JP3729626B2 - Latex composition and sheet material - Google Patents

Description

【００２７】
【化８】

【００２８】
【化９】

【００２９】
次にフッ素原子を有する重合可能なモノマーについて説明する。
本発明で好ましく用いることができるモノマーは、下記一般式（Ｆ１）及び（Ｆ２）で表される化合物である。
【００３０】
【化１０】

式中、Ｒは水素原子、又はフッ素原子で置換されてもよいメチル基を表し、Ｒｆはフッ素原子で置換された直鎖、分岐又は環状のアルキル基を表し、このアルキル基は好ましくは炭素原子数が１〜１０であり、フッ素原子以外の基又は原子によって置換されていてもよく、これらの基又は原子としては、例えば、ヒドロキシ基、ハロゲン原子（例えば、Ｃｌ、Ｂｒ等）等が挙げられる。
【００３１】
【化１１】

式中、Ｒ^１は水素原子、塩素原子又は炭素数１〜３のアルキル基を表す。Ｒ^２は１価の置換基を表し、Ｒ^２は互いに連結して環を形成してもよい。Ｒ^ｆは少なくとも１個の水素原子がフッ素原子で置換された炭素数１〜３０のアルキル基、アラルキル基、アリール基又はアルキルアリール基を表す。Ｘは一般式
【００３２】
【化１２】

で表される２価の連結基を表し、ここにＲは炭素数１〜１０のアルキレン基、アリーレン基又はアラルキレン基を表し、−Ｌ−は−Ｏ−基、−Ｓ−基、−ＮＲ^３−基（ここにＲ^３は炭素数１〜４のアルキル基を表す。以下同じ）、−ＣＯ−基、−ＯＣＯ−基、−ＳＣＯ−基、−ＣＯＮＲ^３−基、−ＳＯ_２−基、−ＮＲ^３ＳＯ_２−基、−ＳＯ_２ＮＲ^３−基、−ＳＯ−基を表し、
【００３３】
【外１】

は０又は１である。ｌは０〜４の整数であり、好ましくは０〜２の整数であり、ｍは０〜４の整数であり、好ましくは０又は１であり、ｎは１〜５の整数であり、特に１又は２が好ましい。
【００３４】
次に本発明で用いられるモノマーの例を挙げる。
【００３５】
【化１３】

【００３６】
【化１４】

【００３７】
【化１５】

【００３８】
【化１６】

【００３９】
フッ素原子を有する重合可能なモノマーと共重合可能なモノマーとしては、ビニル基を持つ化合物であり、例えば、メチルアクリレート、エチルアクリレート、ブチルアクリレート、シクロヘキシルアクリレート等のアクリル酸エステル、メチルメタクリレート、エチルメタクリレート、シクロヘキシルメタクリレート、スルホプロピルメタクリレート等のメタクリル酸エステル、酢酸ビニル、プロピオン酸ビニル等のビニールエステル類、メチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類、メチルビニルケトン、エチルビニルケトン等のビニルケトン類、スチレン、メチルスチレン、クロロメチルスチレン等のスチレン類、アクリロニトリル、塩化ビニル、ビニリデンクロライド、ブタジエン、イソプレン等が挙げられる。
フッ素原子を有する重合可能なモノマーと共重合可能なモノマーの好ましい共重合比は、重量比で前者が３％以上あればよいが、好ましくは５〜８０％である。
【００４０】
本発明のシート状材料は、支持体上に親水性コロイド層を有していれば特に限定されない。
本発明の親水性コロイド層とは、親水性コロイドをバインダー（結合剤）とする塗膜である。
【００４１】
本発明のラテックスの好ましい含有率は、バインダーに対し固形分にして１〜４０重量％である。また、複数の種類を併用してもよい。
本発明のポリマーは、シート状材料、特にハロゲン化銀写真感光材料に好適である。
【００４２】
【実施例】
次に本発明に係るラテックス組成物の合成例、その他本発明の実施例を挙げる。
先ず、ラテックス製造例を挙げる。
ラテックス製造例１
１リットルのコルベンにＮ_２ガスで脱気した蒸留水３６０ｍｌと、親水性高分子（ＳＰ−４）４．５ｇを入れ８０℃にまで昇温する。これに蒸留水５ｍｌに溶解した過硫酸アンモニウム０．５０ｇを素早く添加し、そこにフッ素原子を有する重合可能なモノマーＦ−１（但し、ｎ＝４）５０ｇ、スチレン４０ｇ、アクリル酸０．５ｇの混合物を約１時間で滴下し、滴下終了後、更に３時間攪拌する。過硫酸アンモニウムを０．２ｇ加え、更に室温まで冷却、目的とするラテックスＡを得た。得られたラテックスの平均粒径は約０．２μｍであった。
【００４３】
ラテックス製造例２〜１２
表１のように使用する親水性高分子、フッ素原子を有する重合可能なモノマー、及び共重合可能なモノマーの種類と量を変更した以外は上記ラテックス製造例１と同様に作成した。
【００４４】
【表１】

