JP3552986B2 - Recording material for ink jet recording and waterproofing agent for ink jet recording - Google Patents

Description

【００１０】
（上式中、Ｒ^１ はそれぞれ独立に炭素数１〜４のアルキルもしくはヒドロキシアルキル基又は炭素数２〜４のアルケニル基を表し、Ｙは炭素数２〜１０のアルキレン基を表し、Ｚは炭素数２〜１０のヘテロ原子含有のアルキレン基を表し、Ａ⁻ はアニオンを表し、ｎは３〜５００の整数を表す）
本発明は、また、上記一般式（１）で表される第四級アンモニウム塩化合物を含有するインクジェット記録用耐水化剤を提供する。
【００１１】
【発明の実施の形態】
本発明で用いられる一般式（１）で表される第四級アンモニウム塩化合物は、例えば、下記一般式（２）
【００１２】
【化４】

【００１３】
（上式中、Ｒ^１ はそれぞれ独立に炭素数１〜４のアルキルもしくはヒドロキシアルキル基又は炭素数２〜４のアルケニル基を表し、Ｙは炭素数２〜１０のアルキレン基を表す）
で表されるアルキレンジアミン化合物と、下記一般式（３）
【００１４】
【化５】

【００１５】
（上式中、Ｚは炭素数２〜１０のヘテロ原子含有のアルキレン基を表し、Ｘはハロゲン原子を表す）
で表されるジハロアルキレン化合物とを、６０〜１５０℃で数時間〜数十時間重合させることによって得られる。
ここで、上記一般式（２）で表されるアルキレンジアミン化合物としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルブチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサメチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルデカメチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラエチルエチレンジアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）−Ｎ’，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）−Ｎ’，Ｎ’−ジエチルエチレンジアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）−Ｎ’，Ｎ’−ジメチルプロピレンジアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）−Ｎ’，Ｎ’−ジエチルプロピレンジアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）−Ｎ’，Ｎ’−ジブチルプロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシエチル）エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシエチル）プロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラアリルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラアリルブチレンジアミンなどが挙げられる。また、一般式（３）で表されるジハロアルキレン化合物としては、例えば、ジ（クロロメチル）エーテル、ビス（２−クロロエチル）エーテル、ビス（３−クロロプロピル）エーテル、ジ（クロロジメチル）ホルマール、ビス（２−クロロエチル）ホルマール、ビス（２−クロロエトキシ）エタン、ビス（４−クロロブチル）エーテル、ビス（２−クロロエチル）スルフィド及びこれらの化合物のの塩素原子が臭素原子やヨウ素原子に置き換わった化合物などが挙げられる。
【００１６】
本発明に有用な上記一般式（１）で表される第四級アンモニウム塩化合物において、Ｙは炭素数２〜１０のアルキレン基であり、その具体例としてはエチレン基、プロピレン基、ブチレン基、ヘキサメチレン基、デカメチレン基などが挙げられる。また、Ｚは炭素数２〜１０のヘテロ原子含有のアルキレン基であり、その具体例としては２−オキサプロピレン基、３−オキサペンチレン基、４−オキサヘプチレン基、２，４−ジオキサペンチレン基、３，５−ジオキサヘプチレン基、３−チオペンチレン基、３，６−ジオキサオクチレン基、５−オキサノニレン基などが挙げられる。
【００１７】
さらに、Ａ⁻ としては、第四級アンモニウム塩を形成するアニオンであれば特に制限はなく、例えば、塩素イオン、臭素イオン、ヨウ素イオン、もしくはこれらのハロゲンイオンとのイオン交換によって得られる、硫酸イオン、硝酸イオン、リン酸イオン、炭酸イオン、又はギ酸、酢酸、プロピオン酸、グルコン酸、乳酸、フマル酸、アジピン酸などの酸から派生する一価又は多価のカルボン酸イオンなどが挙げられる。これらのアニオンのうちでは、塩素イオンが好ましい。
