JPH0826520B2 - Water repellent paper and method for producing the same - Google Patents
Water repellent paper and method for producing the sameInfo
- Publication number
- JPH0826520B2 JPH0826520B2 JP3008322A JP832291A JPH0826520B2 JP H0826520 B2 JPH0826520 B2 JP H0826520B2 JP 3008322 A JP3008322 A JP 3008322A JP 832291 A JP832291 A JP 832291A JP H0826520 B2 JPH0826520 B2 JP H0826520B2
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- paper
- water
- repellent
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- sicl
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、撥水性の紙及び撥水性
の紙の製造方法に関し、特に、撥水性で且つ撥油性の紙
または撥水性で且つ親油性の紙に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent paper and a method for producing a water-repellent paper, and more particularly to a water-repellent and oil-repellent paper or a water-repellent and lipophilic paper.
【０００２】[0002]
【従来の技術】従来、撥水性の紙の製造方法としては、
例えば紙の表面にポリテトラフルオロエチレン薄膜をコ
ートする方法やパラフィンを紙に含浸する方法があっ
た。2. Description of the Related Art Conventionally, as a method for producing water-repellent paper,
For example, there are a method of coating a polytetrafluoroethylene thin film on the surface of paper and a method of impregnating paper with paraffin.
【０００３】[0003]
【発明が解決しようとする課題】従来の撥水性で且つ撥
油性の紙又は撥水性で且つ親油性の紙は、何れも紙の光
沢や感触を損なうものであった。All of the conventional water-repellent and oil-repellent papers or water-repellent and lipophilic papers impair the gloss and feel of the paper.
【０００４】本発明の目的は、紙本来の光沢や感触を損
なわずに撥水性で、且つ撥油性または親油性にした紙を
提供することである。An object of the present invention is to provide a paper which is water-repellent and oil-repellent or lipophilic without impairing the original gloss and feel of the paper.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
に、この発明の撥水性の紙は、フッ化炭素基や炭化水素
基のような撥水性基及びシロキサン結合を含む化学吸着
膜が、そのシロキサン結合を介して紙の表面に形成され
ていることを特徴とする。同じく、この発明の撥水性の
紙の製造方法は、一端にクロルシラン基を有し他端に撥
水性基を有するクロルシラン系界面活性剤を溶かした有
機溶媒に、親水性の紙を接触させることにより、紙の表
面に化学吸着膜を形成する化学吸着膜形成工程を含むこ
とを特徴とする。In order to achieve the above object, the water-repellent paper of the present invention has a chemical adsorption film containing a water-repellent group such as a fluorocarbon group or a hydrocarbon group and a siloxane bond. It is characterized in that it is formed on the surface of the paper through the siloxane bond. Similarly, the method for producing the water-repellent paper of the present invention comprises contacting the hydrophilic paper with an organic solvent in which a chlorosilane-based surfactant having a chlorosilane group at one end and a water-repellent group at the other end is dissolved. And a chemical adsorption film forming step of forming a chemical adsorption film on the surface of the paper.
【０００６】[0006]
【作用】本発明においては、きわめて薄いナノメータレ
ベルの膜厚のフッ化炭素系あるいは炭化水素系化学吸着
膜を親水性の紙繊維最表面に形成するため、紙本来の色
調や光沢を損なうことがない。なお、フッ化炭素系化学
吸着膜では撥水性と撥油性を高めることが可能である。
一方、炭化水素系化学吸着膜では、撥水性と親油性を高
めることが可能である。従って、撥水性の紙、さらに詳
しくは防汚効果の高い高性能撥水撥油性または撥水親油
性紙を提供できる作用がある。In the present invention, since the fluorocarbon-based or hydrocarbon-based chemical adsorption film having an extremely thin film thickness of nanometer level is formed on the outermost surface of the hydrophilic paper fiber, the original color tone and gloss of the paper may be impaired. Absent. The fluorocarbon-based chemical adsorption film can enhance water repellency and oil repellency.
On the other hand, a hydrocarbon-based chemical adsorption film can improve water repellency and lipophilicity. Therefore, there is an effect that water-repellent paper, more specifically, high-performance water- and oil-repellent or water- and lipophilic paper having a high antifouling effect can be provided.