【００４５】
次に、シート材料製造例を挙げる。
ゼラチン５ｇに水６０ｍｌを加え、ラテックスの固形分が０．５ｇとなるようラテックス液を加え、加熱溶解後、平均粒径３μｍのポリメチルメタアクリレート微粒子０．０２ｇと架橋剤（Ｈ−１）０．０５ｇを加え、水を加えて１００ｍｌに仕上げた液を、下引き済のポリエチレンテレフタレート支持体（厚さ１００μｍ）の両面にそれぞれゼラチン量が２ｇ／ｍ^２となるように塗布乾燥した試料を作成した。また、塗布液に加えるラテックスの量を変えてラテックスの量を変化させた試料も作成した。
【００４６】
＜べとつき評価＞
作成した試料を３ｃｍ平方の大きさに５枚切取り、それぞれお互いが接触しないように２３℃・８０％ＲＨの条件下に１日放置し、その後、５枚を重ねて当て木をあて１００ｇの加重をかけて、４０℃・８０％ＲＨ下に半日放置した。試料を取り出し、重ね合わせた試料を手で剥がして、剥がれ易さを下記評価基準にて評価した。結果を表２に示す。
５：さらっと剥がれる
４：かすかに抵抗がある
３：抵抗がある
２：かなり抵抗がある
１：塗膜が一部剥がれる
【００４７】
＜ゴミ付着評価＞
作成した試料を５ｃｍ平方の大きさに５枚切取り、それぞれお互いが接触しないように２３℃・２０％ＲＨの条件下に１日放置し、その後、試料の表面をナイロンの布でこすり、たばこの灰の入った灰皿の上にかざして、灰の付着する状態を観察し、下記評価基準にて評価した。結果を表２に示す。
５：全く灰がつかない
４：よく見ると灰がついている
３：容易に気がつく程度に灰がついている
２：灰がついている
１：灰がかなりついている
【００４８】
【表２】

【００４９】
上記の評価結果から明らかなように、本発明のラテックスは、公知のラテックス（上記ハのもの）と異なり、べとつきにくく、且つ静電気によるゴミ付着が起きにくい。また、本発明のラテックスは、少量でも優れた耐静電気特性を有している。
更に、ハロゲン化銀写真感光材料の製造例を挙げる。
即ち、本発明のラテックスを用いたハロゲン化銀写真感光材料の製造例を挙げる。
【００５０】
感光材料１の作成
（乳剤Ｅｍ−１の調製）
下記のようにして平板状沃臭化銀粒子からなる乳剤Ｅｍ−１を調製した。

