JP3741377B2 - Roll film with reduced curling and silver halide photographic light-sensitive material - Google Patents

Description

【００３６】
前記共重合ポリエステルは、本発明の効果を損なわない範囲で共重合成分として、ポリアルキレングリコール及び／又は飽和脂肪族ジカルボン酸ポリエーテルジカルボン酸を用いているのが好ましい。
【００３７】
前記ポリアルキレングリコールとしては、ポリエチレングリコール、ポリテトラメチレングリコール等を挙げることができる。使用することのできるポリアルキレングリコールの分子量は特に限定されないが、好ましくは、300〜20,000、より好ましくは600〜10,000、特に好ましくは1,000〜5,000である。特にポリアルキレングリコールとしてはポリエチレングリコールが好ましい。
【００３８】
飽和脂肪族ジカルボン酸としては、例えばそのエステル形成誘導体が好ましく、アジピン酸、セバシン酸のエステルであるアジピン酸ジメチル、セバシン酸ジメチルなどが用いられる。好ましくはアジピン酸ジメチルである。
【００３９】
ポリエーテルジカルボン酸としては、ポリエチレンオキシジカルボン酸、ポリプロピレンオキシジカルボン酸、ポリ（エチレン／プロピレン）オキシジカルボン酸、ポリテトラメチレンオキシジカルボン酸及びその共重合体などが好ましいが、ポリエステルの重合反応性やフィルムの平面安定性の点で特に、下記式で示されるポリエチレンオキシジカルボン酸がより好ましい。
【００４０】
R¹OOCCH₂−(O−CH₂CH₂)，−OCH₂COOR²
（Ｒ¹，Ｒ²：Ｈまたは炭素数１〜８のアルキル基、ｎ：正の整数）
また、ポリエーテルジカルボン酸成分の共重合割合としては、反応生成物のポリエステルに対して２〜30重量％、好ましくは５〜15重量％、特に好ましくは７〜12重量％である。
【００４１】
本発明に用いられるポリエステル樹脂には、本発明の効果を阻害しない範囲で、更に他の成分が共重合されていても良いし、他のポリマーがブレンドされていてもかまわない。ブレンドされるポリマーとしては、ポリエステル系のポリマーが好ましい。
【００４２】
−ポリエステルの製造−
本発明に用いられるポリエステルはともに、重合段階でリン酸、亜リン酸およびそれらのエステルならびに無機粒子（シリカ、カオリン、炭酸カルシウム、リン酸カルシウム、二酸化チタンなど）が含まれていてもよいし、重合後ポリマーに無機粒子などがブレンドされていてもよい。さらに重合段階、重合後のいずれかの段階で適宜に顔料、紫外線吸収剤、酸化防止剤などを添加してもかまわない。
【００４３】
共重合ポリエステルを得るには、酸成分とグリコール成分とをエステル交換した後に、前述の共重合成分を添加し、溶融重合を行っても良いし、又、共重合成分をエステル交換する前に添加し、エステル交換した後に溶融重合を行っても良いし、または溶融重合で得られたポリマーを固相重合するなど公知の合成方法を採用することができる。
【００４４】
このエステル交換時に用いる触媒としては、マンガン、カルシウム、亜鉛、コバルト等の金属の酢酸塩、脂肪酸塩、炭酸塩等を挙げることができる。これらの中でも、酢酸マンガン、酢酸カルシウムの水和物が好ましく、さらにはこれらを混合したものが好ましい。前記エステル交換時及び／又は重合時に反応を阻害したりポリマーを着色したりしない範囲で水酸化物や脂肪族カルボン酸の金属塩、第四級アンモニウム塩などを添加することも有効であり、中でも水酸化ナトリウム、酢酸ナトリウム、テトラエチルヒドロキシアンモニウムなどが好ましく、特に酢酸ナトリウムが好ましい。
【００４５】
本発明に用いるポリエステルには、種々の添加剤を含有せしめることができる。たとえば、写真乳剤層を塗設した写真用支持体のエッジから光が入射したときに起こるライトパイピング現象（ふちかぶり）を防止する目的で、該ポリエステルに染料を添加することもできる。この染料につき、その種類は特に限定されないが、製膜工程上、耐熱性に優れたものが好ましく、例えば、アンスラキノン系化学染料などが挙げられる。
【００４６】
本発明に用いるポリエステルフィルムの層構造としては、二層以上任意の数の層が積層された積層構造であれば良い。なお、本発明の支持体に含まれるポリエステル層とは、例えば下引層などの塗設層はポリエステル層とはみなさない。
【００４７】
積層構造のフィルムの厚みの総和は特に限定されず、用途に応じて任意に定めることができるのが通常40〜250μm、特に65〜180μmが好ましい。
【００４８】
また、ポリエステル層における積層構造が二層、三層である場合を含め、四層以上の積層構成であっても、積層構造のポリエステル層をその厚みを二等分する位置を中心として両表面側に二分割した場合に、その分割した両側における層構成が非対称であることが好ましい。
【００４９】
ここでいう非対称とは物理的、機械的あるいは化学的に相違することを意味し、例えばポリエステル層、共重合ポリエステル層または他の素材からなる層の構成順序、ポリエステル層、共重合ポリエステル層または他の素材からなる層の厚さ、半分に分割する面の上下でのポリエステルもしくは共重合ポリエステルを構成する主構成成分量が異なるとか、共重合成分又は共重合成分量が異なるとか、さらには固有粘度が異なることとか、又、分割面でのそれぞれのポリエステル層のいずれかが共重合成分の種類または共重合成分の含有量が相違することも含まれる。これらの相違のうち、化学的相違によるものが効果の点が好ましい。
【００５０】
これら積層ポリエステル層の非対称性を確認する方法としては、各種分析機器を用いることを挙げることができ、特に限定されないが、層構成についてはフィルムの断面を顕微鏡観察により確認することができ、また顕微鏡写真を撮影することによっても確認することができる。また、これを顕微鏡観察を行いながら、各層を削り取るか、これを半分に分割する面まで、それぞれ上下から削り取り上下の層もしくは各層それぞれの分析対象物を得て、加水分解をおこない液体クロマトグラフィーとかNMRとかの各種測定装置で測定してもよいし、分析対象物を溶媒に溶解した後にNMR分析や、GPC（ゲルパーミションクロマトグラフィー）分析や、固有粘度を測定する等してもよいし、分析対象物をそのまま粉末でＸ線分光分析をし、もしくはKBr等に混ぜてIR（赤外分光機器）等の分析をし、結果として絶対量、もしくはそれに相当する測定結果のピークの位置、強度の違い等でも両外層の非対称性を確認ないし測定することができる。
【００５１】
このような樹脂を組み合わせて二層以上の積層構造を有するフィルムは、次のようにして製造することができる。すなわち、例えば２種のポリエステルを別々の押出機から溶融押出した後、溶融ポリマーの導管内または押出口金内において層流状で多層に接合せしめて押出し、冷却ドラム上で冷却固化し未延伸フィルムを得た後に、二軸延伸し熱固定する方法、もしくはポリエステル又は共重合ポリエステル単体及び、積層フィルムを押出機から溶融押出し、冷却ドラム上で冷却固化した未延伸フィルムまたは該未延伸フィルムを一軸延伸した一軸配向フィルムの面に、必要に応じてアンカー剤、接着剤等をコーティングした後その上にポリエステル又は共重合ポリエステル単体及び、積層フィルムをエクストルージョンラミネートし、次いで二軸延伸を完了した後熱固定するエクストルージョンラミネート方法などがあるが、工程の簡易性から共押出法が好ましい。
【００５２】
延伸条件は特に限定されないが、一般的には複数のポリエステル層のガラス転移温度（Tg）の高い方のTgからTg＋100℃の温度範囲で二軸方向に延伸する。このとき上記単層ポリエステル層の延伸方法と同様に下記Ａ、Ｂ、Ｃの方法を採ることができる。延伸倍率は面積比で４〜16倍の範囲で行われることが好ましい。また熱固定は150〜240℃の温度範囲で行うことができる。
【００５３】
（Ａ）未延伸シートをまず縦方向に延伸し、次いで横方向に延伸する方法
（Ｂ）未延伸シートをまず横方向に延伸し、次いで縦方向に延伸する方法
（Ｃ）未延伸シートを１段または多段で縦方向に延伸した後、再度縦方向に延伸し、次いで横方向に延伸する方法。
【００５４】
この様な支持体の経時カールのコントロールは、積層比率、ポリエステル樹脂の種類を任意で選ぶことで行なうことができる。特に、経時収縮性の異なる樹脂層を積層すれば、経時カール性を発現することができる。ここで言う、経時収縮とは、同一の温度，湿度の平衡状態のもとでも、経時によって寸法変化（収縮）が起こる現象であり、経時カール性を有する積層フィルムにおいて、特に好ましくは積層フィルムを構成する樹脂層を単層で製膜した場合には最大の経時収縮性を有する樹脂フィルムの経時収縮率は、最小の樹脂層の経時収縮率の２倍以上あることである。
【００５５】
本発明の積層重合体フィルムをより効果的なものとするためには、積層フィルムの経時カールを大きくする必要があるが、そのためには積層フィルムを構成する各樹脂間のTgの差を大きくし、該積層重合体フィルムの貯蔵温度をT_Hとすると、少なくとも１層の樹脂層のTgを、Tg≦T_H＋50℃とすることが望ましい。
【００５６】
また経時収縮は熱収縮と同様に製造時の延伸条件や熱固定条件に影響されるため、これらの製膜条件についても決定しておくことが望ましい。
【００５７】
またTACフィルムのように既に形成されたコアセットカールに対しての優れた現像処理後のカール解消性を本発明の積層重合体フィルムに付与するには、吸水性の高い樹脂層がフィルムの表面層になるようにフィルムを設計すれば良い。
【００５８】
ロール状に巻取るときの条件としてはフィルムの巻取り曲率（Ｒ）を以下の式に示される範囲内とすることによりこのような効果はより大きく得られ好ましい。
【００５９】
0＜Ｒ(m^-1)＜Ｒ₀ Ｒ₀＝900a／（400−9b＋9a）
ａ：フィルムを平板の上に静置した状態で、23℃、55％RHで１年間保存した場合の経時カール値の増加量
ｂ：フィルムを曲率100m^-1となる巻取り径（φ20mm）で巻いた状態で、23℃、 55％RHで１年間保存した場合のカール値の増加量
驚くべきことに、本発明の積層重合体フィルムは、Ｒを上式の範囲内とすることにより、該積層フィルム構成している各樹脂を単独で使用し同じ製膜条件で作成した、どの単一樹脂（単層）フィルムよりコアセットカール値は小さくなる。
【００６０】
このような積層重合体フィルムに感光層などの機能性膜に塗設することで、ロール状機能性フィルムの使用時のコアセットカールは軽減される。
【００６１】
但し、一般的なフィルムの巻取り径としては、写真ネガフィルムのパトローネ径の約10mmから、その製造工程での元巻ロールの約１ｍ程度であり、この場合の巻取り曲率としては２m^-1から200m^-1程度であるので、上記Ｒ値がこの範囲内となるフィルムが特に望ましい。
【００６２】
本明細書においてフィルムの巻き径又は巻取り曲率とはコアがある場合と無い場合の両者を意味し、また巻取ったロール状フィルムの断面は真円でなくてもかまわない。
【００６３】
また本発明は自己支持性フィルム自体がロール状で貯蔵されながら使用されるロール状OHPシートやロール状製図用フィルムまたはロール状印刷用シートなどに用いられるが、これに限定されるものではない。
【００６４】
本発明における配向結晶完了前に下引樹脂を塗設するとは、前述の熱固定を行う前に下引樹脂を塗設することである。即ち、未延伸後あるいは、二軸延伸後に下引樹脂を塗設し、少なくとも１層の下引樹脂が設けられた後に、熱固定を行うことを言う。これらの中で、好ましくは、未延伸後または、一軸延伸後に塗設するのが好ましい。
【００６５】
本発明において使用する下引樹脂は熱固定を行う前に塗設される公知のものが使用できる。例えば、米国特許第2,852,378号、同第358,608号、同第3,630,741号、同2,627,088号、同2,698,235号、特開昭51-135991号、特公昭52-48312号、ベルギー特許第721,469号、同742,769号等に記載のビニルハロゲノエステル含有コポリマーまたはビニルハロゲノエステル含有コポリマーと塩化ビニルおよび／または塩化ビニリデン含有コポリマー、特公昭58-58661、特公昭58-55497、特開昭52-108114等に記載のジオレフィン類を単量体として含むコポリマー、特開昭61-204242、特開昭61-204241等に記載のアクリル系ポリマー、特公昭57-971、特開昭61-204240、特開昭60-248231、特開平3-265624等に記載のポリエステル系ポリマー等が挙げられる。
【００６６】
【実施例】
以下実施例により本発明を具体的に詳述する。
【００６７】
［サンプルの作成］
サンプル１
テレフタル酸100重量部、エチレングリコール64重量部に酢酸カルシウム水和物0.1重量部を添加し、常法によりエステル化反応を行った。得られた生成物に5-ナトリウムスルホジ(β-ヒドロキシエチル)イソフタル酸のエチレングリコール溶液（濃度35重量％）28重量部（５モル％／全酸成分）、ポリエチレングリコール（数平均分子量3000）8.1重量部（７重量％／ポリマー）、三酸化アンチモン0.05重量部、リン酸トリメチルエステル0.13重量部を添加した。次いで徐々に昇温、減圧にし、280℃、0.5mmHgで重合を行い固有粘度0.55を有する共重合ポリエステルを得た。
【００６８】
この共重合ポリエステル（略号Ｍ）と市販の固有粘度0.65のポリエチレンテレフタレート（略号Ｐ）を各々150℃で真空乾燥した後、３台の押出幾を用いて285℃で溶融押出し、３層が表１に示す素材からなるようにＴダイ内で層状に接合し、静電密着方法で冷却ドラムに密着させながら急冷固化させ、積層未延伸フィルムを得た。この時、各素材の押出量を調整し各層の厚さが９：10：７となるようにした。次いで85℃でタテ方向に3.5倍延伸し、更に95℃でヨコ方向に3.5倍延伸した後210℃で熱固定して厚さ50μmの二軸延伸フィルムを得た。
【００６９】
尚、固有粘度は、下記の方法にて測定した。
【００７０】
〈固有粘度〉
ウベローデ型粘度計を用いて行った。混合溶媒としてフェノールと1,1,2,2-テトラクロロエタンの重量比約55：45（流下時間42.0±0.1秒に調整）のものを用い、サンプル濃度0.2，0.6，1.0（ｇ／dl）の溶液（温度20℃）を作製した。ウベローデ型粘度計によって、それぞれの濃度（Ｃ）における比粘度（η_sp）を求め、次式