【００１８】
よって、一般式（１）で表される第四級アンモニウム塩化合物としては、例えば、ポリ［オキシエチレン（ジメチルイミニオ）エチレン（ジメチルイミニオ）エチレンジクロライド］、ポリ［オキシエチレン（ジメチルイミニオ）プロピレン（ジメチルイミニオ）エチレンジクロライド］、ポリ［オキシメチレンオキシエチレン（ジメチルイミニオ）エチレン（ジメチルイミニオ）エチレンジクロライド］、ポリ［オキシメチレンオキシエチレン（ジメチルイミニオ）プロピレン（ジメチルイミニオ）エチレンジクロライド］などを挙げることができる。
【００１９】
一般式（１）において、ｎはこの単位の繰り返し数を意味するが、本発明においてはｎは３〜５００の範囲である。この繰り返し数が３未満の場合は、インクの滲みの防止性や水に対する流れ出しの防止が十分でなくなる。また、ｎが５００を超えると、この第四級アンモニウム塩化合物のポリマー度が大きくなり、取り扱いが難しくなる。さらに詳しく述べると、一般式（１）で表される第四級アンモニウム塩化合物の重量平均分子量は、７００〜２０００００であるのが好ましく、２０００〜５００００であるのが特に好ましい。
【００２０】
本発明の被記録材の原材料としては、紙材、繊維材及び樹脂フィルムが挙げられ、紙材としては、パルプからなる紙、パルプにポリエステル、ナイロン、アクリルなどの合成繊維が配合された紙、及びポリエステル、ポリプロピレン、ポリスチレン、ポリ塩化ビニルなどのベースフィルムの上に多数の微細孔を有するポリマーを積層した構造の合成紙などが挙げられる。これらの紙材は、インクジェット記録用被記録材として好適に用いられる。また、繊維材としては、ポリエステル、ナイロン、アクリル、ポリウレタンなどの合成繊維、ウール、絹、綿、麻などの天然繊維、アセテート、スフ、レーヨンなどの半合成繊維、これらの繊維を複合した繊維などからなる織物及び不織布などが挙げられる。また、熱可塑性樹脂などからなる不織布であってもよい。さらに、樹脂フィルムとしては、ポリエステルフィルム、ポリ塩化ビニルフィルム、ポリオレフィンフィルムなどが挙げられる。これらのフィルムには必要に応じて表面処理がされていてもよい。
【００２１】
本発明の被記録材を製造する方法としては、特に制限はなく、従来より行われている製造方法が好ましく使用できる。被記録材原材料がパルプからなる紙、又はパルプに合成繊維が配合されている紙である場合の製造方法としては、例えば、パルプ繊維、又はパルプ繊維と合成繊維との配合物の抄紙工程で、パルプスラリー中に一般式（１）で表される第四級アンモニウム塩化合物又はその溶液を添加する方法、もしくはこれらの紙材を抄紙した後に、一般式（１）で表される第四級アンモニウム塩化合物の溶液をコーティング又はスプレー処理する方法が挙げられる。被記録材原材料が合成紙、繊維材又は樹脂フィルムである場合の製造方法として、例えば、一般式（１）で表される第四級アンモニウム塩化合物の溶液をコーティング又はスプレー処理する方法が挙げられる。
【００２２】
被記録材原材料に対する一般式（１）の第四級アンモニウム塩化合物の付与量は、被記録材原材料１００重量部に対して、０．０１〜１０重量部の範囲であるのが好ましい。このとき、第四級アンモニウム塩化合物を被記録材原材料の表面に付着させてもよいし、内部にしみ込ませて被記録材全体に一様に分布させてもよい。第四級アンモニウム塩化合物の含有量が被記録材原材料１００重量部に対して０．０１重量部未満の場合には、水に対するインクの流れ出しや滲みを抑えるのに十分でないことがあり、１０重量部を超える場合には、被記録材の風合いが、第四級アンモニウム塩を含有しない時に比べて大きく変化してしまうことがある。
【００２３】
本発明においては、印字の際にインクが滲まず、印字したものが水で流れ出ないようにするためには、被記録材原材料の表面に上記の第四級アンモニウム塩化合物を含有させることが特に好ましい。このとき、被記録材の表面１ｍ^２ 当たり第四級アンモニウム塩化合物を０．０１〜１０ｇ含有させるのが好ましく、０．０１ｇ未満の場合には、水に対するインクの流れ出し防止や滲みを抑えるのに十分でないことがあり、１０ｇを超える場合には、被記録材の風合いが、第四級アンモニウム塩化合物を含有しない時に比べて大きく変化してしまうことがある。上記第四級アンモニウム塩化合物を被記録材原材料の表面に含有させる方法としては、コーティング法やスプレー法が好ましい。
【００２４】