【００５１】
特公昭５８−５８２８８号明細書に示されている混合撹拌機を用いて、３５℃でＡ１液にＢ１液及びＣ１液各々４７５．０ｍｌを同時混合法（ダブルジェット法）により２．０分で添加し、核形成を行った。
Ｂ１液及びＣ１液の添加終了後、６０分かけてＡ１液の温度を６０℃に上昇させ、Ｄ１液の全量を添加し、ＫＯＨ３％水溶液でｐＨを５．５とし、再びＢ１液及びＣ１液を各々５５．４ｍｌ／分の添加速度で４２分間添加した。この間、Ｅ１液を用いて銀電位（飽和銀−塩化銀電極を比較電極として銀イオン選択電極で測定）を＋８ｍＶ及び＋３０ｍＶになるように制御した。
添加終了後、ＫＯＨ３％水溶液でｐＨを６．０とし、直ちに脱塩、水洗を行って種乳剤を得た。この種乳剤を電子顕微鏡によって観察したところ、ハロゲン化銀粒子の全投影面積の９０％以上が最大隣接辺比が１．０〜２．０の六角平板粒子よりなり、六角平板粒子の平均厚さは０．０９０μｍ、平均円相当直径は０．５１０μｍであった。
【００５２】
得られた種乳剤を５３℃にし、分光増感色素Ａ（５，５´−ジクロロ−９−エチル−３，３´−ジ−（３−スルホプロピル）オキサカルボシアニンナトリウム塩の無水物）４５０ｍｇ、分光増感色素Ｂ｛５，５´−ジ−（ブトキシカルボニル）−１，１´−ジ−エチル−３，３´−ジ−（４−スルホブチル）ベンゾイミダゾロカルボシアニンナトリウムの無水物）８ｍｇを固体微粒子状の分散物として添加後に、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデン（ＴＡＩ）６０ｍｇ、アデニン１５ｍｇ、チオシアン酸アンモニウム５０ｍｇ、塩化金酸２．５ｍｇ及びチオ硫酸ナトリウム５．０ｍｇを含有する水溶液、沃化銀微粒子乳剤（平均粒径０．０５μｍ）５ミリモル相当、トリフェニルホスフィンセレナイド６．０ｍｇの分散液を加え、総計２時間３０分の熟成を施した。熟成終了時に安定剤としてＴＡＩを７５０ｍｇ添加した。
【００５３】
尚、分光増感色素の固体微粒子分散物は、２７℃の水に色素を加え高速攪拌機（ディゾルバー）で３５００ｒ．ｐ．ｍ．にて３０〜１２０分攪拌して得た。またトリフェニルホスフィンセレナイドの分散液は、トリフェニルホスフィンセレナイド１２０ｇを５０℃の酢酸エチル３０ｋｇ中に添加して攪拌し、完全に溶解させ、他方でゼラチン３．８ｋｇを純水３８ｋｇに溶解し、これにドデシルベンゼンスルホン酸ナトリウム２５重量％水溶液９３ｇを添加し、これらの２液を混合して直径１０ｃｍのディゾルバーを有する高速攪拌型分散機により５０℃、分散翼周速４０ｍ／秒で３０分間分散し、その後速やかに減圧して酢酸エチルの残留濃度が０．３重量％以下になるまで、攪拌を行いつつ酢酸エチルを除去し、純水で希釈して８０ｋｇに仕上げて得た。
【００５４】
（乳剤Ｅｍ−２の調製）
乳剤Ｅｍ−１を種乳剤として、以下の溶液を用いて平板状沃臭化銀粒子からなる乳剤Ｅｍ−２を調製した。

【００５５】
＊０．０６モルの沃化カリウムを含む５．０重量％のゼラチン水溶液６．６４リットルに、７．０６モルの硝酸銀と、７．０６モルの沃化カリウムを含む水溶液それぞれ２リットルを１０分間かけて添加した。微粒子形成中のｐＨは硝酸を用いて２．０に、温度は４０℃に制御した。粒子形成後、炭酸ナトリウム水溶液を用いてｐＨを６．０とした。
【００５６】
反応容器内でＡ２液を５５℃に保ちながら激しく攪拌し、Ｂ２液及びＣ２液のそれぞれ半量を３５分かけて同時混合法にて添加した。この間ｐＨは５．８に保った。１％ＫＯＨ水溶液にてｐＨを８．８とし、Ｂ２液、Ｃ２液及びＤ２液をＤ２液がなくなるまで同時混合法で添加した。０．３％クエン酸水溶液にてｐＨを６．０とし、Ｂ２液及びＣ２液の残量を２５分かけて同時混合法で添加した。この間のｐＡｇは８．９に保った。尚、Ｂ２液とＣ２液の添加速度は臨界成長速度に応じて関数様に変化させ、小粒子の発生とオストワルド熟成による多分散化を抑えた。
添加終了後、Ｅｍ−１と同様に脱塩、水洗、再分散を行い、再分散後４０℃でｐＨを５．８０、ｐＡｇを８．２に調製した。
【００５７】
得られたハロゲン化銀乳剤を電子顕微鏡によって観察したところ、平均円相当直径０．９１μｍ、平均厚さ０．２３μｍ、平均アスペクト比約４．０、粒径分布の広さ（粒径分布の標準偏差／平均粒径）２０．５％の平板状ハロゲン化銀粒子からなる乳剤であった。
【００５８】
得られた乳剤を４７℃にし、沃化銀微粒子乳剤（平均粒径０．０５μｍ）５ミリモル相当、分光増感色素Ａを３９０ｍｇ及び分光増感色素Ｂを４ｍｇを固体微粒子状の分散物として添加後に、アデニン１０ｍｇ、チオシアン酸アンモニウム５０ｍｇ、塩化金酸２．０ｍｇ及びチオ硫酸ナトリウム３．３ｍｇを含有する水溶液、トリフェニルホスフィンセレナイド４．０ｍｇの分散液を加え、総計２時間３０分の熟成を施した。熟成終了時に安定剤としてＴＡＩを７５０ｍｇを添加した。
【００５９】
調製したＥｍ−１とＥｍ−２それぞれを重量比で６：４に混合した乳剤を用いて以下の処方で試料を作製した。
濃度０．１５に青色着色した厚さ１７５μｍのポリエチレンテレフタレートフィルムベースの両面に、下記処方（片面当たり）でクロスオーバーカット層、乳剤層、中間層、保護層の順に、片面当たりの銀付量１．８ｇ／ｍ^２、保護層ゼラチン量０．４ｇ／ｍ^２、中間層ゼラチン量０．４ｇ／ｍ^２、乳剤層ゼラチン量１．５ｇ／ｍ^２、クロスオーバーカット層ゼラチン量０．２ｇ／ｍ^２になるように塗布し、乾燥して試料を作製した。
【００６０】