により濃度零に補外し固有粘度［η］を求めた。
【００７１】
サンプル２
上記サンプル１と同様にして厚さ75μmのフィルムを得た。
【００７２】
サンプル３
上記サンプル１と同様にして厚さ100μmのフィルムを得た。
【００７３】
サンプル４
上記サンプル１と同様にして厚さ125μmのフィルムを得た。
【００７４】
サンプル５
上記サンプル１における共重合ポリエステルと市販のポリエチレンテレフタレート（固有粘度0.65）の２層とし各層の比率を１：39とし、厚さ50μmとした以外はサンプル１と同様にしてフィルムを得た。
【００７５】
サンプル６
上記サンプル５と同様にして厚さ75μmのフィルムを得た。
【００７６】
サンプル７
上記サンプル５と同様にして厚さ100μmのフィルムを得た。
【００７７】
サンプル８
上記サンプル５と同様にして厚さ125μmのフィルムを得た。
【００７８】
サンプル９
上記サンプル５における２層の比率を４：36とした以外はサンプル５と同様にして50μmのフィルムを得た。
【００７９】
サンプル 10
上記サンプル９と同様にして厚さ75μmのフィルムを得た。
【００８０】
サンプル 11
上記サンプル８と同様にして厚さ100μmのフィルムを得た。
【００８１】
サンプル 12
上記サンプル８と同様にして厚さ125μmのフィルムを得た。
【００８２】
サンプル 13
上記サンプル１における各層の厚さの比を３：２：１とした以外はサンプル１と同様にして厚さ50μmのフィルムを得た。
【００８３】
サンプル 14
上記サンプル13と同様にして厚さ75μmのフィルムを得た。
【００８４】
サンプル 15
上記サンプル13と同様にして厚さ90μmのフィルムを得た。
【００８５】
サンプル 16
上記サンプル13と同様にして厚さ100μmのフィルムを得た。
【００８６】
サンプル 17
上記サンプル13と同様にして厚さ125μmのフィルムを得た。
【００８７】
サンプル 18
上記サンプル５における２層の比率を８：32とした以外はサンプル５と同様にして50μmのフィルムを得た。
【００８８】
サンプル 19
上記サンプル18と同様にして厚さ75μmのフィルムを得た。
【００８９】
サンプル 20
上記サンプル18と同様にして厚さ90μmのフィルムを得た。
【００９０】
サンプル 21
上記サンプル18と同様にして厚さ100μmのフィルムを得た。
【００９１】
サンプル 22
上記サンプル５における２層の比率を28：12とした以外はサンプル５と同様にして50μmのフィルムを得た。
【００９２】
サンプル 23
上記サンプル22と同様にして厚さ75μmのフィルムを得た。
【００９３】
サンプル 24
上記サンプル22と同様にして厚さ100μmのフィルムを得た。
【００９４】
サンプル 25
上記サンプル５における２層の比率を12：28とした以外はサンプル５と同様にして50μmのフィルムを得た。
【００９５】
サンプル 26
上記サンプル25と同様にして厚さ75μmのフィルムを得た。
【００９６】
サンプル 27
上記サンプル25と同様にして厚さ90μmのフィルムを得た。
【００９７】
サンプル 28
上記サンプル25と同様にして厚さ100μmのフィルムを得た。
【００９８】
サンプル 29
上記サンプル５における２層の比率を20：20とした以外はサンプル５と同様にして50μmのフィルムを得た。
【００９９】
サンプル 30
上記サンプル29と同様にして厚さ75μmのフィルムを得た。
【０１００】
サンプル 31
上記サンプル29と同様にして厚さ100μmのフィルムを得た。
【０１０１】
サンプル 32
上記サンプル１における共重合ポリエステルのみの単層フィルムとした以外はサンプル１と同様にして50μmのフィルムを得た。
【０１０２】
尚、この単層フィルムのガラス転移温度（Tg）は61℃であった。
【０１０３】
サンプル 33
上記サンプル32と同様にして厚さ75μmのフィルムを得た。
【０１０４】
サンプル 34
上記サンプル32と同様にして厚さ90μmのフィルムを得た。
【０１０５】
サンプル 35
上記サンプル32と同様にして厚さ100μmのフィルムを得た。
【０１０６】
サンプル 36
上記サンプル32と同様にして厚さ125μmのフィルムを得た。
【０１０７】
サンプル 37
上記サンプル１における市販のポリエチレンテレフタレート（固有粘度0.65）のみの単層フィルムとした以外はサンプル１と同様にして50μmのフィルムを得た。
【０１０８】
尚、この単層フィルムのガラス転移温度（Tg）は77℃であった。
【０１０９】
サンプル 38
上記サンプル37と同様にして厚さ75μmのフィルムを得た。
【０１１０】
サンプル 39
上記サンプル37と同様にして厚さ90μmのフィルムを得た。
【０１１１】
サンプル 40
上記サンプル37と同様にして厚さ100μmのフィルムを得た。
【０１１２】
サンプル 41
上記サンプル37と同様にして厚さ125μmのフィルムを得た。
【０１１３】
サンプル 42
上記サンプル１における各層の厚さの比を１：１：１とした以外はサンプル１と同様にして厚さ50μmのフィルムを得た。
【０１１４】
サンプル 43
上記サンプル42と同様にして厚さ75μmのフィルムを得た。
【０１１５】
サンプル 44
上記サンプル42と同様にして厚さ90μmのフィルムを得た。
【０１１６】
サンプル 45
上記サンプル42と同様にして厚さ100μmのフィルムを得た。
【０１１７】
サンプル 46
上記サンプル42と同様にして厚さ125μmのフィルムを得た。
【０１１８】
（カール値の測定方法）
▲１▼平板（曲率０m^-1）の上に静置した状態での経時カール値の測定
上記１〜46のサンプルは全て製膜直後カールはほぼ０であり、この初期カールのないサンプルを120mm×35mmのサイズ（縦延伸方向に120mm、横延伸方向に35mm）に断裁し、平板上に静置し、温度23℃、相対湿度55％に調湿された部屋に12ヶ月放置した後のカール値（１/ｍ）を測定し表１に示した。
【０１１９】
但し、この場合の静置とはフィルムにフィルム自身の自重以外は何の外力も働かない状態のことである。
【０１２０】
▲２▼曲率100m^-1で保存した場合のコアセットカール値の測定
上記と同様のサンプルを曲率100m^-1（φ20mm）の樹脂製のコアに経時でカールする方向に対して逆方向にまいて端部をテープで固定し、温度23℃、相対湿度55％に調整された部屋に12ヶ月放置した後に解放してカール値（１/ｍ）を測定し表１に示した。
【０１２１】
（経時収縮量の測定）
単層のサンプルについては下記の要領で経時収縮率を測定し表１に示した。サンプルサイズ120mm×35mmのフィルムに100mmの間隔でマークをつけ、温度23℃、相対湿度55％で12ヶ月放置した後のマーク間の寸法変化から収縮量を計算した。
【０１２２】
単層フィルムや積層構造が対称な比較サンプルフィルムでは経時カールは発生しなかった。また経時カールが発生した本発明のフィルムは全て経時収縮率が大である共重合ポリエステル成分が多い側に凹なカールとなった。
【０１２３】
また上記▲１▼、▲２▼の測定より計算したＲ₀（ｍ^-1）の値も表１に示した。
【０１２４】
単層フィルムや積層構造が対称なフィルムではＲ₀＝０となるために請求項３の巻取り曲率Ｒは存在しない。
【０１２５】
【表１】