本発明の被記録材には、必要に応じて、本発明の効果を損なわない限り、さらに他の成分を含有させてもよい。そのような成分としては、例えば、従来より使用されているバインダー、無機顔料や有機顔料が挙げられる。バインダーとしては、酸化デンプン、ポリビニルアルコールなどが挙げられ、無機顔料としては、軟質炭酸カルシウム、重質炭酸カルシウム、カオリン（ 白土） 、タルク、硫酸カルシウム、硫酸バリウム、酸化チタン、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、合成シリカ、水酸化アルミニウム、アルミナなどが挙げられ、有機顔料としては、スチレン系プラスチックピグメント、アクリル系プラスチックピグメント、マイクロカプセル化顔料、炭素樹脂顔料などが挙げられる。
【００２５】
【実施例】
以下、実施例を挙げて本発明をさらに説明するが、本発明はこれらの実施例により何ら限定されるものではない。
第四級アンモニウム塩化合物の重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）［ＨＬＣ−８１２０ＧＰＣ：東ソー（株）製］を用い、ポリオキシエチレングリコールに換算した重量平均分子量を測定した。なお、測定の溶離液には、酢酸緩衝液（ｐＨ４．７）を用いた。
【００２６】
実施例１
水５０ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン２５ｇ及びビス（２−クロロエチル）エーテル２８ｇを反応容器に仕込み、６０℃で７２時間反応させた後、水２８ｇを加えて、第四級アンモニウム塩化合物の濃度を４０重量％に調整した。得られたポリ［オキシエチレン（ジメチルイミニオ）プロピレン（ジメチルイミニオ）エチレンジクロライド］の重量平均分子量は７５００であり、一般式（１）におけるｎの値は２７であった。
【００２７】
実施例２
水５０ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン２５ｇ及びビス（２−クロロエチル）エーテル２８ｇを反応容器に仕込み、９５℃で３０時間反応させた後、水２８ｇを加えて、第四級アンモニウム塩化合物の濃度を４０重量％に調整した。得られたポリ［オキシエチレン（ジメチルイミニオ）プロピレン（ジメチルイミニオ）エチレンジクロライド］の重量平均分子量は３２０００であり、一般式（１）におけるｎの値は１１７であった。
【００２８】
実施例３
水５０ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサメチレンジアミン２５ｇ及びビス（２−クロロエチル）エーテル２１ｇを反応容器に仕込み、１００℃で４８時間反応させた後、水１９ｇを加えて、第四級アンモニウム塩化合物の濃度を４０重量％に調整した。得られたポリ［オキシエチレン（ジメチルイミニオ）ヘキサメチレン（ジメチルイミニオ）エチレンジクロライド］の重量平均分子量は３５０００であり、一般式（１）におけるｎの値は１１１であった。
【００２９】
実施例４
水５０ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン２３ｇ及び８３重量％のビス（２−クロロエチル）ホルマール３７ｇを反応容器に仕込み、１０５℃で２０時間反応させた後、未反応のビス（２−クロロエチル）ホルマールを分層除去し、水を２２ｇ加えて、第四級アンモニウム塩化合物の濃度を４０重量％に調整した。得られたポリ［オキシメチレンオキシエチレン（ジメチルイミニオ）プロピレン（ジメチルイミニオ）エチレンジクロライド］の重量平均分子量は１３０００であり、一般式（１）におけるｎの値は４３であった。
【００３０】
比較例１
ポリエチレンイミン（重量平均分子量１，２００）の４０重量％溶液。
評価方法
被記録材としての紙、繊維又はポリエステルフィルムについて、以下の方法で評価した。
【００３１】
１．耐水性
エプソン製（ＭＪ−７００Ｖ２Ｃ）インクジェットプリンターで、黒色（ＢＬＡＣＫ）、シアン（ＣＹＡＮ）、マゼンタ（ＭＡＧＥＮＴＡ）、黄色（ＹＥＬＬＯＷ）の各単色をベタ印刷したインクジェット記録材を１時間放置した後、流水に５分間浸漬し、印字部の変化を目視観察し、以下の基準で評価した。
【００３２】
○：印字部分が水で流されたり、滲んだりしない
△：印字部分がやや滲む
×：印字部分が、明らかに水で流され、滲む
２．インク滲み性
エプソン製（ＭＪ−７００Ｖ２Ｃ）インクジェットプリンターで黒色単色をドット印字したインクジェット記録材について、ルーペ（倍率５０倍）でドット部分を目視観察し、以下の基準で評価した。
【００３３】
○：滲み無し
△：やや滲み有り
×：滲み有り
被記録紙
実施例１で得られた第四級アンモニウム塩化合物の２重量％（固形分）水溶液を、バーコーターにて上質紙に塗工し、乾燥後の塗工量が０．５ｇ／ｍ^２ である被記録材を作成した。得られた被記録材を用い、耐水性及びインク滲み性の評価を行った。その結果を表１に示す。
【００３４】
上記と同様の方法により、実施例２〜４及び比較例１の化合物を用いて得られた被記録材についても、耐水性及びインク滲み性の評価を行った。結果を表１に併せて示す。
【００３５】
【表１】