【０００７】[0007]
【実施例】一般に紙は、セルロース等でできており、繊
維表面に水酸基等の親水性基を含む。そこで、一端にク
ロルシラン基を有し他端にフッ化炭素又は炭化水素鎖を
含むクロルシラン系界面活性剤を含有する非水系溶液に
接触させると、繊維表面の親水性基とクロルシラン基と
が脱塩酸反応し、親水性の紙繊維表面にクロルシラン系
界面活性剤が化学吸着して、末端にフッ化炭化水素基を
含む場合には撥水性で且つ撥油性化され、また、末端に
炭化水素基を含む場合には撥水性で且つ親油性化された
紙が得られる。なお、化学繊維製の紙や合成紙のように
表面に親水性基の密度が低い場合には、表面をプラズマ
処理して親水性化すればよい。EXAMPLES Generally, paper is made of cellulose or the like, and the surface of the fiber contains hydrophilic groups such as hydroxyl groups. Therefore, when contacted with a non-aqueous solution containing a chlorosilane-based surfactant having a chlorosilane group at one end and a fluorocarbon or a hydrocarbon chain at the other end, the hydrophilic group and chlorosilane group on the fiber surface are dehydrochlorinated. Reacting, the chlorosilane-based surfactant is chemically adsorbed on the hydrophilic paper fiber surface to make it water-repellent and oil-repellent when it contains a fluorinated hydrocarbon group at the terminal, and a hydrocarbon group at the terminal. When it is contained, a water-repellent and lipophilic paper is obtained. When the density of hydrophilic groups on the surface is low, such as chemical fiber paper or synthetic paper, the surface may be treated with plasma to make it hydrophilic.
【０００８】本発明の紙は、クロルシラン系界面活性剤
を繊維表面に化学吸着することによって撥水性で且つ撥
油性もしくは撥水性で且つ親油性が付与されている。こ
のような化学吸着膜は単分子膜一層でも充分機能を発揮
する。単分子膜一層だけを化学吸着させるには、クロル
シラン系界面活性剤を親水性紙に接触した後非水系有機
溶媒で洗浄することにより、未反応の界面活性剤を洗浄
除去する手法を採る。しかしながら、本発明の紙では化
学吸着された膜が必ずしも単分子膜である必要はなく、
ポリマー状の化学吸着薄膜であっても基本的目的は達成
できる。The paper of the present invention is imparted with water repellency and oil repellency or water repellency and lipophilicity by chemically adsorbing a chlorosilane type surfactant on the fiber surface. Such a chemisorption film has a sufficient function even with a single monolayer film. In order to chemically adsorb only one layer of the monomolecular film, a method of washing and removing the unreacted surfactant by contacting the chlorosilane-based surfactant with the hydrophilic paper and then washing with a non-aqueous organic solvent is adopted. However, in the paper of the present invention, the chemically adsorbed film does not necessarily have to be a monomolecular film,
The basic purpose can be achieved even with a polymer chemisorption thin film.
【０００９】また、本発明の紙に予めクロロシリル結合
を複数個含む物質を接触させた後水と反応させることに
より紙の繊維表面にシロキサン結合を多数含むシロキサ
ン系の化学吸着膜が形成でき、紙表面の親水性基の密度
を増加させることができる。このクロロシリル結合を複
数個含む物質よりできた層も、前述したのと同じように
単分子膜でも充分機能を発揮できるが、必ずしも単分子
膜である必要はない。ただし、単分子膜とするために
は、クロロシリル結合を複数個含む物質を親水性紙に接
触させた後非水系有機溶媒で洗浄し、しかる後水と反応
させてシラノール化させることにより、シラノール基を
複数個含む化学吸着単分子膜が形成できる。Further, a substance having a plurality of chlorosilyl bonds is brought into contact with the paper of the present invention in advance and then reacted with water to form a siloxane-based chemical adsorption film having a large number of siloxane bonds on the fiber surface of the paper. The density of hydrophilic groups on the surface can be increased. A layer made of a substance containing a plurality of chlorosilyl bonds can also exhibit a sufficient function as a monomolecular film as described above, but it is not necessarily a monomolecular film. However, in order to form a monomolecular film, a substance containing a plurality of chlorosilyl bonds is brought into contact with hydrophilic paper, washed with a non-aqueous organic solvent, and then reacted with water to form a silanol group. It is possible to form a chemisorption monomolecular film containing a plurality of chemical adsorption molecules.