【００６１】

【００６２】

【００６３】

【００６４】
表３に記載の如く、ラテックス種、ラテックスの添加量を変更した以外は同様にしてＮｏ．２〜２１を作成した。
【００６５】
【化１７】

【００６６】
【化１８】

【００６７】
【化１９】

【００６８】
（評価方法）
＜スタチックマーク発生テスト＞
ゴムシート上に未露光感光材料を置き、試料を２３℃・２０％ＲＨ下で調湿し、暗やみ中で、上からネオプレンゴムロールでしごいて圧着後、剥離することによりスタチックマークを発生させ、現像処理後、スタチックマークの発生の程度を目視で下記の５段階に評価した。結果を表３に示す。
Ａ：スタチックマークの発生が認められない
Ｂ：スタチックマークが少し発生
Ｃ：スタチックマークが相当発生
Ｄ：スタチックマークが著しく発生
Ｅ：スタチックマークが全面に発生
【００６９】
＜ゴミ付着評価＞
作成した試料を５ｃｍ平方の大きさに切取り、それぞれ互いが接触しないように２３℃・２０％ＲＨの条件下に１日放置し、その後、試料の表面をナイロンの布でこすり、たばこの灰の入った灰皿の上にかざして灰の付着する状態を観察した。結果を表３に示す。
５：全くつかない
４：よく見るとついている
３：ついているのに容易に気がつく
２：ついている
１：かなりついている
【００７０】
【表３】