【０１２６】
実施例１
No.１〜12のサンプルをＡ２判のサイズ（縦延伸方向が長手方向になるようにして）に断裁し、直径90mm（曲率22m^-1）の図面保管用の丸筒に、それぞれ経時カールに対して逆方向に巻いて入れた（本発明例No.１〜12）。また比較例として同じサンプルを経時カールと同方向に巻いて入れた（比較例No.１〜12）。
【０１２７】
また経時カールをしないサンプル32，33，35，36，37，38，40，41，42，43，45，46も同様に比較例として、それぞれ丸筒に入れた（比較例No.13〜24）。
【０１２８】
これらのフィルム入った丸筒を蓋をあけたまま23℃、湿度55％、の環境で12ヶ月保管し、そのカール値を測定し表２に示した。
【０１２９】
尚、カール値の測定はＡ２判のサイズのフィルムのほぼ中央部から長手方向に120mm、巾手方向に35mmのサイズのピースを切り出して測定した。
【０１３０】
【表２】

【０１３１】
実施例２
No.１〜14，16，17のサンプルを実施例１と同様にＡ２判のサイズに断裁し、直径47mm（曲率43m^-1）の図面保管用の丸筒に、それぞれ経時でカールする方向に対して逆方向に巻いて入れた（本発明例No.13〜28）。また比較例として同じサンプルを経時カールと同方向に巻いて入れた（比較例No.25〜40）。
【０１３２】
また経時カールをしないサンプル32，33，35，36，37，38，40，41，42，43，45，46も同様に比較例として、それぞれ丸筒に入れた（比較例No.41〜52）。
【０１３３】
これらのフィルム入った丸筒を23℃、湿度55％、の環境で12ヶ月保管し、そのカール値を測定し表３に示した。
尚、カール値の測定方法は実施例１と同じである。
【０１３４】
【表３】

【０１３５】
実施例３
No.１〜12のサンプルを巾16cmにスリッテングし、外径３インチのコアに巻の外径が6.4インチなるまでロール状に巻取り、フィルムの端はテープで止めた。但しこの時、本発明例として経時カールに対して逆方向に巻いたロールと、比較例として同方向に巻いたロールの両方を同時に作成した（本発明例No.29〜40、比較例No.53〜64）。
【０１３６】
また経時カールをしないサンプル32，33，35，36，37，38，40，41，42，43，45，46も同様に比較例としてロール状に巻取った（比較例No.65〜76）。
【０１３７】
これらのロール状のフィルムを23℃、湿度55％、の環境で12ヶ月保管し、その巻芯部と巻外部のカール値を測定し表４に示した。
【０１３８】
尚、カール値の測定は長手方向に120mm、巾手方向に35mmのサイズのピースを切り出して測定した。
【０１３９】
本発明例のNo.29〜32のフィルムの巻外側のコアセットカール値はPET単層（比較例No.69〜72）の巻外側より小さくなっているが、絶対値で比較すると逆にPETより大きくなる。しかしながらフィルム全長におけるカール値（絶対値）の最大や平均のカール値はPETよりかなり小さなものとなる。
【０１４０】
【表４】

【０１４１】
実施例４
No.１〜３，５〜７，９〜11，13，14，16，18，19，21〜24のサンプルを120mm×35mmのサイズ（縦延伸方向に120mm、横延伸方 向に35mm）に断裁し、直径
30mm（曲率67m^-1）の樹脂製のコアにまいて端部をテープで固定した。但しこの時、本発明例として経時カールと逆方向に巻いたものと、比較例として同方向に巻いたもの両方を同時に作成した（本発明例No.41〜58、比較例No.77〜94）。
【０１４２】
また経時カールをしないサンプル32，33，35，37，38，40，42，43，45も同様に比較例として、それぞれコアに巻いた（比較例No.95〜103）。
【０１４３】
これらのサンプルを23℃、湿度55％、の環境で12ヶ月保管し、そのカール値を測定し表５に示した。
【０１４４】
【表５】

【０１４５】
実施例５
No.２〜３，６〜７，10〜11，14，16，19，21，23〜24，26，28，30〜31のサンプルを120mm×35mmのサイズ（縦延伸方向に120mm、横延伸方向に35mm）に断裁し、直径20mm（曲率100m^-1）の樹脂製のコアにまいて端部をテープで固定した。但しこの時、本発明例として経時カールに対して逆方向に巻いたものと、比較例として同方向に巻いたもの両方を同時に作成した（本発明例No.59〜74、比較例No.104〜119）。
【０１４６】
また経時カールをしないサンプル33，35，38，40，43，45も同様に比較例として、それぞれコアに巻いた（比較例No.120〜125）。
【０１４７】
これらのサンプルを23℃、湿度55％、の環境で12ヶ月保管し、そのカール値を測定し表６に示した。
【０１４８】
【表６】

【０１４９】
実施例６
No.２，６，10，14，15，19，20，23，26，27，30のサンプルを120mm×35mm
のサイズ（縦延伸方向に120mm、横延伸方向に35mm）に断裁し、直径10.8mmの写真ネガフィルムのスプール（曲率185m^-1）にまいて端部をテープで固定した。但しこの時、本発明例として経時でカールする方向に対して逆方向に巻いたものと、比較例として同方向に巻いたもの両方を同時に作成した（本発明例No.75〜85、比較例No.126〜136）。
【０１５０】
また経時カールをしないサンプル33、34，38，39，43，44も同様に比較例として、それぞれスプールに巻いた（比較例No.137〜142）。
【０１５１】
これらのサンプルを23℃、湿度55％、の環境で12ヶ月保管し、そのカール値を測定し表７に示した。
【０１５２】
【表７】