【００１０】本発明の紙に供されるフッ化炭素基を含む
クロルシラン系界面活性剤としては、例えばCF3(CF2)
7(CH2)2SiCl3，CF3CH2O(CH2)15SiCl3，CF3(CH2)2Si(C
H3)2(CH2)15SiCl3，F(CF2)4(CH2)2Si(CH3)2(CH2)9SiC
l3，F(CF2)8(CH2)2Si(CH3)2(CH2)9SiCl3，CF3COO(CH2)
15SiCl3，CF3(CF2)5(CH2)2SiCl3等のようなトリクロル
シラン系界面活性剤がある。さらにCF3(CF2)7(CH2)2SiC
ln(CH3)3-n，CF3(CF2)7(CH2)2SiCln(C2H5)3-n，CF3CH2O
(CH2)15SiCln(CH3)3-n，CF3CH2O(CH2)15SiCln(C
2H5)3-n，CF3(CH2)2Si(CH3)2(CH2)15SiCln(CH3)3-n，F
(CF2)4(CH2)2Si(CH3)2(CH2)9SiCln(C2H5)3-n，F(CF2)
8(CH2)2Si(CH3)2(CH2)9SiCln(CH3)3-n，CF3COO(CH2)15S
iCln(CH3)3-n，CF3(CF2)5(CH2)2SiCln(CH3)3-n（但し式
中のｎは何れも１又は２）等のような低級アルキル基置
換のモノクロルシラン系あるいはジクロルシラン系界面
活性剤が挙げられる。また、本発明に供される炭化水素
鎖を含むクロルシラン系界面活性剤としては、例えばCH
3(CH2)18SiCl3，CH3(CH2)15SiCl3，CH3(CH2)10SiCl3，C
H3(CH2)25SiCl3等のようなトリクロルシラン系界面活性
剤がある。さらに、CH3(CH2)18SiCln(CH3)3-n，CH3(C
H2)18SiCln(C2H5)3-n，CH3(CH2)15SiCln(CH3)3-n，CH
3(CH2)10SiCln(CH3)3-n，CH3(CH2)25SiCln(C2H5)3-n等
のような低級アルキル基置換のモノクロルシラン系ある
いはジクロルシラン系界面活性剤が挙げられる。これら
の中でも、特にトリクロルシラン系界面活性剤を用いる
と隣合う分子のクロルシラン基とも脱塩酸反応してシロ
キサン結合を形成するため、より強固な化学吸着膜とな
り好ましい。Examples of the chlorosilane-based surfactant containing a fluorocarbon group used for the paper of the present invention include CF 3 (CF 2 )
7 (CH 2 ) 2 SiCl 3 , CF 3 CH 2 O (CH 2 ) 15 SiCl 3 , CF 3 (CH 2 ) 2 Si (C
H 3 ) 2 (CH 2 ) 15 SiCl 3 , F (CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (CH2) 9 SiC
l 3 , F (CF 2 ) 8 (CH 2 ) 2 Si (CH 3 ) 2 (CH2) 9 SiCl 3 , CF 3 COO (CH 2 )
There are trichlorosilane-based surfactants such as 15 SiCl 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3, etc. Furthermore, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiC
l n (CH 3 ) 3-n , CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl n (C 2 H 5 ) 3-n , CF 3 CH 2 O
(CH 2 ) 15 SiCl n (CH 3 ) 3-n , CF 3 CH 2 O (CH 2 ) 15 SiCl n (C
2 H 5 ) 3-n , CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiCl n (CH 3 ) 3-n , F
(CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (CH2) 9 SiCl n (C 2 H 5 ) 3-n , F (CF 2 )
8 (CH 2 ) 2 Si (CH 3 ) 2 (CH2) 9 SiCl n (CH 3 ) 3-n , CF 3 COO (CH 2 ) 15 S
iCl n (CH 3 ) 3-n , CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl n (CH 3 ) 3-n (where n in the formula is either 1 or 2) etc. Examples thereof include group-substituted monochlorosilane-based or dichlorosilane-based surfactants. Further, as the chlorosilane-based surfactant containing a hydrocarbon chain used in the present invention, for example, CH
3 (CH 2 ) 18 SiCl 3 , CH 3 (CH 2 ) 15 SiCl 3 , CH 3 (CH 2 ) 10 SiCl 3 , C
There are trichlorosilane based surfactants such as H 3 (CH 2) 25 SiCl 3 . In addition, CH 3 (CH 2 ) 18 SiCl n (CH 3 ) 3-n , CH 3 (C
H 2 ) 18 SiCl n (C 2 H 5 ) 3-n , CH 3 (CH 2 ) 15 SiCl n (CH 3 ) 3-n , CH
3 (CH 2 ) 10 SiCl n (CH 3 ) 3-n , CH 3 (CH 2) 25 SiCl n (C 2 H 5 ) 3-n, etc. Lower alkyl group-substituted monochlorosilane-based or dichlorosilane-based surfactants Agents. Among these, particularly when a trichlorosilane-based surfactant is used, a chlorosilane group of an adjacent molecule is dehydrochlorinated to form a siloxane bond, which is preferable because a stronger chemisorption film is obtained.