【００３６】
被記録繊維
ポリエステルポンジ布を実施例１の第四級アンモニウム塩化合物の３重量％（固形分）水溶液の処理液でパディング処理（ピックアップ８０％）した後、１０５℃で３分間乾燥して被記録材を作成した。得られた被記録材を用い、耐水性及びインク滲み性の評価を行った。結果を表２に示す。
【００３７】
上記と同様にして、実施例２〜４及び比較例１の化合物についても評価を行った。結果を併せて表２に示す。
【００３８】
【表２】

【００３９】
被記録フィルム
実施例１の第四級アンモニウム塩化合物の２重量％（固形分）水溶液とフィルム用アンカー剤のネオステッカー７００（日華化学（株）製）２重量％との混合液を、バーコーターにてポリエステルフィルムに塗工した。これにより乾燥後の塗工量が第四級アンモニウム塩化合物で０．５ｇ／ｍ^２ である被記録材が得られた。得られた被記録材を用い、耐水性及びインク滲み性の評価を行った。結果を表３に示す。
【００４０】
上記と同様にして、実施例２〜４及び比較例１の化合物についても評価を行った。結果を併せて表３に示す。
【００４１】
【表３】

【００４２】
【発明の効果】
本発明によれば、被記録材にインクが付着したとき（印字したとき）にインクの滲みがなく、またインク付着後（印字後）も水によるインクの流れ出しや滲みのない被記録材を提供することが可能となる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a recording material containing a quaternary ammonium salt compound, particularly to a recording material used in inkjet recording and a waterproofing agent for inkjet recording.
[0002]
[Prior art]
2. Description of the Related Art In recent years, personal computers have become widespread not only in companies but also in ordinary households, and with this, information has been increasingly printed on printers. In particular, recently, the performance of personal computers has been improved, and image information including a large amount of information can be easily handled, and printing of images in full color has been increasing.
[0003]
Examples of the recording method of this printing include ink jet recording, melt heat transfer recording, sublimation transfer recording, direct thermal recording, and the like. In any of the recording methods, the recording material has a high print density and excellent color development. It is required to have such characteristics as being printed, not bleeding at the time of printing, and that the printed matter does not flow or bleed with water. Above all, in ink jet recording in which recording is performed by adhering minute droplets of ink to a recording material such as paper, the ink does not bleed when printed on the recording material, and the recording material wets with water after printing. Even in such a case, it is particularly important that the ink does not flow or bleed.
[0004]
In order to satisfy the various requirements described above, attempts have been made to incorporate various compounds into the recording material. For example, polyethyleneimine and polyvinyl pyridine disclosed in JP-A-56-89992 are disclosed. Compounds such as quaternaries, condensates of polyalkylenepolyamines and dicyandiamide disclosed in JP-A-60-49990, and reaction products of secondary amines and epihalohydrins disclosed in JP-A-6-92012. The use of is being considered.
[0005]
However, in the above-mentioned various print recording methods, there is no recording material that satisfies all the requirements, and in particular, in the case of ink jet recording, with the above-described compounds, the problem of ink bleeding at the time of printing, At present, it has not been possible to solve the problems of ink flowing out and bleeding from the recording material due to water.
[0006]
[Problems to be solved by the invention]
The present invention is directed to a recording material having improved water resistance during printing and after printing, and particularly to a recording material in which ink does not bleed during printing by an ink jet recording method and ink does not flow or bleed into water even after printing. The object of the present invention is to provide a recording material and a waterproofing agent for inkjet recording.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on the above problems, and as a result, a recording material containing a quaternary ammonium salt compound having a hetero atom-containing alkylene group was printed without bleeding during printing. Was found to be useful as a recording material for ink jet recording, and the present invention was completed based on this finding.
[0008]
That is, the present invention provides a recording material for inkjet recording containing a quaternary ammonium salt compound represented by the following general formula (1).
[0009]
Embedded image

[0010]
(In the above formula, R ¹ each independently represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, Y represents an alkylene group having 2 to 10 carbon atoms, and Z represents Represents a heteroatom-containing alkylene group of the number 2 to 10, A ⁻ represents an anion, and n represents an integer of 3 to 500)
The present invention also provides a waterproofing agent for inkjet recording containing a quaternary ammonium salt compound represented by the general formula (1).
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The quaternary ammonium salt compound represented by the general formula (1) used in the present invention is, for example, a compound represented by the following general formula (2)
[0012]
Embedded image

[0013]
(In the above formula, R ¹ each independently represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and Y represents an alkylene group having 2 to 10 carbon atoms.)
An alkylenediamine compound represented by the following general formula (3)
[0014]
Embedded image