【０１５３】
実施例より、積層重合体フィルムを経時カールの方向と逆方向に巻くと、順方向に巻いた場合より、コアセットカール値が大幅に低減することが判る。
【０１５４】
また積層重合体フィルムの巻取り曲率（Ｒ）を該フィルムのＲ₀値より小さくすることにより、該積層重合体フィルム構成している各樹脂の、何れの単層フィルムよりコアセットカール値は小さくなる。
【０１５５】
従って、本発明により、ロール状重合体フィルムや重合体フィルムにハロゲン化銀乳剤層などを塗設したロール状機能性フィルムの使用時のコアセットカールを使用上問題にならない程度まで低減する方法を提供することができた。
【０１５６】
実施例７
熱固定前に下引加工を行う支持体製造例
支持体NO.１
テレフタル酸100重量部、エチレングリコール64重量部に酢酸カルシウム水和物0.1重量部を添加し、常法によりエステル化反応を行った。得られた生成物に5-ナトリウムスルホジ（β-ヒドロキシエチル）イソフタル酸のエチレングリコール溶液（濃度35重量％）28重量部（５モル％／全酸性分）、ポリエチレングリコール（数平均分子量3000）8.1重量部（７重量％／ポリマー）、三酸化アンチモン0.05重量部、リン酸トリメチルエステル0.13重量部を添加した。次いで徐々に昇温、減圧し、280℃、0.5mmHgで重合を行い固有粘度0.55を有する共重合ポリエステルを得た。
【０１５７】
この共重合ポリエステル（略号Ｍ）と市販の固有粘度0.65のポリエチレンテレフタレート（略号Ｐ）を各々150℃で真空乾燥した後、３台の押出機を用いて285℃で溶融押出し、静電密着方法で冷却ドラムに密着させながら急冷固化させ、積層未延伸フィルムを得た。この時、各素材の押出量を調整し各層の厚さが９：１０：７となるようにした。
【０１５８】
次いで85℃でタテ方向に3.5倍延伸した。
【０１５９】
次いで、テレフタル酸ジメチル37重量部、イソフタル酸ジメチル30重量部、5-スルホイソフタル酸ジメチルナトリウム塩10重量部、エチレングリコール52重量部、1,4-シクロヘキサンジカルボン酸16重量部、ポリエチレングリコール（数平均分子量1、000）５重量部を重合した共重合ポリエステル（固有粘度0.52）の８％水溶液を下引層塗布液とし、このタテ延伸後のフィルムの両面に乾燥重量で0.3ｇ／m²の下引層を有するように塗布した。
【０１６０】
次いで、更に95℃でヨコ方向に3.5倍延伸した後210℃で熱固定して厚さ90μmの二軸延伸フィルムを得た。
【０１６１】
支持体NO.２
支持体NO.１と同様に積層未延伸フィルムを得、次いで、スチレン-ブタジエン（92−８重量％）共重合体70重量部、ポリエチルアクリレート重合体10重量部、ゼラチン10重量部の溶液を下引塗布液とし、未延伸のフィルムの両面に乾燥重量で４ｇ／m²の下引層を有するように塗布した。
【０１６２】
次いで85℃でタテ方向に3.5倍延伸し、更に95℃でヨコ方向に3.5倍延伸した後210℃で熱固定して厚さ90μmの二軸延伸フィルムを得た。
【０１６３】
支持体NO.３、５、７、９、11、13
積層比率及び層構成及びフィルム膜厚を下記の表８のように変化させた以外はNO.１と同様に作製した支持体をNO.３、５、７、９、11、13とする。
【０１６４】
支持体N0.４、６、８、10、12、14
積層比率及び層構成及びフィルム膜厚を表１のように変化させた以外はNO.２と同様に作製した支持体をNO.４、６、８、10、12、14とする。 これらの支持体は、経時で縦延伸方向にカールしてゆく性質があった。
【０１６５】
これらのサンプルを縦延伸方向が長手になるように3.5cm×10cmに切り23℃55％条件下で平板上に一枚づつ12ケ月放置した。放置後のカール量と放置前のカール量の差の絶対値（経時カール値）を表８に示す。
【０１６６】
【表８】

【０１６７】
比較支持体例
構成比を1/1/1とした以外は支持体１と同様に作成したフィルムを支持体NO.15とする。
【０１６８】
共重合ポリエステル（Ｍ）のみをもちいた以外は支持体１と同様に作成したフィルムを支持体NO.16とする。
【０１６９】
これら、二つの支持体の経時のカール値は、絶対値で２未満であった。
【０１７０】
また、先のポリエチレンテレフタレート樹脂を支持体１と同様に製膜したフィルムの23℃での１年の経時収縮率と支持体NO.16の経時収縮率の差は、約0.3％であった。
【０１７１】
熱固定後に下引加工を行う支持体製造例
熱固定前の下引加工を行わない以外は支持体NO.３と同様に２軸延伸熱固定終了後のポリエステルフィルムの両面に以下で示される水溶性高分子化合物0.5ｇを５ccの水に溶解しこの液を４ｇのレゾルシンを含む95ccのメタノール溶液に混合溶解させた処理液を、水溶性高分子がm²あたり50mgとなるように塗布し、100℃２分で乾燥させた。この支持体をN0.17とする。
【０１７２】
熱固定前の下引加工を行わない以外は支持体NO.16と同様に２軸延伸熱固定し、その後NO.17と同様の下引加工を施した支持体をNO.18とする。
【０１７３】
以下のバッキング層及び乳剤層を塗布しカラーネガハロゲン化銀写真感光材料を作成した。尚、カール値が経時で一方向に連続的にカールするポリエステル支持体は、カールで凸面となる側に乳剤層を設けた。
【０１７４】
《巻きぐせカール量の測定》
かくして作製したハロゲン化銀写真感光材料を、支持体の縦延伸方向が長手になるように巾3.5cmに裁断し長さ10cmにきって、直径10.8mmの芯に巻き付け端をテープで固定して23℃55％条件下で12ケ月放置した。放置後テープを剥し、カール値を測定し、巻きぐせカール量とした。得られた値を表９に示した。
【０１７５】
【表９】