【００１１】さらに、本発明に供されるクロロシリル基
を複数個含む物質としては、例えばＳｉＣｌ4、ＳｉＨ
Ｃｌ3、ＳｉＨ2Ｃｌ2、Ｃｌ−（ＳｉＣｌ2Ｏ）n−Ｓｉ
Ｃｌ3（但し式中ｎは自然数）、ＳｉＣｌm（Ｃ
Ｈ3）4-m、ＳｉＣｌm（Ｃ2Ｈ5）4-m（但し式中ｍは１〜
３の整数）、ＨＳｉＣｌl（ＣＨ3）3-l、ＨＳｉＣｌ
l（Ｃ2Ｈ5）3-l（但し式中ｌは１又は２）等が挙げられ
る。この中でもＳｉＣｌ4、ＳｉＨＣｌ3、ＳｉＨ2Ｃ
ｌ2、Ｃｌ−（ＳｉＣｌ2Ｏ）n−ＳｉＣｌ3が反応性の点
で好ましく、特にＳｉＣｌ4は反応性が高く分子量も小
さいためより高密度にシラノール基を付与できるため好
ましい。Further, examples of the substance containing a plurality of chlorosilyl groups used in the present invention include SiCl 4 and SiH.
Cl 3, SiH 2 Cl 2, Cl- (SiCl 2 O) n -Si
Cl 3 (where n is a natural number), SiCl m (C
H 3) 4-m, SiCl m (C 2 H 5) 4-m ( where Shikichu m is 1
3 integer), HSiCl l (CH 3) 3-l, HSiCl
l (C 2 H 5 ) 3-l (wherein l is 1 or 2) and the like. Among these, SiCl 4 , SiHCl 3 , SiH 2 C
l 2 and Cl- (SiCl 2 O) n -SiCl 3 are preferable from the viewpoint of reactivity, and SiCl 4 is particularly preferable because it has a high reactivity and a small molecular weight and can give a silanol group at a higher density.
【００１２】本発明の紙の製造方法では、抄紙工程を経
た紙を直接クロルシラン系界面活性剤溶液に浸漬するだ
けで撥水性で且つ撥油性処理又は撥水性で且つ親油性処
理された紙が得られる。なお、クロルシラン系界面活性
剤は親水性基の活性水素に優先的に化学吸着するため、
一般に抄紙した紙の繊維自体に化学吸着するが、例えば
サイズ剤等に活性水素がある場合にはサイズ剤等にも化
学吸着する。According to the method for producing paper of the present invention, water-repellent and oil-repellent treated or water-repellent and lipophilic treated paper can be obtained only by directly dipping the paper that has undergone the papermaking process in the chlorosilane-based surfactant solution. To be Since the chlorosilane-based surfactant preferentially chemisorbs to the active hydrogen of the hydrophilic group,
Generally, it is chemically adsorbed to the fiber itself of the paper made, but when the sizing agent or the like has active hydrogen, it is also chemically adsorbed to the sizing agent or the like.
【００１３】本発明に供される溶媒としては、例えばヘ
キサデカン，トルエン，キシレン，ジクロロヘキシル，
四塩化炭素，クロロホルム等の非水系有機溶媒である。Examples of the solvent used in the present invention include hexadecane, toluene, xylene, dichlorohexyl,
It is a non-aqueous organic solvent such as carbon tetrachloride and chloroform.
【００１４】本発明に関する撥水性で且つ撥油性の紙と
して、包装用紙、紙パック、紙コンテナー、または撥水
性で且つ親油性紙として包装用紙、紙パック、紙コンテ
ナー、印刷用紙等で代表される高性能撥水性で且つ撥油
性または撥水性で且つ親油性紙があるが、以下代表例と
して包装用紙を取り上げ順に説明する。The water-repellent and oil-repellent paper relating to the present invention is represented by a packaging paper, a paper pack, a paper container, or a water-repellent and lipophilic paper such as a packaging paper, a paper pack, a paper container and a printing paper. Although there are high-performance water-repellent and oil-repellent or water-repellent and lipophilic papers, packaging paper will be described below as a typical example in order.