【００７１】
上記の評価結果から明らかなように、本発明のラテックスは、公知のラテックス（上記ハのもの）と異なり、スタチックマークが発生しにくく、且つ静電気によるゴミ付着が起きにくい。また、本発明のラテックスは、少量でも優れた耐静電気特性を有している。
【００７２】
【発明の効果】
本発明によれば、静電気障害の起きにくいシート状材料及び該シート状材料用の新規な素材を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel latex composition and a sheet-like material having an improved antistatic property using the same.
[0002]
[Prior art]
In general, a sheet material composed of a support having electrical insulation and a hydrophilic layer having a certain function is often charged by contact with and peeling from the same or different substances during the production of the sheet material and at the time of use. This charging phenomenon may cause sheet materials to stick to each other due to electrification and deteriorate handling properties, or dust may adhere to deteriorate quality, or a discharge phenomenon may occur and adversely affect the functional layer. Or make it uncomfortable.
[0003]
In order to eliminate these problems caused by static electricity, a conductive layer is provided on the support or a surfactant is added to the hydrophilic colloid layer. In the former case, the cost increases. May be different or affect functionality. Also, there is a method of adding a conductive water-soluble polymer to the hydrophilic colloid layer, but the surface is easy to stick and the materials tend to stick to each other.
[0004]
U.S. Pat. No. 4,266,015 discloses a technique in which a fluorine-containing polymer latex is added to a hydrophilic colloid layer of a silver halide photographic light-sensitive material to reduce electrostatic interference. However, with this technique, the silver halide photosensitive material prepared by adding the latex in the examples tends to be sticky on the surface and easily stick to each other. Such a problem is not only a silver halide material but also a material in which a functional layer is formed by applying and drying a coating solution containing water-soluble polymer or water-dispersed polymer as a binder material on a support using water as a solvent. Recognized in common.
[0005]
As a result of earnestly examining the improvement of the fluorine-containing polymer latex in order to improve the stickiness phenomenon, the present inventors have found that the material obtained by polymerizing the fluorine-containing monomer in the presence of the hydrophilic polymer reduces the stickiness. Furthermore, it has been found that when a latex obtained by polymerizing a fluorine-containing monomer in the presence of a conductive water-soluble polymer is added to a hydrophilic binder, not only the stickiness is reduced, but also electrostatic damage is remarkably reduced. It was.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a sheet-like material that is less prone to static electricity damage and a novel material for the sheet-like material.
[0007]
[Means for Solving the Problems]
The present invention for solving the above problems has the following configuration.
1. A latex composition polymerized by using a polymerizable monomer having a fluorine atom in the presence of a hydrophilic polymer, wherein the hydrophilic polymer has vinylbenzenesulfonic acid or a salt thereof as a monomer unit. the latex composition characterized in that it.
[0008]
2. In a sheet-form material having at least one hydrophilic colloid layer on a support, 1 to 40% by weight of the latex composition described in 1 is contained in the hydrophilic colloid binder as a solid content in the hydrophilic colloid layer. A sheet-like material characterized by:
[0011]
3. 3. The sheet material as described in 2 above, wherein the sheet material is a photographic photosensitive material.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Details of the present invention will be described below.
First, the hydrophilic polymer will be described.
The hydrophilic polymer includes a synthetic water-soluble polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention.
[0013]
Among these, examples of the synthetic water-soluble polymer include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure. Nonionic groups include, for example, ether groups, ethylene oxide groups, hydroxy groups, and anionic groups include, for example, sulfonic acid groups or salts thereof, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof. , Etc.
[0014]
Examples of the natural water-soluble polymer include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.
[0015]
As the polymer having a hydrophilic group, those having an anionic group and those having a nonionic group and an anionic group can be preferably used in both the synthetic water-soluble polymer and the natural water-soluble polymer. In the present invention, the hydrophilic polymer may be dissolved in an amount of 0.05 g or more with respect to 100 g of water at 20 ° C., and preferably 0.1 g or more.
[0023]
Examples of natural water-soluble polymers include gelatin, lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, nigeran, and derivatives thereof.
[0024]
In addition, examples of natural water-soluble polymer derivatives include sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkyl phosphorylated, and salts thereof, and particularly dextran and derivatives thereof. preferable.
In the present invention, two or more hydrophilic polymers may be used in combination.
[0025]
Examples of polymers having vinylbenzenesulfonic acid or a salt thereof as a monomer unit are given below.
[0026]
[Chemical 7]

[0027]
[Chemical 8]

[0028]
[Chemical 9]

[0029]
Next, a polymerizable monomer having a fluorine atom will be described.
Monomers that can be preferably used in the present invention are compounds represented by the following general formulas (F1) and (F2).
[0030]
[Chemical Formula 10]

In the formula, R represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom, Rf represents a linear, branched or cyclic alkyl group substituted with a fluorine atom, and this alkyl group is preferably a carbon atom. The number is 1 to 10, and it may be substituted with a group or atom other than a fluorine atom. Examples of these groups or atoms include a hydroxy group, a halogen atom (for example, Cl, Br, etc.), and the like. .
[0031]
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In the formula, R ¹ represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms. R ² represents a monovalent substituent, and R ² may be linked to each other to form a ring. R ^f represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group, an aryl group, or an alkylaryl group in which at least one hydrogen atom is substituted with a fluorine atom. X is a general formula.
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In which R represents an alkylene group having 1 to 10 carbon atoms, an arylene group or an aralkylene group, -L- represents an -O- group, an -S- group, -NR ^3. A group (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms; the same shall apply hereinafter), a —CO— group, a —OCO— group, a —SCO— group, a —CONR ³ — group, a —SO ₂ — group, -NR ³ SO ₂ - group, _-SO 2 NR ³ - group, an -SO- group,
[0033]
[Outside 1]