[0015]
(In the above formula, Z represents a heteroatom-containing alkylene group having 2 to 10 carbon atoms, and X represents a halogen atom.)
Is obtained by polymerizing the dihaloalkylene compound represented by the formula at 60 to 150 ° C. for several hours to several tens of hours.
Here, examples of the alkylenediamine compound represented by the general formula (2) include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ', N'-tetramethylbutylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N ', N'-tetramethyldecamethylenediamine, N, N , N ', N'-tetraethylethylenediamine, N, N-di (2-hydroxyethyl) -N', N'-dimethylethylenediamine, N, N-di (2-hydroxyethyl) -N ', N'-diethyl Ethylenediamine, N, N-di (2-hydroxyethyl) -N ′, N′-dimethylpropylenediamine, N, N-di (2-hydroxyethyl) -N ′, N′-diethylpropylenediamine, -Di (2-hydroxyethyl) -N ', N'-dibutylpropylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ', N'-tetrakis ( 2-hydroxyethyl) propylenediamine, N, N, N ', N'-tetraallylethylenediamine, N, N, N', N'-tetraallylbutylenediamine and the like. Examples of the dihaloalkylene compound represented by the general formula (3) include di (chloromethyl) ether, bis (2-chloroethyl) ether, bis (3-chloropropyl) ether, and di (chlorodimethyl) formal , Bis (2-chloroethyl) formal, bis (2-chloroethoxy) ethane, bis (4-chlorobutyl) ether, bis (2-chloroethyl) sulfide and the chlorine atom of these compounds have been replaced by bromine and iodine atoms And the like.
[0016]
In the quaternary ammonium salt compound represented by the general formula (1) useful in the present invention, Y is an alkylene group having 2 to 10 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, a butylene group, Examples include a hexamethylene group and a decamethylene group. Z is a heteroatom-containing alkylene group having 2 to 10 carbon atoms, and specific examples thereof include a 2-oxapropylene group, a 3-oxapentylene group, a 4-oxaheptylene group, and a 2,4-dioxapentylene group. Groups, 3,5-dioxaheptylene group, 3-thiopentylene group, 3,6-dioxaoctylene group, 5-oxanonylene group, and the like.
[0017]
Furthermore, A ⁻ is not particularly limited as long as it is an anion that forms a quaternary ammonium salt. For example, a sulfate ion obtained by ion exchange with a chloride ion, a bromine ion, an iodine ion, or a halogen ion thereof. And monovalent or polyvalent carboxylic acid ions derived from acids such as formic acid, acetic acid, propionic acid, gluconic acid, lactic acid, fumaric acid and adipic acid. Among these anions, chloride ions are preferred.
[0018]
Therefore, as the quaternary ammonium salt compound represented by the general formula (1), for example, poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride], poly [oxyethylene (dimethyliminio) Propylene (dimethyliminio) ethylene dichloride], poly [oxymethyleneoxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride], poly [oxymethyleneoxyethylene (dimethyliminio) propylene (dimethyliminio) ethylene dichloride ] And the like.
[0019]
In the general formula (1), n means the number of repetitions of this unit, but in the present invention, n ranges from 3 to 500. If the number of repetitions is less than 3, the prevention of ink bleeding and the prevention of flow out of water will not be sufficient. If n exceeds 500, the degree of polymerization of the quaternary ammonium salt compound increases, and handling becomes difficult. More specifically, the weight average molecular weight of the quaternary ammonium salt compound represented by the general formula (1) is preferably from 700 to 200,000, and particularly preferably from 2,000 to 50,000.
[0020]
Raw materials of the recording material of the present invention include paper materials, fiber materials and resin films, and as the paper materials, paper made of pulp, paper mixed with synthetic fibers such as polyester, nylon, and acryl, And synthetic paper having a structure in which a polymer having a large number of micropores is laminated on a base film such as polyester, polypropylene, polystyrene, or polyvinyl chloride. These paper materials are suitably used as a recording material for inkjet recording. Examples of the fiber material include synthetic fibers such as polyester, nylon, acrylic, and polyurethane; natural fibers such as wool, silk, cotton, and hemp; semi-synthetic fibers such as acetate, soup, and rayon; and fibers obtained by combining these fibers. And woven fabrics and non-woven fabrics. Further, a non-woven fabric made of a thermoplastic resin or the like may be used. Further, examples of the resin film include a polyester film, a polyvinyl chloride film, and a polyolefin film. These films may be subjected to a surface treatment as necessary.