【００１５】実施例１ 抄紙加工の終了したセルロース製包装用紙１を準備し、
フッ化炭素基及びクロロシラン基を含む物質としてCF
3(CF2)7(CH2)2SiCl3を、８０％ｎ-ヘキサデカン、１２
％四塩化炭素、８％クロロホルムの非水系の混合溶媒
に、１０％の濃度で溶かした化学吸着溶液を調整し、紙
１を２時間程度浸漬すると、紙１のセルロース繊維表面
の水酸基とフッ化炭素基及びクロロシラン基を含む物質
のＳｉＣｌ基とが脱塩酸反応して、紙１のセルロース繊
維表面全面に亘り図１に示したような（化１）の結合が
生成され、Example 1 A cellulose wrapping paper 1 which has been subjected to papermaking processing is prepared,
CF as a substance containing fluorocarbon groups and chlorosilane groups
3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 with 80% n-hexadecane, 12
% Chemosorption solution prepared by dissolving 10% concentration in a non-aqueous mixed solvent of carbon tetrachloride and 8% chloroform, and immersing the paper 1 for about 2 hours The SiCl group of the substance containing a carbon group and a chlorosilane group undergoes a dehydrochlorination reaction to form a bond (Chemical Formula 1) as shown in FIG. 1 over the entire surface of the cellulose fiber of the paper 1,
【００１６】[0016]
【化１】 Embedded image
【００１７】フッ化炭素基を含む撥水性の化学吸着膜２
が紙の繊維の表面と化学結合した状態でおよそ１５Åの
膜厚で形成できた。この包装用紙は、撥水性で且つ撥油
性であり、紙本来の光沢や感触は損なわれていなかっ
た。Water-repellent chemisorption film 2 containing fluorocarbon groups
Was formed with a film thickness of approximately 15Å in a state of being chemically bonded to the surface of the fiber of the paper. This wrapping paper was water-repellent and oil-repellent, and the original gloss and feel of the paper were not impaired.
【００１８】この紙を用い実使用を試みたが、処理しな
いものに比べ汚物の付着を大幅に低減でき、たとえ付着
した場合にもブラシ等でこする程度で簡単に除去でき
た。また、撥水性があり油脂分汚れでも除去は水洗のみ
で可能であった。An attempt was made to actually use this paper, but it was possible to significantly reduce the attachment of dirt compared to the untreated paper, and even if it was attached, it could be easily removed by rubbing it with a brush or the like. Further, it has water repellency and even oil and fat stains can be removed only by washing with water.
【００１９】なお、このとき化学吸着用界面活性剤とし
て、例えばCH3(CH2)18SiCl3のような炭化水素鎖を含む
試薬を用いれば、撥水性と親油性を備え、紙本来の光沢
や感触を損なわない紙が得られた。At this time, if a reagent containing a hydrocarbon chain such as CH 3 (CH 2 ) 18 SiCl 3 is used as the surface active agent for chemisorption, it has water repellency and lipophilicity, and has a gloss original to paper. A paper was obtained that did not impair the feel.
【００２０】実施例２ 親水性ではあるが水酸基を含む割合が少ないポリプロピ
レン系の合成紙を３００Ｗ１０分程度プラズマ処理して
図２に示したように繊維１１の表面に水酸基（以下ＯＨ
基と称す）１２を形成させてある程度親水化した。次
に、トリクロロシリル基を複数個含む物質としてＳｉＣ
ｌ4を用い、非水系溶媒であるクロロホルムに１重量パ
ーセント溶解した化学吸着溶液に３０分間程度浸漬する
と、紙の繊維１１表面に存在する親水性のＯＨ基１２と
Ｓｉ−Ｃｌ結合とが表面で脱塩酸反応して、トリクロロ
シリル基を複数個含む物質よりできた（化２）で示され
るクロロシラン化学吸着膜が−ＳｉＯ−結合を介して繊
維１１の表面に固定された。Example 2 A polypropylene-based synthetic paper which is hydrophilic but has a small proportion of hydroxyl groups was subjected to plasma treatment for about 300 W for 10 minutes, and as shown in FIG.
(Referred to as a group) 12 was formed to be hydrophilic to some extent. Next, as a substance containing a plurality of trichlorosilyl groups, SiC
When l 4 was used and immersed in a chemisorption solution in which 1 wt% was dissolved in chloroform, which is a non-aqueous solvent, for about 30 minutes, hydrophilic OH groups 12 and Si—Cl bonds existing on the surface of the paper fiber 11 were formed on the surface. After the dehydrochlorination reaction, a chlorosilane chemisorption film represented by the chemical formula (2) made of a substance containing a plurality of trichlorosilyl groups was fixed on the surface of the fiber 11 via a —SiO— bond.