Is 0 or 1. l is an integer of 0 to 4, preferably an integer of 0 to 2, m is an integer of 0 to 4, preferably 0 or 1, and n is an integer of 1 to 5, particularly 1. Or 2 is preferable.
[0034]
Next, examples of the monomer used in the present invention will be given.
[0035]
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[0036]
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[0037]
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[0038]
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[0039]
As a monomer copolymerizable with a polymerizable monomer having a fluorine atom, a compound having a vinyl group, for example, an acrylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, Methacrylic acid esters such as cyclohexyl methacrylate and sulfopropyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, styrene, methyl styrene Styrenes such as chloromethylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, isoprene, etc. .
The preferred copolymerization ratio of the polymerizable monomer having a fluorine atom and the copolymerizable monomer may be 3% or more by weight, but preferably 5 to 80%.
[0040]
The sheet-like material of the present invention is not particularly limited as long as it has a hydrophilic colloid layer on the support.
The hydrophilic colloid layer of the present invention is a coating film using hydrophilic colloid as a binder (binder).
[0041]
A preferable content of the latex of the present invention is 1 to 40% by weight in solid content with respect to the binder. A plurality of types may be used in combination.
The polymer of the present invention is suitable for a sheet-like material, particularly a silver halide photographic light-sensitive material.
[0042]
【Example】
Next, synthesis examples of the latex composition according to the present invention and other examples of the present invention will be given.
First, examples of latex production are given.
Latex production example 1
360 ml of distilled water degassed with N ₂ gas and 4.5 g of hydrophilic polymer (SP-4) are added to 1 liter of Kolben and heated to 80 ° C. To this, 0.50 g of ammonium persulfate dissolved in 5 ml of distilled water was quickly added, and there was a mixture of 50 g of polymerizable monomer F-1 (where n = 4) having fluorine atoms, 40 g of styrene and 0.5 g of acrylic acid. In about 1 hour, and after the completion of the addition, the mixture is further stirred for 3 hours. 0.2 g of ammonium persulfate was added, and the mixture was further cooled to room temperature to obtain the intended latex A. The average particle size of the obtained latex was about 0.2 μm.
[0043]
Latex production examples 2-12
As shown in Table 1, it was prepared in the same manner as in Latex Production Example 1 except that the types and amounts of the hydrophilic polymer, the polymerizable monomer having a fluorine atom, and the copolymerizable monomer were changed.
[0044]
[Table 1]

[0045]
Next, a sheet material production example will be given.
60 ml of water is added to 5 g of gelatin, a latex solution is added so that the solid content of the latex is 0.5 g, and after dissolution by heating, 0.02 g of polymethyl methacrylate fine particles having an average particle diameter of 3 μm and a crosslinking agent (H-1) 0 are added. .05 g, water was added to finish the solution to 100 ml, and a sample was prepared by coating and drying on both sides of an underdrawn polyethylene terephthalate support (thickness: 100 μm) so that the amount of gelatin was 2 g / m ^2. did. In addition, samples in which the amount of latex was changed by changing the amount of latex added to the coating solution were also prepared.
[0046]
<Evaluation of stickiness>
Cut out 5 pieces of the prepared sample to a size of 3 cm square and leave them for one day under the conditions of 23 ° C and 80% RH so that they do not touch each other. And left at 40 ° C. and 80% RH for half a day. The sample was taken out, the overlapped sample was peeled off by hand, and the ease of peeling was evaluated according to the following evaluation criteria. The results are shown in Table 2.
5: Removes gently 4: Slightly resistant 3: Resistant 2: Very resistant 1: Part of the coating film is peeled off
<Evaluation of dust adhesion>
Cut out 5 pieces of the prepared sample to a size of 5 cm square, and leave them for one day under conditions of 23 ° C. and 20% RH so that they do not contact each other. Then, rub the surface of the sample with a nylon cloth, and tobacco It was held over an ashtray containing ash, and the state of ash adhesion was observed and evaluated according to the following evaluation criteria. The results are shown in Table 2.
5: No ash at all 4: Ashes are closely observed 3: Ashes are easily noticed 2: Ashes are attached 1: Ashes are considerably attached [0048]
[Table 2]

[0049]
As is clear from the above evaluation results, the latex of the present invention is unlikely to be sticky and does not easily adhere to dust due to static electricity, unlike the known latex (the above-mentioned one). Further, the latex of the present invention has excellent antistatic properties even in a small amount.
Furthermore, production examples of silver halide photographic light-sensitive materials are given.
That is, a production example of a silver halide photographic light-sensitive material using the latex of the present invention is given.
[0050]
Preparation of photosensitive material 1 (Preparation of emulsion Em-1)
Emulsion Em-1 consisting of tabular silver iodobromide grains was prepared as follows.