[0021]
The method for manufacturing the recording material of the present invention is not particularly limited, and a conventionally used manufacturing method can be preferably used. As a manufacturing method when the recording material raw material is paper made of pulp, or paper in which synthetic fibers are blended into pulp, for example, in the papermaking process of pulp fibers, or a blend of pulp fibers and synthetic fibers, A method of adding a quaternary ammonium salt compound represented by the general formula (1) or a solution thereof to a pulp slurry, or a method of forming a paper material from these, and then forming a quaternary ammonium compound represented by the general formula (1) A method of coating or spraying a solution of a salt compound may be mentioned. When the recording material raw material is a synthetic paper, a fiber material or a resin film, for example, a method of coating or spraying a solution of a quaternary ammonium salt compound represented by the general formula (1) can be mentioned. .
[0022]
The amount of the quaternary ammonium salt compound of the general formula (1) applied to the recording material raw material is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the recording material raw material. At this time, the quaternary ammonium salt compound may be adhered to the surface of the recording material raw material, or may be impregnated into the inside and uniformly distributed throughout the recording material. When the content of the quaternary ammonium salt compound is less than 0.01 part by weight based on 100 parts by weight of the recording material raw material, the content may not be enough to suppress the ink from flowing out and bleeding into water. If the amount exceeds the limit, the texture of the recording material may change significantly as compared with when the quaternary ammonium salt is not contained.
[0023]
In the present invention, in order to prevent the ink from bleeding at the time of printing, and to prevent the printed matter from flowing out with water, it is particularly preferable to include the quaternary ammonium salt compound on the surface of the recording material raw material. preferable. At this time, it is preferable to contain 0.01 to 10 g of the quaternary ammonium salt compound per 1 m ² of the surface of the recording material. If the amount is less than 0.01 g, it is necessary to prevent the ink from flowing out to water and to suppress bleeding. If it is not sufficient, and if it exceeds 10 g, the hand of the recording material may change greatly as compared with when the quaternary ammonium salt compound is not contained. As a method for incorporating the quaternary ammonium salt compound into the surface of the recording material raw material, a coating method or a spray method is preferable.
[0024]
The recording material of the present invention may further contain other components, if necessary, as long as the effects of the present invention are not impaired. Such components include, for example, conventionally used binders, inorganic pigments and organic pigments. Examples of the binder include starch oxide and polyvinyl alcohol, and examples of the inorganic pigment include soft calcium carbonate, heavy calcium carbonate, kaolin (white clay), talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfate, and the like. Examples include zinc carbonate, aluminum silicate, diatomaceous earth, calcium silicate, synthetic silica, aluminum hydroxide, and alumina.Examples of organic pigments include styrene-based plastic pigments, acrylic-based plastic pigments, microencapsulated pigments, and carbon resin pigments. No.
[0025]
【Example】
Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.
The weight average molecular weight of the quaternary ammonium salt compound was measured by gel permeation chromatography (GPC) [HLC-8120GPC: manufactured by Tosoh Corporation] in terms of polyoxyethylene glycol. Note that an acetate buffer (pH 4.7) was used as an eluent for measurement.
[0026]
Example 1
50 g of water, 25 g of N, N, N ′, N′-tetramethylpropylenediamine and 28 g of bis (2-chloroethyl) ether were charged into a reaction vessel, reacted at 60 ° C. for 72 hours, and 28 g of water was added. The concentration of the quaternary ammonium salt compound was adjusted to 40% by weight. The weight average molecular weight of the obtained poly [oxyethylene (dimethyliminio) propylene (dimethyliminio) ethylene dichloride] was 7,500, and the value of n in the general formula (1) was 27.
[0027]
Example 2
50 g of water, 25 g of N, N, N ′, N′-tetramethylpropylenediamine and 28 g of bis (2-chloroethyl) ether were charged into a reaction vessel, reacted at 95 ° C. for 30 hours, and 28 g of water was added. The concentration of the quaternary ammonium salt compound was adjusted to 40% by weight. The weight average molecular weight of the obtained poly [oxyethylene (dimethyliminio) propylene (dimethyliminio) ethylenedichloride] was 32,000, and the value of n in the general formula (1) was 117.
[0028]
Example 3
50 g of water, 25 g of N, N, N ′, N′-tetramethylhexamethylenediamine and 21 g of bis (2-chloroethyl) ether were charged into a reaction vessel, reacted at 100 ° C. for 48 hours, and 19 g of water was added. The concentration of the quaternary ammonium salt compound was adjusted to 40% by weight. The weight average molecular weight of the obtained poly [oxyethylene (dimethyliminio) hexamethylene (dimethyliminio) ethylene dichloride] was 35,000, and the value of n in the general formula (1) was 111.
[0029]
Example 4
50 g of water, 23 g of N, N, N ′, N′-tetramethylpropylenediamine and 37 g of 83% by weight bis (2-chloroethyl) formal were charged into a reaction vessel, reacted at 105 ° C. for 20 hours, and unreacted. Bis (2-chloroethyl) formal was separated and separated, and 22 g of water was added to adjust the concentration of the quaternary ammonium salt compound to 40% by weight. The weight average molecular weight of the obtained poly [oxymethyleneoxyethylene (dimethyliminio) propylene (dimethyliminio) ethylene dichloride] was 13,000, and the value of n in the general formula (1) was 43.
[0030]
Comparative Example 1
40% by weight solution of polyethyleneimine (weight average molecular weight 1,200).
Evaluation method A paper, fiber or polyester film as a recording material was evaluated by the following method.
[0031]
1. Using an Epson (MJ-700V2C) inkjet printer, the inkjet recording material solid-printed with a single color of black (BLACK), cyan (CYAN), magenta (MAGENTA), and yellow (YELLOW) was allowed to stand for 1 hour, and then was flushed. For 5 minutes, and the change in the printed portion was visually observed and evaluated according to the following criteria.
[0032]
：: The printed portion is not washed away or bleed with water. △: The printed portion is slightly bleeding. X: The printed portion is clearly washed with water and bleeding. The ink bleeding property The dot portion of the ink jet recording material printed with dots of a single black color by an Epson (MJ-700V2C) ink jet printer was visually observed with a loupe (magnification: 50 times) and evaluated according to the following criteria.
[0033]
：: No bleeding Δ: Slightly bleeding X: Slightly bleeding Recording paper A 2% by weight (solid content) aqueous solution of the quaternary ammonium salt compound obtained in Example 1 was coated on high quality paper with a bar coater. A recording material having a coating amount after drying of 0.5 g / m ² was prepared. Water resistance and ink bleeding property were evaluated using the obtained recording material. Table 1 shows the results.
[0034]
In the same manner as described above, the recording materials obtained using the compounds of Examples 2 to 4 and Comparative Example 1 were also evaluated for water resistance and ink bleeding. The results are shown in Table 1.
[0035]
[Table 1]