【００２１】[0021]
【化２】 Embedded image
【００２２】その後、例えば非水系の溶媒であるクロロ
ホルムで洗浄して紙の繊維と未反応のＳｉＣｌ4を洗浄
除去し単分子吸着膜化し、さらに水で洗浄すると（化
２）で示した膜のＳｉＣｌ基と水が脱塩酸反応して紙の
繊維表面に（化３）で示したようなシラノール基を複数
個有するシロキサン単分子膜１３が図３に示したように
得られる。Thereafter, for example, the paper fiber and unreacted SiCl 4 are washed away with chloroform, which is a non-aqueous solvent, to form a monomolecular adsorption film, and further washed with water to obtain the film shown in (Chemical formula 2). The SiCl group and water undergo a dehydrochlorination reaction to obtain a siloxane monomolecular film 13 having a plurality of silanol groups as shown in (Chemical Formula 3) on the fiber surface of paper as shown in FIG.
【００２３】[0023]
【化３】 Embedded image
【００２４】なお、このときできたシロキサン単分子膜
１３は、紙の繊維とは−ＳｉＯ−の化学結合を介して完
全に共有結合されているので剥がれることが無い。ま
た、得られた単分子膜は表面にＳｉＯＨ結合を数多く持
ち、水酸基の数は当初のおよそ３倍程度生成される。Since the siloxane monomolecular film 13 formed at this time is completely covalently bonded to the paper fiber through a chemical bond of -SiO-, it does not peel off. Further, the obtained monomolecular film has many SiOH bonds on the surface, and the number of hydroxyl groups is generated about three times as much as the initial number.
【００２５】この後実施例１と同様にして、フッ化炭素
基及びクロロシラン基を含む物質を混ぜた非水系の溶媒
に、表面にＳｉＯＨ結合を数多く持つ単分子膜１３が形
成された紙１１を１時間程度浸漬すると、紙の繊維表面
に（化４）の結合が生成され、図４に示したようにフッ
化炭素基を含む化学吸着膜１４が下層のシロキサン単分
子膜１３と共有結合した状態で、紙１１の繊維表面全面
に亘りおよそ１５Åの膜厚で形成できた。なお、この紙
は撥水性で且つ撥油性であり、紙本来の光沢や感触は処
理前と全く変わらなかった。Thereafter, as in Example 1, the paper 11 having a monomolecular film 13 having a large number of SiOH bonds on the surface thereof was added to a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group. After soaking for about 1 hour, a bond of (Chemical Formula 4) was generated on the fiber surface of the paper, and the chemical adsorption film 14 containing a fluorocarbon group was covalently bonded to the lower siloxane monomolecular film 13 as shown in FIG. In this state, a film having a thickness of about 15Å could be formed over the entire fiber surface of the paper 11. The paper was water-repellent and oil-repellent, and the original gloss and feel of the paper were the same as before treatment.
【００２６】[0026]
【化４】 [Chemical 4]
【００２７】また、同様にシロキサン単分子膜１３を形
成した合成紙１１に炭化水素鎖を含むクロルシラン系界
面活性剤としてCH3(CH2)18SiCl3を用いて化学吸着を行
うと、撥水性で且つ親油性処理された合成紙が得られ
た。Similarly, when CH 3 (CH 2 ) 18 SiCl 3 is used as the chlorosilane-based surfactant containing a hydrocarbon chain for chemical adsorption on the synthetic paper 11 on which the siloxane monomolecular film 13 is similarly formed, water repellency is obtained. And a lipophilically treated synthetic paper was obtained.
【００２８】なお、上記実施例１および２では同一のフ
ッ化炭素基を含むクロルシラン系界面活性剤を用いた例
を示したが、本発明の紙はこの界面活性剤に限定される
ものではなく、他の化学吸着剤を用いても同様の効果が
得られたことは言うまでもない。また、上記実施例１お
よび２は何れもトリクロルシラン系界面活性剤を用いた
例であるが、ジクロルシラン系界面活性剤あるいはモノ
クロルシラン系界面活性剤でもその効果は同様である。
さらに、本実施例１および２では何れも最表面にクロル
シラン系界面活性剤を用いて化学吸着単分子膜を形成し
た例を示したが、単分子累積膜でもよく、また特に単分
子膜化する必要もないことは勿論である。また、実施例
２ではクロロシリル結合を複数個含む物質を用いてシロ
キサン単分子膜を形成した例を示したが、本発明の紙で
適応されるクロロシリル結合を複数個有する物質で作ら
れた膜が単分子膜である必要は必ずしもなく、シロキサ
ン結合をたくさん含むシロキサン系の化学吸着膜であれ
ばよい。さらに、実施例２ではポリプロピレン合成紙の
場合について述べたが、クロロシリル結合を複数個有す
る物質の適用は合成紙に限定されるものではなく、化学
繊維を主体とした紙を始め、パルプ紙であっても表面の
親水性基の密度を調製する目的等多用な処理用途があ
る。In the above-mentioned Examples 1 and 2, an example using the same chlorosilane-based surfactant containing a fluorocarbon group was shown, but the paper of the present invention is not limited to this surfactant. Needless to say, the same effect was obtained by using other chemical adsorbents. In addition, in each of Examples 1 and 2 above, a trichlorosilane-based surfactant was used, but the same effect can be obtained with a dichlorosilane-based surfactant or a monochlorosilane-based surfactant.