【０１７６】
表９から明かなように、経時でカールする支持体は、巻きぐせカールが付きにくい。
【０１７７】
さらに、本発明例３と比較例17、比較例16と比較例18を比べると、結晶配向終了前で下引を行う効果は、経時でカールする支持体で特に顕著である。
【０１７８】
尚、現像処理後の巻きぐせ回復性は、どの試料も問題なかった。
【０１７９】
＜バッキング層＞
第１層；
ゼラチン 4.5mg
ソジウム-ジ-(-2-エチルヘキシル)-スルホサクシネート 1.0mg
トリポリ燐酸ナトリウム 76mg
クエン酸 16mg
カルボキシアルキルデキストラン硫酸エステル 49mg
ビニルスルホン型硬膜剤 30mg
第２層（最外層）；
ゼラチン 1.5ｇ
ポリマービーズ
（平均粒子径：３μm、ポリメチルメタクリレート） 24mg
ビニルスルホン型硬膜剤 45mg
化合物SB−１および化合物SB−２の混合物 30mg
化合物SB−１ 100mg
＜乳剤層＞
第１層；ハレーション防止層（HC）
黒色コロイド銀 0.15ｇ
UV吸収剤（UV−１） 0.20ｇ
化合物（CC−１） 0.02ｇ
高沸点溶媒（Oil−１） 0.20ｇ
高沸点溶媒（Oil−２） 0.20ｇ
ゼラチン 1.6ｇ
第２層；中間層（IL−１）
ゼラチン 1.3ｇ
第３層；低感度赤感性乳剤層（RL）
沃臭化銀乳剤
（平均粒径0.3μm、平均ヨウド含有量2.0モル％） 0.4ｇ
沃臭化銀乳剤
（平均粒径0.4μm、平均ヨウド含有量8.0モル％） 0.3ｇ
増感色素（Ｓ−１） 3.2×10^-4（モル／銀１モル）
増感色素（Ｓ−２） 3.2×10^-4（モル／銀１モル）
増感色素（Ｓ−３） 0.2×10^-4（モル／銀１モル）
シアンカプラー（Ｃ−１） 0.50ｇ
シアンカプラー（Ｃ−２） 0.13ｇ
カラードシアンカプラー（CC−１） 0.07ｇ
DIR化合物（Ｄ−１） 0.006ｇ
DIR化合物（Ｄ−２） 0.01ｇ
高沸点溶媒（Oil−１） 0.55ｇ
ゼラチン 1.0ｇ
第４層；高感度赤感性乳剤層（RH）
沃臭化銀乳剤
（平均粒径0.7μm、平均ヨウド含有量7.5モル％） 0.9ｇ
増感色素（Ｓ−１） 1.7×10^-4（モル／銀１モル）
増感色素（Ｓ−２） 1.6×10^-4（モル／銀１モル）
増感色素（Ｓ−３） 0.1×10^-4（モル／銀１モル）
シアンカプラー（Ｃ−２） 0.23ｇ
カラードシアンカプラー（CC−１） 0.03ｇ
DIR化合物（Ｄ−２） 0.02ｇ
高沸点溶媒（Oil−１） 0.25ｇ
ゼラチン 1.0ｇ
第５層；中間層（IL−２）
ゼラチン 0.8ｇ
第６層；低感度緑感性乳剤層（GL）
沃臭化銀乳剤
（平均粒径0.4μm、平均ヨウド含有量8.0モル％） 0.6ｇ
沃臭化銀乳剤
（平均粒径0.3μm、平均ヨウド含有量2.0モル％） 0.2ｇ
増感色素（Ｓ−４） 6.7×10^-4（モル／銀１モル）
増感色素（Ｓ−５） 0.8×10^-4（モル／銀１モル）
マゼンタカプラー（Ｍ−１） 0.17ｇ
マゼンタカプラー（Ｍ−２） 0.43ｇ
カラードマゼンタカプラー（CM−１） 0.10ｇ
DIR化合物（Ｄ−３） 0.02ｇ
高沸点溶媒（Oil−２） 0.7ｇ
ゼラチン 1.0ｇ
第７層；高感度緑感性乳剤層（GH）
沃臭化銀乳剤
（平均粒径0.7μm、平均ヨウド含有量7.5モル％） 0.9ｇ
増感色素（Ｓ−６） 1.1×10^-4（モル／銀１モル）
増感色素（Ｓ−７） 2.0×10^-4（モル／銀１モル）
増感色素（Ｓ−８） 0.3×10^-4（モル／銀１モル）
マゼンタカプラー（Ｍ−１） 0.30ｇ
マゼンタカプラー（Ｍ−２） 0.13ｇ
カラードマゼンタカプラー（CM−１） 0.04ｇ
DIR化合物（Ｄ−３） 0.004ｇ
高沸点溶媒（Oil−２） 0.35ｇ
ゼラチン 1.0ｇ
第８層；イエローフィルター層（YC）
黄色コロイド銀 0.1ｇ
添加剤（HS−１） 0.07ｇ
添加剤（HS−２） 0.07ｇ
添加剤（SC−１） 0.12ｇ
高沸点溶媒（Oil−２） 0.15ｇ
ゼラチン 1.0ｇ
第９層；低感度青感性乳剤層（BL）
沃臭化銀乳剤
（平均粒径0.3μm、平均ヨウド含有量2.0モル％） 0.25ｇ
沃臭化銀乳剤
（平均粒径0.4μm、平均ヨウド含有量8.0モル％） 0.25ｇ
増感色素（Ｓ−９） 5.8×10^-4（モル／銀１モル）
イエローカプラー（Ｙ−１） 0.6ｇ
イエローカプラー（Ｙ−２） 0.32ｇ
DIR化合物（Ｄ−１） 0.003ｇ
DIR化合物（Ｄ−２） 0.006ｇ
高沸点溶媒（Oil−２） 0.18ｇ
ゼラチン 1.3ｇ
第10層；高感度青感性乳剤層（BH）
沃臭化銀乳剤
（平均粒径0.8μm、平均ヨウド含有量8.5モル％） 0.5ｇ
増感色素（Ｓ−10） ３×10^-4（モル／銀１モル）
増感色素（Ｓ−11） 1.2×10^-4（モル／銀１モル）
イエローカプラー（Ｙ−１） 0.18ｇ
イエローカプラー（Ｙ−２） 0.10ｇ
高沸点溶媒（Oil−２） 0.05ｇ
ゼラチン 2.0ｇ
第11層；第１保護層（PRO−１）
沃臭化銀（平均粒径0.08μm） 0.3ｇ
紫外線吸収剤（UV−１） 0.07ｇ
紫外線吸収剤（UV−２） 0.08ｇ
添加剤（HS−１） 0.2ｇ
添加剤（HS−２） 0.1ｇ
高沸点溶媒（Oil−１） 0.07ｇ
高沸点溶媒（Oil−３） 0.07ｇ
ゼラチン 0.8ｇ
第12層；第２保護層（PRO−２）
化合物（化合物Ａ） 0.04ｇ
化合物（化合物Ｂ） 0.004ｇ
ポリメチルメタアクリレート（平均粒径：３μm） 0.02ｇ
メチルメタアクリレート：エチルメタアクリレート：メタアクリル酸
＝３：３：４（重量比）の共重合体（平均粒径：３μm） 0.13ｇ
ゼラチン 0.7ｇ
−沃臭化銀乳剤の調製−
第10層に使用した沃臭化銀乳剤は以下の方法で調整した。
【０１８０】
平均粒径が0.33μmの単分散沃臭化銀粒子（沃化銀含有率２mol％）を種結晶として、沃臭化銀乳剤をダブルジェット法により調製した。
【０１８１】
下記組成の溶液〈Ｇ−１〉を温度70℃、pAg7.8、pＨ7.0に保ち、よく撹拌しながら0.34モル担当の種乳剤を添加した。
【０１８２】
（内部高沃度相−コア相−の形成）
その後、下記組成の溶液〈Ｈ−１〉と下記組成の溶液〈Ｓ−１〉とを１：１の流量比を保ちながら、加速された流量（終了時の流量が初期流量の3.6倍）で86分をかけて添加した。
【０１８３】
（外部低沃度相−シェル相−の形成）
続いて、pAg10.1、pＨ6.0に保ちながら、〈Ｈ−２〉と〈Ｓ−２〉とを１：１の流量比で加速された流量（終了時の流量が初期流量の5.2倍）で65分を要して添加した。
【０１８４】
粒子形成中のpAgとpＨとは、臭化カリウム水溶液と56％酢酸水溶液とを用いて制御した。粒子形成後に、常法のフロキュレーション法によって水洗処理を施し、その後ゼラチンを加えて再分散し、40℃にてpＨおよびpAgをそれぞれ5.8および8.06に調製した。
【０１８５】
得られた乳剤は、平均粒径0.80μm、分布の広さが12.4％、沃化銀含有率8.5mol％の八面体沃臭化銀粒子を含む単分散乳剤であった。
【０１８６】
〈Ｇ−１〉溶液
オセインゼラチン 100.0ｇ
下記化合物−Ｉの10重量％メタノール溶液 25.0ml
28％アンモニア水溶液 440.0ml
56％酢酸水溶液 660.0ml
水で仕上げる 5000.0ml
＊化合物−Ｉ：ポリプロピレンオキシ・ポリエチレンオキシ・ジ琥珀酸・ナトリウム。
【０１８７】
〈Ｈ−１〉溶液
オセインゼラチン 82.4ｇ
臭化カリウム 151.6ｇ
沃化カリウム 90.6ｇ
水で仕上げる 1030.5ml
〈Ｓ−１〉溶液
硝酸銀 309.2ｇ
28％アンモニア水溶液 当量
水で仕上げる 1030.5ml
28％アンモニア水溶液 当量
水で仕上げる 1030.5ml
〈Ｈ−２〉溶液
オセインゼラチン 302.1ｇ
臭化カリウム 770.0ｇ
沃化カリウム 33.2ｇ
水で仕上げる 3776.8ml
〈Ｓ−２〉溶液
硝酸銀 1133.0ｇ
２８％アンモニア水溶液 当量
水で仕上げる 3776.8ml
第１０層以外の乳剤層に使用される沃臭化銀乳剤についても、同様の方法で、種結晶の平均粒径、温度、pAg、pＨ、流量、添加時間、およびハライド組成を変化させて、平均粒径および沃化銀含有率が異なる前記各乳剤を調製した。
【０１８８】
いずれも分布の広さ20％以下のコア／シェル型単分散乳剤であった。各乳剤は、チオ硫酸ナトリウム、塩化金酸およびチオシアン酸アンモニウムの存在下にて最適な化学熟成を施し、増感色素、4-ヒドロキシ-6-メチル-1,3,3a,7-テトラザインデン、1-フェニル-5-メルカプトテトラゾールを加えた。
【０１８９】
なお、上述の感光材料は、さらに、化合物Su−１、Su−２、粘度調整剤、硬膜剤Ｈ−１、Ｈ−２、安定剤ST−１、カブリ防止剤AF−１、AF−２（重量平均分子量10,000のもの及び1,100,000のもの）、染料AI−１、AI−２および化合物DI−１（9.4mg／m²）を含有する。
【０１９０】
−フィルム現像処理−
【０１９１】
【表１０】