[0036]
The recording fiber polyester ponge cloth was padded (pickup 80%) with a treatment solution of a 3% by weight (solid content) aqueous solution of the quaternary ammonium salt compound of Example 1, dried at 105 ° C. for 3 minutes, and recorded. Made wood. Water resistance and ink bleeding property were evaluated using the obtained recording material. Table 2 shows the results.
[0037]
In the same manner as described above, the compounds of Examples 2 to 4 and Comparative Example 1 were also evaluated. Table 2 also shows the results.
[0038]
[Table 2]

[0039]
A mixed solution of a 2% by weight (solid content) aqueous solution of the quaternary ammonium salt compound of Example 1 of the recording film and 2% by weight of Neosticker 700 (manufactured by Nika Chemical Co., Ltd.) as an anchor agent for a film was applied to a bar. The polyester film was coated with a coater. As a result, a recording material having a coating amount of 0.5 g / m ² of the quaternary ammonium salt compound after drying was obtained. Water resistance and ink bleeding property were evaluated using the obtained recording material. Table 3 shows the results.
[0040]
In the same manner as described above, the compounds of Examples 2 to 4 and Comparative Example 1 were also evaluated. Table 3 also shows the results.
[0041]
[Table 3]

[0042]
【The invention's effect】
According to the present invention, there is provided a recording material in which ink does not bleed when ink adheres to the recording material (when printing is performed), and ink does not flow out or bleed due to water even after ink is adhered (after printing). It is possible to do.

Claims (5)

A recording material for inkjet recording containing a quaternary ammonium salt compound represented by the following general formula (1).

(In the above formula, R ¹ each independently represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, Y represents an alkylene group having 2 to 10 carbon atoms, and Z represents Represents a heteroatom-containing alkylene group of numbers 2 to 10, A ⁻ represents an anion, and n represents an integer of 3 to 500) 2. The recording material for ink jet recording according to claim 1, wherein the quaternary ammonium salt compound is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the recording material raw material. 3. The recording material for ink jet recording according to claim 1, wherein the quaternary ammonium salt compound is contained on the surface of the recording material in an amount of 0.01 to 10 g / m < ² >. The recording material for inkjet recording according to any one of claims 1 to 3, wherein the recording material raw material is a paper material, a fiber material, or a resin film. A water-proofing agent for inkjet recording containing a quaternary ammonium salt compound represented by the following general formula (1).

(In the above formula, R ¹ each independently represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, Y represents an alkylene group having 2 to 10 carbon atoms, and Z represents Represents a heteroatom-containing alkylene group of numbers 2 to 10, A ⁻ represents an anion, and n represents an integer of 3 to 500)