[0051]
Using a mixing stirrer disclosed in Japanese Patent Publication No. 58-58288, 475.0 ml each of B1 liquid and C1 liquid at 35 ° C. in 2.0 minutes by the simultaneous mixing method (double jet method). Added and nucleated.
After the addition of the B1 and C1 liquids, the temperature of the A1 liquid is raised to 60 ° C. over 60 minutes, the entire amount of the D1 liquid is added, the pH is adjusted to 5.5 with a KOH 3% aqueous solution, and the B1 and C1 liquids are added again. Were added at a rate of 55.4 ml / min for 42 minutes each. During this period, the E1 solution was used to control the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a comparison electrode) to be +8 mV and +30 mV.
After the addition was completed, the pH was adjusted to 6.0 with a 3% aqueous solution of KOH, and immediately after desalting and washing with water, a seed emulsion was obtained. When this seed emulsion was observed with an electron microscope, 90% or more of the total projected area of the silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains was Was 0.090 μm and the average equivalent circle diameter was 0.510 μm.
[0052]
The obtained seed emulsion was brought to 53 ° C. and spectral sensitizing dye A (anhydride of 5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) oxacarbocyanine sodium salt) 450 mg , Spectral sensitizing dye B {5,5'-di- (butoxycarbonyl) -1,1'-di-ethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium anhydride] After adding 8 mg as a solid fine particle dispersion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 60 mg, adenine 15 mg, ammonium thiocyanate 50 mg, chloroauric acid 2.5 mg And an aqueous solution containing 5.0 mg of sodium thiosulfate, silver iodide fine grain emulsion (average grain size 0.05 μm) equivalent to 5 mmol, triphenylphosphine selenide 6.0 mg Dispersion was added and subjected to aging for 2 hours 30 minutes total. At the end of aging, 750 mg of TAI was added as a stabilizer.
[0053]
The solid fine particle dispersion of the spectral sensitizing dye was prepared by adding the dye to water at 27 ° C. and using a high-speed stirrer (dissolver) at 3500 r. p. m. And stirred for 30 to 120 minutes. The dispersion of triphenylphosphine selenide was prepared by adding 120 g of triphenylphosphine selenide into 30 kg of ethyl acetate at 50 ° C. and stirring to completely dissolve, while dissolving 3.8 kg of gelatin in 38 kg of pure water. Then, 93 g of a 25% by weight aqueous solution of sodium dodecylbenzenesulfonate was added to the mixture, and these two liquids were mixed and mixed at 50 ° C. for 30 minutes at a dispersion blade peripheral speed of 40 m / sec using a high-speed stirring disperser having a 10 cm diameter dissolver. The mixture was dispersed, and then rapidly decompressed to remove ethyl acetate while stirring until the residual concentration of ethyl acetate was 0.3% by weight or less, and diluted with pure water to obtain 80 kg.
[0054]
(Preparation of emulsion Em-2)
Emulsion Em-2 comprising tabular silver iodobromide grains was prepared using Emulsion Em-1 as a seed emulsion and the following solution.