【０１９２】
表10において、補充量は写真感光材料１m²当たりの値である。
【０１９３】
発色現像液、漂白液、定着液、安定液及びその補充液は、下記のようにして調製されたものを使用した。
【０１９４】
〈発色現像液〉
水 800ml
炭酸カリウム 30ｇ
炭酸水素ナトリウム 2.5ｇ
亜硫酸カリウム 3.0ｇ
臭化ナトリウム 1.3ｇ
沃化カリウム 1.2mg
ヒドロキシルアミン硫酸塩 2.5ｇ
塩化ナトリウム 0.6ｇ
4-アミノ-3-メチル-N-エチル-N-
（β-ヒドロキシルエチル）アニリン硫酸塩 4.5ｇ
ジエチレントリアミン五酢酸 3.0ｇ
水酸化カリウム 1.2ｇ
水を加えて１リットルとし、水酸化カリウムまたは20％硫酸を用いてpH10.06に調製した。
【０１９５】
〈発色現像補充液〉
水 800ml
炭酸カリウム 35ｇ
炭酸水素ナトリウム ３ｇ
亜硫酸カリウム ５ｇ
臭化ナトリウム 0.4ｇ
ヒドロキシルアミン硫酸塩 3.1ｇ
4-アミノ-3-メチル-N-エチル-N-
（β-ヒドロキシルエチル）アニリン硫酸塩 6.3ｇ
水酸化カリウム ２ｇ
ジエチレントリアミン五酢酸 3.0ｇ
水を加えて１リットルとし、水酸化カリウムまたは20％硫酸を用いてpH10.18に調製した。
【０１９６】
〈漂白液〉
水 700ml
1,3-ジアミノプロパン四酢酸鉄 (III)アンモニウム・125ｇ
エチレンジアミン四酢酸 ２ｇ
硝酸ナトリウム 40ｇ
臭化アンモニウム 150ｇ
氷酢酸 40ｇ
水を加えて１リットルとし、アンモニア水又は氷酢酸を用いてpＨ4.4に調製した。
【０１９７】
〈漂白補充液〉
水 700ml
1,3-ジアミノプロパン四酢酸鉄 (III)アンモニウム・175ｇ
エチレンジアミン四酢酸 ２ｇ
硝酸ナトリウム 50ｇ
臭化アンモニウム 200ｇ
氷酢酸 56ｇ
アンモニア水又は氷酢酸を用いてpＨ4.0に調整した後に水を加えて１リットルにした。
【０１９８】
〈定着液〉
水 800ml
チオシアン酸アンモニウム 120ｇ
チオ硫酸アンモニウム 150ｇ
亜硫酸ナトリウム 15ｇ
エチレンジアミン四酢酸 ２ｇ
アンモニア水又は氷酢酸を用いてpＨ6.2に調整した後、水を加えて１リットルにした。
【０１９９】
〈定着補充液〉
水 800ml
チオシアン酸アンモニウム 150ｇ
チオ硫酸アンモニウム 180ｇ
亜硫酸ナトリウム 20ｇ
エチレンジアミン四酢酸 ２ｇ
アンモニウム水又は氷酢酸を用いてpＨ6.5に調整した後水を加えて１リットルにした。
【０２００】
〈安定液及び安定補充液〉
水 900ml
下記（化２）で表わせられる化合物 2.0ｇ
ジメチロール尿素 0.5ｇ
ヘキサメチレンテトラミン 0.2ｇ
1,2-ベンズイソチアゾリン-3-オン 0.1ｇ
シロキサン（ＵＣＣ製：Ｌ−77） 0.1ｇ
アンモニア水 0.5ml
水を加えて１リットルとした後、アンモニア水又は50％硫酸を用いてpH8.5に調製した。
【０２０１】
【化２】

【０２０２】
以下に、この発明に係るハロゲン化銀写真感光材料を形成するのに用いた各化合物の構造を示す。
【０２０３】
【化３】

【０２０４】
【化４】

【０２０５】
【化５】

【０２０６】
【化６】

【０２０７】
【化７】

【０２０８】
【化８】

【０２０９】
【化９】

【０２１０】
【化１０】

【０２１１】
【化１１】

【０２１２】
【化１２】

【０２１３】
【化１３】

【０２１４】
【化１４】

【０２１５】
【化１５】

【０２１６】
【化１６】

【０２１７】
【発明の効果】
本発明によれば、ロール状に貯蔵された重合体フィルムや重合体フィルムにハロゲン化銀乳剤層などを塗設した機能性のフィルムの使用時のコアセットカールが使用上問題にならない程度まで低減されたロール状フィルムを提供することができる。又、巻きぐせがつきにくく、且つ、現像処理で巻きぐせが取れ易いハロゲン化銀写真感光材料を提供することができる。
【図面の簡単な説明】
【図１】フィルムのカール状態を示す説明図。[0001]
[Industrial application fields]
The present invention relates to a polymer film that is difficult to curl even when stored in a roll form, or a functional film coated with a photosensitive layer, and a silver halide photographic light-sensitive material that is difficult to curl.
[0002]
[Prior art]
Generally, the curl is called a core set, and when the self-supporting film is wound and stored, a concave curl is formed on the core side. Of course, such a core set can also occur when wound without a winding core. In particular, a film once wrinkled is generally difficult to handle, and may be used after being subjected to a treatment such as reverse rolling before use.
[0003]
The problem of undesired core set during storage of such a thermoplastic polymer film in roll form is that a thermoplastic polymer film having a high core set tendency, for example, a photosensitive film using polyethylene terephthalate as a support. In particular, this is a problem.
[0004]
By the way, the curled film is in a state as shown in FIG. Here, the reciprocal of the radius of curvature r (unit: m) from the center of curvature O is the curvature, and this curvature is called the core set curl value or curl value of the film. Moreover, the reciprocal of the winding radius (unit is shown by m) which wound up the film is called winding curvature or core curvature.
[0005]
In the present specification, the term “film” simply means a polymer film, a + curl value indicates a core set direction, that is, a curl that is concave on the core side, and a − curl value indicates a curl that is convex on the core side. Indicates.
[0006]
In general, the photosensitive material is in the form of a sheet and in the form of a roll, and triacetyl cellulose (hereinafter referred to as TAC) and polyethylene terephthalate (hereinafter referred to as PET) have been mainly used as the support. PET has the advantage of high strength, but there is a problem that it is difficult to remove curl even if it is developed, and there are restrictions on its use.
[0007]
Thus, various means have been studied in order to improve the core set of thermoplastic polymer films.
[0008]
For example, the film for about 0.1-1500 hours at a relative humidity of less than 100% and a temperature ranging from about 30 ° C. to the glass transition temperature (Tg) of the polymer until core set curl formation of the self-supporting film is reduced by at least 15% Is disclosed in U.S. Pat.No. 4,141,735 and Japanese Patent Application Laid-Open No. 51-16358, and a polymer film wound into a roll is cut into a sheet shape. No. 60-16611 discloses a method in which the above sheets are stacked in an atmosphere of 10 to 40 ° C. and a dew point temperature of 25 ° C. or less, hermetically packaged, and heat-treated at 28 to 65 ° C. for 1 hour or longer. However, both require time for heat treatment and may cause damage to the film surface.
[0009]
Also, a method of applying reverse curl stepwise and continuously from the core to the outer periphery when winding the film into a roll is disclosed in Japanese Patent Laid-Open No. 4-166929, so that the emulsion layer side is externally wound during production. Japanese Patent Application Laid-Open No. 4-273239 discloses a method in which a heat treatment is performed in the form of a roll, a roll, and the emulsion layer is rewound so that the emulsion layer side is internally wound at the time of shipment. However, these methods also require new equipment and work, which increases costs.
[0010]
Furthermore, JP-A-64-70748 has a temperature gradient ΔT of greater than 10 ° C. from one surface of the film to the other during the production of the polymer film, and the longitudinal tension during stretching is 10 N / mm.²A method of winding a film produced in the presence of such a temperature gradient ΔT in a roll shape and heating and conditioning in a range from about 30 ° C. to Tg at a relative relative humidity of less than 100% is disclosed. It is disclosed in JP-A-2-54254. Further, a method for heating and then cooling the photosensitive material is disclosed in Japanese Patent Application Laid-Open No. 62-31653, but none of them can sufficiently reduce the core set curl.
[0011]
Japanese Patent Application Laid-Open No. 1-244446 discloses a technique for making the polyester easy to remove the wrapping. However, as described above, it is easy to remove the wrapping in the development process simply by making the polyester support hydrophilic. Although the handleability after the development process is improved, the wrapping itself is easier to attach, and the handleability before the development process is deteriorated compared to PET.
[0012]
[Problems to be solved by the invention]
For the above problems, the problem of the present invention is that the core set curl at the time of use of a polymer film stored in a roll shape or a functional film in which a silver halide emulsion layer is coated on the polymer film is used. An object of the present invention is to provide a roll film that is reduced to a level that does not cause a problem in use. Another object of the present invention is to provide a silver halide photographic light-sensitive material that is difficult to curl and that can be easily curled by development processing.
[0013]
[Means for Solving the Problems]
The above-described problems of the present invention are as follows.▲ 3 ▼This is achieved by either
[0014]