Further, in each of Examples 1 and 2, an example was shown in which a chemisorption monomolecular film was formed on the outermost surface by using a chlorosilane-based surfactant, but a monomolecular cumulative film may be used, and particularly a monomolecular film is formed. Of course, it is not necessary. Also, in Example 2, an example of forming a siloxane monomolecular film using a substance containing a plurality of chlorosilyl bonds was shown, but a film made of a substance having a plurality of chlorosilyl bonds, which is applicable to the paper of the present invention, is formed. It does not necessarily have to be a monomolecular film, and may be a siloxane-based chemical adsorption film containing many siloxane bonds. Further, although the case of the polypropylene synthetic paper is described in Example 2, the application of the substance having a plurality of chlorosilyl bonds is not limited to the synthetic paper, and it is not limited to the synthetic fiber but also the pulp paper such as the paper mainly including the chemical fiber. However, there are various treatment applications such as the purpose of adjusting the density of hydrophilic groups on the surface.
【００２９】[0029]
【発明の効果】以上述べてきたように、本発明はきわめ
て薄いナノメータレベルの膜厚のフッ化炭素系化学吸着
膜や炭化水素系化学吸着膜を紙の繊維表面に形成するた
め、紙本来の光沢を損なうことがない。また、このフッ
化炭素系単分子膜は撥水性で且つ撥油性にも優れてお
り、紙表面の防汚効果を高めることが可能となる。ま
た、炭化水素系単分子膜を吸着した紙では撥水性で且つ
親油性が優れているので、油性インクを用いた印刷用の
紙として使用するとインクの乗りがよく、きわめて好都
合である。As described above, according to the present invention, since the fluorocarbon-based chemical adsorption film or the hydrocarbon-based chemical adsorption film having an extremely thin nanometer level film thickness is formed on the fiber surface of the paper, Does not spoil the gloss. Further, this fluorocarbon monomolecular film is excellent in water repellency and oil repellency, and it becomes possible to enhance the antifouling effect on the paper surface. Further, since the paper having the hydrocarbon monomolecular film adsorbed is excellent in water repellency and lipophilicity, it is very convenient when used as a paper for printing using an oil-based ink, because the ink can ride well.
【図１】本発明の実施例１を説明するためのものであ
り、紙繊維の表面を分子レベルまで拡大した断面概念図FIG. 1 is a cross-sectional conceptual view in which a surface of a paper fiber is enlarged to a molecular level for explaining Example 1 of the present invention.
【図２】本発明の別の実施例２を説明するためのもので
あり、親水性化処理を施した紙繊維の表面を分子レベル
まで拡大した断面概念図FIG. 2 is a cross-sectional conceptual view for explaining another embodiment 2 of the present invention, in which the surface of the paper fiber subjected to the hydrophilization treatment is enlarged to the molecular level.
【図３】本発明の別の実施例２を説明するためのもので
あり、クロロシリル基を複数個有する物質を化学吸着し
た紙繊維表面を分子レベルまで拡大した断面概念図FIG. 3 is a cross-sectional conceptual view in which another surface of a paper fiber chemically adsorbed with a substance having a plurality of chlorosilyl groups is enlarged to a molecular level for explaining another embodiment 2 of the present invention.
【図４】本発明の別の実施例２を説明するためのもので
あり、紙繊維表面を分子レベルまで拡大した断面概念図FIG. 4 is a conceptual cross-sectional view in which the surface of a paper fiber is enlarged to a molecular level for explaining another embodiment 2 of the present invention.