[0055]
* Into 6.64 liters of a 5.0 wt% gelatin aqueous solution containing 0.06 mol potassium iodide, 2 liters each of an aqueous solution containing 7.06 mol silver nitrate and 7.06 mol potassium iodide for 10 minutes. Added over time. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.
[0056]
The A2 liquid was vigorously stirred while maintaining the temperature at 55 ° C. in the reaction vessel, and half of each of the B2 liquid and C2 liquid was added over 35 minutes by the simultaneous mixing method. During this time, the pH was kept at 5.8. The pH was adjusted to 8.8 with a 1% aqueous KOH solution, and the B2, C2, and D2 solutions were added by the simultaneous mixing method until the D2 solution disappeared. The pH was adjusted to 6.0 with a 0.3% citric acid aqueous solution, and the remaining amounts of the B2 liquid and the C2 liquid were added by a simultaneous mixing method over 25 minutes. During this time, pAg was kept at 8.9. Note that the addition rates of the B2 solution and the C2 solution were changed in a function manner according to the critical growth rate to suppress the generation of small particles and polydispersion due to Ostwald ripening.
After completion of addition, desalting, washing with water and redispersion were carried out in the same manner as Em-1, and after redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.2 at 40 ° C.
[0057]
When the obtained silver halide emulsion was observed with an electron microscope, the average equivalent circle diameter was 0.91 μm, the average thickness was 0.23 μm, the average aspect ratio was about 4.0, and the breadth of the grain size distribution (standard of grain size distribution). Deviation / average grain size) The emulsion was composed of 20.5% tabular silver halide grains.
[0058]
The obtained emulsion was brought to 47 ° C., silver iodide fine grain emulsion (average grain size 0.05 μm) equivalent to 5 mmol, spectral sensitizing dye A 390 mg and spectral sensitizing dye B 4 mg were added as a solid fine particle dispersion. Later, an aqueous solution containing 10 mg of adenine, 50 mg of ammonium thiocyanate, 2.0 mg of chloroauric acid and 3.3 mg of sodium thiosulfate, and a dispersion of 4.0 mg of triphenylphosphine selenide were added, and the aging was carried out for a total of 2 hours 30 minutes. gave. At the end of aging, 750 mg of TAI was added as a stabilizer.
[0059]
A sample was prepared with the following formulation using an emulsion prepared by mixing Em-1 and Em-2 in a weight ratio of 6: 4.
On both sides of a 175 μm-thick polyethylene terephthalate film base colored blue with a concentration of 0.15, the amount of silver applied on one side in the order of crossover cut layer, emulsion layer, intermediate layer and protective layer is as follows: 0.8 g / m ² , protective layer gelatin amount 0.4 g / m ² , intermediate layer gelatin amount 0.4 g / m ² , emulsion layer gelatin amount 1.5 g / m ² , crossover cut layer gelatin amount 0.2 g / m ² was applied and dried to prepare a sample.
[0060]

[0061]

[0062]

[0063]

[0064]
As shown in Table 3, No. 1 was changed in the same manner except that the addition amount of latex type and latex was changed. 2 to 21 were created.
[0065]
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[0066]
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[0067]
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[0068]
(Evaluation methods)
<Static mark generation test>
An unexposed photosensitive material is placed on a rubber sheet, the sample is conditioned at 23 ° C and 20% RH, and after pressing with a neoprene rubber roll from the top in the dark, pressure is generated and a static mark is generated. After development, the degree of occurrence of static marks was visually evaluated in the following five levels. The results are shown in Table 3.
A: Static mark generation is not observed B: Static mark is slightly generated C: Static mark is considerably generated D: Static mark is significantly generated E: Static mark is generated on the entire surface
<Evaluation of dust adhesion>
Cut the prepared sample to a size of 5 cm square and leave it at 23 ° C and 20% RH for 1 day so that they do not touch each other. Then, rub the surface of the sample with a nylon cloth and remove the tobacco ash The ash was attached to the ashtray and observed. The results are shown in Table 3.
5: Not attached at all 4: Attach when you look closely 3: You can easily notice it is attached 2: Attach 1: Pretty attached
[Table 3]

[0071]
As is clear from the above evaluation results, the latex of the present invention is unlikely to generate a static mark and is unlikely to cause dust adhesion due to static electricity, unlike the known latex (the above-mentioned one). Further, the latex of the present invention has excellent antistatic properties even in a small amount.
[0072]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the sheet-like material which does not generate | occur | produce an electrostatic failure easily, and the novel raw material for this sheet-like material can be provided.

Claims (3)

A latex composition polymerized by using a polymerizable monomer having a fluorine atom in the presence of a hydrophilic polymer, wherein the hydrophilic polymer has vinylbenzenesulfonic acid or a salt thereof as a monomer unit. the latex composition characterized in that it. In a sheet-like material having at least one hydrophilic colloid layer on a support, 1 to 40% by weight of the latex composition according to claim 1 as a solid content in the hydrophilic colloid binder in the hydrophilic colloid layer. A sheet-like material characterized by containing. The sheet-like material according to claim 2, wherein the sheet-like material is a photographic photosensitive material.