(1) A curl value (curvature in the longitudinal direction of the film when at least two layers of resins having different shrinkage with time are laminated asymmetrically with respect to the center plane with respect to both sides of the film and the film is left below the glass transition temperature. (Reciprocal of radius) changes in one direction over timeAnd the direction in which the curl change occurs is the longitudinal direction, 3.5cm × 12cm Cut into strips twenty three ℃, 55 On the lithographic plate under% conditions 12 The curl value over time, which is the absolute value of the difference between the curl values before and after being left for months, is 2 to 250 m. ^-1 InA roll film, wherein the roll film is wound in a roll shape in a direction opposite to the curl direction of the film.
[0015]
(2) The rolled film according to the above, wherein the winding curvature (R) is within the range represented by the following formula.
0 <R (m^-1) <R₀   R₀= 900a / (400-9b + 9a)
a: Curling over time when stored for one year at 23 ° C. and 55% RH with the film standing on a flat platevalue
b: Curvature is 100m^-1Increase in curl value when stored for one year at 23 ° C and 55% RH with a winding diameter of φ20mm
[0016]
(3) A rolled silver halide photographic light-sensitive material having at least one silver halide emulsion layer on at least one side of a polyester support, wherein the support has at least two layers of resins having different shrinkage over time. Is laminated asymmetrically with respect to the center plane with respect to both sides of the support.IsCurl value changes in one direction over timeAnd the direction in which the curl change occurs is the longitudinal direction, 3.5cm × 12cm Cut into strips twenty three ℃, 55 On a flat plate under% conditions 12 The curl value over time, which is the absolute value of the difference between the curl values before and after being left for months, is 2 to 250 m. ^-1 InIn addition, the substrate is wound in a roll shape in a direction opposite to the curl direction of the support provided with a hydrophilic colloid layer by coating an undercoating resin before completion of the oriented crystal of the support. Rolled silver halide photographic light-sensitive material.
[0018]
Hereinafter, the present invention will be specifically described.
[0019]
In the present invention, the glass transition point (Tg) means an extrapolated glass transition start temperature of a DSC curve obtained by DSC measurement (JISK7121) at a heating rate of 20 ° C./min.
[0020]
Also, the curl value of the film (or support) has a characteristic that changes in one direction with time. The fact that the radius of the circle when the curled film is extrapolated to the circumference as a circular arc decreases with time. This means that the curl that increases with time is hereinafter referred to as curl over time. In such curling with time, the direction in which curling with time occurs in the film (or the support before applying the hydrophilic colloid layer or the support after removing the applied hydrophilic colloid layer) is the longitudinal direction. Thus, it can be measured by cutting into a 3.5 cm × 12 cm strip and leaving it on a planographic plate at 23 ° C. and 55% for 12 months and measuring the absolute value of the difference in curl value before and after being left. In addition, the curling over time referred to in the present invention does not complete within a few hours or days but occurs continuously for a long period of time, and whether or not the film wound in a roll is curled over time. The film may be unwound and whether or not the curl value continuously increases in a period of several days to several months may be confirmed by the above method.
[0021]
The curl value over time of the support of the present invention may be appropriately selected depending on the type of photosensitive material used, but is usually 2 to 250 m.^-1More preferably 30-200m^-1It is.
[0022]
The curl value here is the reciprocal of the radius (R, unit: m) of the circle when extrapolated to the circumference as a circular arc of the longitudinal direction of the sample cut into a short shape (curl value = 1) / R).
[0023]
The direction of change of the curl value is preferably one direction, and the curl value in the longitudinal direction during film formation is preferably changed.
[0024]
In addition, a polymer film that causes curling over time can be obtained if the layer structure on both sides of the divided substrate is asymmetric when the thickness of the support before subbing is divided into two equal parts.
[0025]
Such a film can be obtained by laminating at least two kinds of polyester resins, and it is particularly preferred to laminate resins having different shrinkage with time.
[0026]
The polyester resin used in the present invention is one having a repeating unit of dicarboxylic acid and diol as a main constituent, preferably a polyester having a repeating unit of aromatic dibasic acid and glycol as a main constituent. Can do.
[0027]
Examples of the dibasic acid include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acids. Examples of the diol or glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol. And p-xylene glycol. Of these, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents and polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents are preferred.
[0028]
In addition, the main repeating unit may be a copolymer of 85 mol% or more, preferably 90 mol% or more, as long as the original excellent properties of the polyester are not impaired, and other polymers are blended. Also good.
[0029]
The intrinsic viscosity of the preferred polyester is not particularly limited, but is preferably from 0.35 to 0.80, particularly preferably from 0.45 to 0.70, from the viewpoint of stretchability when preparing a laminated film.
[0030]
Among the copolyesters, there are copolymerized polyethylene terephthalate mainly composed of terephthalic acid and ethylene glycol, and copolymer polyethylene-2,6-naphthalate mainly composed of 2,6-naphthalenedicarboxylic acid and ethylene glycol. preferable.
[0031]
In addition, the main repeating unit may be a copolymer of 85 mol% or more, preferably 90 mol% or more, as long as the original excellent properties of the polyester are not impaired, and other polymers are blended. Also good.
[0032]
The intrinsic viscosity of the preferred polyester is not particularly limited, but is preferably from 0.35 to 0.80, particularly preferably from 0.45 to 0.70, from the viewpoint of stretchability when preparing a laminated film.
[0033]
Among the copolyesters, there are copolymerized polyethylene terephthalate mainly composed of terephthalic acid and ethylene glycol, and copolymer polyethylene-2,6-naphthalate mainly composed of 2,6-naphthalenedicarboxylic acid and ethylene glycol. preferable.
[0034]
The aromatic dicarboxylic acid containing a metal sulfonate group as a copolymerization component in the copolymerized polyester is 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoterephthalic acid, 4-sodium sulfo-2,6. -Naphthalenedicarboxylic acid or ester-forming derivatives represented by the following chemical formula 1, and compounds obtained by replacing these sodium with other metals such as potassium and lithium.
[0035]
[Chemical 1]

