en) | 1993-09-24 |
Family
ID=17286100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59255970A Granted JPS61134291A (en) | 1984-12-03 | 1984-12-03 | Ink jet recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61134291A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162275A (en) * | 1986-12-26 | 1988-07-05 | Jujo Paper Co Ltd | Sheet for ink jet recording |
| JPH09207425A (en) * | 1996-02-02 | 1997-08-12 | Kuraray Co Ltd | Material to be recorded |
| US6348256B1 (en) | 1998-09-29 | 2002-02-19 | Celanese International Corporation | Ink jet paper coatings containing amine functional monomer grafted poly(vinyl alcohol) |
| US6485609B1 (en) | 2001-03-08 | 2002-11-26 | Celanese International Corporation | Ink jet printing paper incorporating amine functional poly(vinyl alcohol) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1193092A (en) * | 1997-09-11 | 1999-04-06 | Hymo Corp | Surface coating agent for paper |
| US6455134B1 (en) | 1999-08-26 | 2002-09-24 | Air Products Polymers, L.P. | Ink jet media comprising a coating containing amine functional emulsion polymers |
| US7059715B2 (en) | 2002-09-13 | 2006-06-13 | Fuji Photo Film Co., Ltd. | Sheet for ink jet recording, ink for ink jet recording, manufacturing method of ink for ink jet recording, ink set for ink jet recording, and ink jet recording method |
| WO2005030888A1 (en) | 2003-09-29 | 2005-04-07 | Fuji Photo Film Co., Ltd. | Ink for inkjet printing, ink set for inkjet printing, inkjet recording material and producing method for inkjet recording material, and inkjet recording method. |
| EP1571181A3 (en) | 2004-02-24 | 2008-08-13 | FUJIFILM Corporation | Inorganic fine particle dispersion and manufacturing method thereof as well as image-recording material |
| EP1609613B1 (en) | 2004-06-22 | 2007-07-25 | FUJIFILM Corporation | Image recording medium manufacturing method |
| JP5185594B2 (en) | 2007-10-31 | 2013-04-17 | 富士フイルム株式会社 | Ink jet recording medium and ink jet recording method using the ink jet recording medium |
| JP2009107254A (en) | 2007-10-31 | 2009-05-21 | Fujifilm Corp | Inkjet recording medium and inkjet recording method using the same |
| JP2010253925A (en) | 2009-03-31 | 2010-11-11 | Fujifilm Corp | Manufacturing method for recording medium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57191084A (en) * | 1981-05-22 | 1982-11-24 | Canon Inc | Recording medium for ink jet and recording method using thereof |
| JPS5824492A (en) * | 1981-08-06 | 1983-02-14 | Canon Inc | Recording method |
-
1984
- 1984-12-03 JP JP59255970A patent/JPS61134291A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57191084A (en) * | 1981-05-22 | 1982-11-24 | Canon Inc | Recording medium for ink jet and recording method using thereof |
| JPS5824492A (en) * | 1981-08-06 | 1983-02-14 | Canon Inc | Recording method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162275A (en) * | 1986-12-26 | 1988-07-05 | Jujo Paper Co Ltd | Sheet for ink jet recording |
| JPH09207425A (en) * | 1996-02-02 | 1997-08-12 | Kuraray Co Ltd | Material to be recorded |
| US6348256B1 (en) | 1998-09-29 | 2002-02-19 | Celanese International Corporation | Ink jet paper coatings containing amine functional monomer grafted poly(vinyl alcohol) |
| US6485609B1 (en) | 2001-03-08 | 2002-11-26 | Celanese International Corporation | Ink jet printing paper incorporating amine functional poly(vinyl alcohol) |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0567432B2 (en) | 1993-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01206088A (en) | Ink jet recording paper | |
| JPS63115780A (en) | Ink jet recording sheet | |
| US4877688A (en) | Ink-jet recording sheet | |
| JPS61134291A (en) | Ink jet recording paper | |
| JPS61134290A (en) | Ink jet recording paper | |
| IL140754A (en) | Ink-receptive coatings and recording medium prepared therefrom | |
| JP2604367B2 (en) | Ink jet recording sheet with excellent water resistance | |
| JPS61163886A (en) | Ink jet recording medium | |
| JPS63176173A (en) | Sheet for ink jet recording | |
| JP2661120B2 (en) | Recording material | |
| JPS63183873A (en) | Ink jet recording sheet superior in water resistance | |
| JP3053231B2 (en) | Inkjet recording sheet | |
| JPS61189985A (en) | Ink jet recording paper having strong gloss | |
| JP2645299B2 (en) | Recording material | |
| JPH09207425A (en) | Material to be recorded | |
| US6238804B1 (en) | Ink jet recording medium having a coating containing cellulose ethers and optical brighteners | |
| JPS6189082A (en) | Paper for ink jet recording | |
| KR20150115801A (en) | Cationic emulsion having polymer core-shell structure, aqueous ink, and recording medium | |
| JP3892220B2 (en) | Inkjet recording medium | |
| JPH08324105A (en) | Ink jet recording paper | |
| US6174611B1 (en) | Recording medium and ink jet recording method | |
| JPS62174184A (en) | Ink jet recording paper | |
| JPS6198580A (en) | Paper for color printer | |
| JPS63162275A (en) | Sheet for ink jet recording | |
| JPH06155892A (en) | Ink-jet recording paper having intense gloss |