１ 包装用紙 ２ 化学吸着膜 １１ 合成紙 １２ 水酸基 １３ シロキサン単分子膜 １４ 化学吸着膜 1 Wrapping paper 2 Chemical adsorption film 11 Synthetic paper 12 Hydroxyl group 13 Siloxane monomolecular film 14 Chemical adsorption film
Claims (9)
吸着膜が、そのシロキサン結合を介して紙の表面に形成
されていることを特徴とした撥水性の紙。1. A water-repellent paper, characterized in that a chemical adsorption film containing a water-repellent group and a siloxane bond is formed on the surface of the paper through the siloxane bond.
記載の撥水性の紙。2. The water repellent group is a fluorocarbon group.
The water-repellent paper described.
載の撥水性の紙。3. The water-repellent paper according to claim 1, wherein the water-repellent group is a hydrocarbon group.
性基を有するクロルシラン系界面活性剤を溶かした有機
溶媒に、親水性の紙を接触させることにより、紙の表面
に化学吸着膜を形成する化学吸着膜形成工程を含むこと
を特徴とする撥水性の紙の製造方法。4. A chemical adsorption film is formed on the surface of a paper by bringing a hydrophilic paper into contact with an organic solvent in which a chlorosilane-based surfactant having a chlorosilane group at one end and a water-repellent group at the other end is dissolved. A method for producing water-repellent paper, which comprises a step of forming a chemical adsorption film.
記載の撥水性の紙の製造方法。5. The water repellent group is a fluorocarbon group.
A method for producing the water-repellent paper described.
載の撥水性の紙の製造方法。6. The method for producing water-repellent paper according to claim 4, wherein the water-repellent group is a hydrocarbon group.
ル結合を複数個含む物質を含む非水系溶液に親水性紙を
接触させる接触工程と、水と反応させて前記親水性紙上
の前記物質のクロロシリル結合をシラノール結合に置換
するシラノール基形成工程とを介在させ、紙の表面にシ
ラノール基及び化学吸着膜を累積形成する請求項４〜６
のいずれかに記載の撥水性の紙の製造方法。7. A contact step of bringing a hydrophilic paper into contact with a non-aqueous solution containing a substance containing a plurality of chlorosilyl bonds before the chemisorption film forming step, and a step of reacting the hydrophilic paper with water to react the substance on the hydrophilic paper. 7. A silanol group and a chemisorption film are cumulatively formed on the surface of the paper by interposing a silanol group forming step of substituting a chlorosilyl bond with a silanol bond.
5. The method for producing a water-repellent paper according to any one of 1.
に、親水性紙上に残った未反応のクロロシリル結合を複
数個含む物質を洗浄除去する洗浄工程を設ける請求項７
記載の撥水性の紙の製造方法。8. A washing step for washing and removing a substance containing a plurality of unreacted chlorosilyl bonds remaining on the hydrophilic paper is provided between the contacting step and the silanol group forming step.
A method for producing the water-repellent paper described.
ＳｉＣｌ4、ＳｉＨＣｌ3、ＳｉＨ2Ｃｌ2、Ｃｌ−（Ｓｉ
Ｃｌ2Ｏ）n−ＳｉＣｌ3（ｎは整数）の何れかである請
求項７又は８に記載の撥水性の紙の製造方法。9. A substance containing a plurality of chlorosilyl bonds,
SiCl 4 , SiHCl 3 , SiH 2 Cl 2 , Cl- (Si
Cl 2 O) n -SiCl 3 ( n is the method of manufacturing paper water repellent according to claim 7 or 8 is any integer).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3008322A JPH0826520B2 (en) | 1991-01-28 | 1991-01-28 | Water repellent paper and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3008322A JPH0826520B2 (en) | 1991-01-28 | 1991-01-28 | Water repellent paper and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04245999A JPH04245999A (en) | 1992-09-02 |
| JPH0826520B2 true JPH0826520B2 (en) | 1996-03-13 |
Family
ID=11689936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3008322A Expired - Fee Related JPH0826520B2 (en) | 1991-01-28 | 1991-01-28 | Water repellent paper and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0826520B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100821B (en) * | 2007-07-04 | 2010-05-26 | 中国科学院长春应用化学研究所 | Preparation method and application of superhydrophobic cotton fiber material or superhydrophobic paper fiber material |
| JP2009106240A (en) * | 2007-10-31 | 2009-05-21 | Kagawa Gakusei Venture:Kk | Water repellent paper for storing live fish and live fish container using the same |
| US20120248034A1 (en) * | 2011-04-01 | 2012-10-04 | Lydall, Inc. | Methods of making and using liquid filter media |
-
1991
- 1991-01-28 JP JP3008322A patent/JPH0826520B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04245999A (en) | 1992-09-02 |
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