[0036]
The copolymer polyester preferably uses a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid polyether dicarboxylic acid as a copolymer component as long as the effects of the present invention are not impaired.
[0037]
Examples of the polyalkylene glycol include polyethylene glycol and polytetramethylene glycol. The molecular weight of the polyalkylene glycol that can be used is not particularly limited, but is preferably 300 to 20,000, more preferably 600 to 10,000, and particularly preferably 1,000 to 5,000. In particular, polyethylene glycol is preferable as the polyalkylene glycol.
[0038]
As the saturated aliphatic dicarboxylic acid, for example, an ester-forming derivative thereof is preferable, and adipic acid, dimethyl adipate, dimethyl sebacate and the like that are esters of adipic acid and sebacic acid are used. Preferred is dimethyl adipate.
[0039]
As the polyether dicarboxylic acid, polyethyleneoxydicarboxylic acid, polypropyleneoxydicarboxylic acid, poly (ethylene / propylene) oxydicarboxylic acid, polytetramethyleneoxydicarboxylic acid and copolymers thereof are preferable. In particular, polyethyleneoxydicarboxylic acid represented by the following formula is more preferable in terms of planar stability.
[0040]
R¹OOCCH₂− (O−CH₂CH₂), -OCH₂COOR²
(R¹, R²: H or an alkyl group having 1 to 8 carbon atoms, n: a positive integer)
Further, the copolymerization ratio of the polyether dicarboxylic acid component is 2 to 30% by weight, preferably 5 to 15% by weight, particularly preferably 7 to 12% by weight, based on the polyester of the reaction product.
[0041]
In the polyester resin used in the present invention, other components may be copolymerized or other polymers may be blended as long as the effects of the present invention are not impaired. The polymer to be blended is preferably a polyester polymer.
[0042]
-Production of polyester-
Both polyesters used in the present invention may contain phosphoric acid, phosphorous acid and esters thereof and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.) in the polymerization stage, or after polymerization. Inorganic particles may be blended with the polymer. Further, a pigment, an ultraviolet absorber, an antioxidant, or the like may be appropriately added at any stage of polymerization or after polymerization.
[0043]
In order to obtain a copolymerized polyester, the acid component and the glycol component may be transesterified, and then the above-described copolymerized component may be added to perform melt polymerization. Alternatively, the copolymerized component may be added before transesterification. Then, melt polymerization may be performed after transesterification, or a known synthesis method such as solid-phase polymerization of a polymer obtained by melt polymerization may be employed.
[0044]
Examples of the catalyst used in the transesterification include acetates, fatty acid salts, carbonates and the like of metals such as manganese, calcium, zinc, and cobalt. Of these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable. It is also effective to add a hydroxide, a metal salt of an aliphatic carboxylic acid, a quaternary ammonium salt, etc. within a range that does not inhibit the reaction or color the polymer during the transesterification and / or polymerization. Sodium hydroxide, sodium acetate, tetraethylhydroxyammonium and the like are preferable, and sodium acetate is particularly preferable.
[0045]
The polyester used in the present invention can contain various additives. For example, a dye may be added to the polyester for the purpose of preventing a light piping phenomenon (edge fogging) that occurs when light enters from the edge of a photographic support on which a photographic emulsion layer is coated. The type of the dye is not particularly limited, but is preferably excellent in heat resistance in the film forming process, and examples thereof include anthraquinone chemical dyes.
[0046]
The layer structure of the polyester film used in the present invention may be a laminated structure in which two or more layers are laminated in an arbitrary number. In addition, the polyester layer contained in the support body of this invention does not consider coating layers, such as an undercoat layer, for example as a polyester layer.
[0047]
The total thickness of the films having a laminated structure is not particularly limited, and can be arbitrarily determined according to the use, and is usually 40 to 250 μm, and particularly preferably 65 to 180 μm.
[0048]
In addition, even if the laminated structure in the polyester layer is a two-layered or three-layered structure, even if the laminated structure has four or more layers, both sides of the polyester layer in the laminated structure center on the position where the thickness is divided into two equal parts. When divided into two, it is preferable that the layer configuration on both sides of the division is asymmetric.
[0049]
Asymmetry here means physically, mechanically or chemically different, for example, the composition order of polyester layer, copolyester layer or other material layer, polyester layer, copolyester layer or other The thickness of the layer made of the above materials, the amount of the main component constituting the polyester or copolymer polyester on the upper and lower sides of the surface to be divided in half, the amount of the copolymer component or copolymer component is different, and the intrinsic viscosity And the difference in the type of copolymerization component or the content of the copolymerization component in any of the polyester layers on the dividing surface. Of these differences, chemical differences are preferable in terms of effects.
[0050]
As a method for confirming the asymmetry of these laminated polyester layers, various analytical instruments can be used, and there is no particular limitation, but the layer structure can be confirmed by microscopic observation of the cross section of the film. It can also be confirmed by taking a picture. Also, while observing this under a microscope, each layer is scraped off, or it is scraped from the top and the bottom to obtain a half-divided surface, and the upper and lower layers or the analytes of each layer are obtained, followed by hydrolysis and liquid chromatography. It may be measured with various measuring devices such as NMR, or the analysis object may be dissolved in a solvent, followed by NMR analysis, GPC (gel permeation chromatography) analysis, or measuring intrinsic viscosity. Perform X-ray spectroscopic analysis of the object as it is, or mix it with KBr etc. and analyze IR (infrared spectroscopic instrument) etc. As a result, the absolute position or the corresponding peak position and intensity of the measurement result The asymmetry of both outer layers can be confirmed or measured even by differences.
[0051]
A film having a laminated structure of two or more layers by combining such resins can be produced as follows. That is, for example, two types of polyesters are melt-extruded from separate extruders, then laminated and extruded in a laminar flow in a molten polymer conduit or extrusion die, cooled and solidified on a cooling drum, and unstretched film Is obtained by biaxially stretching and heat-setting, or a polyester or copolymer polyester alone and a laminated film are melt-extruded from an extruder and cooled and solidified on a cooling drum, or the unstretched film is uniaxially stretched After coating the surface of the uniaxially oriented film with an anchor agent, adhesive, etc., if necessary, the polyester or copolymer polyester alone and the laminated film are extrusion laminated, and then after biaxial stretching is completed, heat is applied. There are extrusion lamination methods to fix, but co-extrusion method due to the simplicity of the process Preferred.
[0052]
Stretching conditions are not particularly limited, but in general, stretching is performed biaxially in a temperature range from Tg to Tg + 100 ° C., which has a higher glass transition temperature (Tg) of a plurality of polyester layers. At this time, the following methods A, B, and C can be employed in the same manner as the stretching method of the single-layer polyester layer. The draw ratio is preferably 4 to 16 times in terms of area ratio. Moreover, heat setting can be performed in the temperature range of 150-240 degreeC.
[0053]
(A) A method of first stretching an unstretched sheet in the longitudinal direction and then stretching in the lateral direction
(B) A method of first stretching an unstretched sheet in the transverse direction and then stretching in the longitudinal direction
(C) A method in which an unstretched sheet is stretched in the longitudinal direction in one or more stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction.
[0054]
Such curling of the support over time can be controlled by arbitrarily selecting the lamination ratio and the type of polyester resin. In particular, if resin layers having different shrinkages with time are laminated, curling properties with time can be exhibited. The shrinkage with time referred to here is a phenomenon in which a dimensional change (shrinkage) occurs with time even under the same temperature and humidity equilibrium state. When the constituent resin layers are formed as a single layer, the shrinkage ratio with time of the resin film having the maximum shrinkage with time is two times or more of the shrinkage ratio with time of the minimum resin layer.
[0055]
In order to make the laminated polymer film of the present invention more effective, it is necessary to increase the curl over time of the laminated film. To that end, the difference in Tg between the resins constituting the laminated film is increased. The storage temperature of the laminated polymer film is T_HThen, Tg of at least one resin layer is Tg ≦ T_H+ 50 ° C is desirable.
[0056]
Further, since the shrinkage with time is affected by the stretching conditions and the heat setting conditions during the production, similarly to the heat shrinkage, it is desirable to determine these film forming conditions.
[0057]
In addition, in order to provide the laminated polymer film of the present invention with excellent curl-removing property after development processing for a core set curl that has already been formed like a TAC film, a resin layer with high water absorption is used on the surface of the film. The film may be designed to be a layer.
[0058]
As a condition for winding the film into a roll, it is preferable that the film winding curvature (R) is within a range represented by the following formula, since such an effect can be obtained more greatly.
[0059]
0 <R (m^-1<R₀   R₀= 900a / (400-9b + 9a)
a: Increase in curl value over time when stored for one year at 23 ° C and 55% RH with the film still on a flat plate
b: Curvature is 100m^-1Increase in curl value when stored at 23 ° C and 55% RH for 1 year with a winding diameter of φ20mm
Surprisingly, the laminated polymer film of the present invention can be obtained by using any one of the resins constituting the laminated film alone under the same film-forming conditions by making R within the range of the above formula. The core set curl value is smaller than that of a single resin (single layer) film.
[0060]
By coating such a laminated polymer film on a functional film such as a photosensitive layer, the core set curl during use of the roll-shaped functional film is reduced.
[0061]
However, the winding diameter of a general film ranges from about 10 mm of the photographic negative film cartridge diameter to about 1 m of the original winding roll in the manufacturing process. In this case, the winding curvature is 2 m.^-1From 200m^-1Therefore, a film having the above R value within this range is particularly desirable.
[0062]
In this specification, the winding diameter or winding curvature of the film means both the case where the core is present and the case where the core is not present, and the cross section of the wound roll film may not be a perfect circle.
[0063]
In addition, the present invention is used for a roll-shaped OHP sheet, a roll-shaped drawing film, a roll-shaped printing sheet or the like used while the self-supporting film itself is stored in a roll shape, but is not limited thereto.
[0064]
Applying the undercoating resin before completion of the oriented crystal in the present invention means applying the undercoating resin before performing the above-described heat setting. That is, it means that after understretching or after biaxial stretching, an undercoating resin is applied and at least one layer of the undercoating resin is provided, followed by heat setting. Among these, it is preferable to coat after unstretching or after uniaxial stretching.
[0065]
The undercoating resin used in the present invention may be a known one that is coated before heat setting. For example, U.S. Pat. Vinyl halide ester-containing copolymers or vinyl halogenoester-containing copolymers and vinyl chloride and / or vinylidene chloride-containing copolymers, JP-B 58-58661, JP-B 58-55497, JP-A 52-108114 Copolymers containing monomers as monomers, acrylic polymers described in JP-A-61-204242, JP-A-61-204241, JP-B-57-971, JP-A-61-204240, JP-A-60-248231, Examples thereof include polyester polymers described in JP-A-3-265624.
[0066]
【Example】
Hereinafter, the present invention will be described in detail by way of examples.
[0067]
[Create sample]
Sample 1
To 100 parts by weight of terephthalic acid and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added, and an esterification reaction was performed by a conventional method. The obtained product was mixed with 28 parts by weight of ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acid component), polyethylene glycol (number average molecular weight 3000) 8.1 parts by weight (7% by weight / polymer), 0.05 parts by weight of antimony trioxide, and 0.13 parts by weight of trimethyl phosphate were added. Next, the temperature was gradually raised and reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.
[0068]
This copolymerized polyester (abbreviation M) and commercially available polyethylene terephthalate (abbreviation P) having an intrinsic viscosity of 0.65 were each vacuum-dried at 150 ° C. and then melt-extruded at 285 ° C. using three extrusion units. The layers were joined in layers in a T-die so as to be composed of the materials shown in (1), and rapidly cooled and solidified while being in close contact with the cooling drum by an electrostatic contact method, to obtain a laminated unstretched film. At this time, the extrusion amount of each material was adjusted so that the thickness of each layer was 9: 10: 7. Next, the film was stretched 3.5 times in the vertical direction at 85 ° C., further stretched 3.5 times in the horizontal direction at 95 ° C., and heat-set at 210 ° C. to obtain a biaxially stretched film having a thickness of 50 μm.
[0069]
The intrinsic viscosity was measured by the following method.
[0070]
<Intrinsic viscosity>
The measurement was performed using an Ubbelohde viscometer. A mixed solvent having a weight ratio of phenol to 1,1,2,2-tetrachloroethane of about 55:45 (adjusted to a flow-down time of 42.0 ± 0.1 seconds) and having a sample concentration of 0.2, 0.6, 1.0 (g / dl) A solution (temperature 20 ° C.) was prepared. The specific viscosity (η at each concentration (C) was measured by an Ubbelohde viscometer._sp)

Was used to extrapolate to zero concentration, and the intrinsic viscosity [η] was determined.
[0071]
Sample 2
A film having a thickness of 75 μm was obtained in the same manner as Sample 1 above.
[0072]
Sample 3
A film having a thickness of 100 μm was obtained in the same manner as Sample 1 above.
[0073]
Sample 4
A film having a thickness of 125 μm was obtained in the same manner as Sample 1 above.
[0074]
Sample 5
A film was obtained in the same manner as in Sample 1 except that the copolymer polyester in Sample 1 and a commercially available polyethylene terephthalate (inherent viscosity 0.65) were formed in a ratio of 1:39 and a thickness of 50 μm.
[0075]
Sample 6
A film having a thickness of 75 μm was obtained in the same manner as Sample 5 above.
[0076]
Sample 7
A film having a thickness of 100 μm was obtained in the same manner as Sample 5 above.
[0077]
Sample 8
A film having a thickness of 125 μm was obtained in the same manner as Sample 5 above.
[0078]
Sample 9
A 50 μm film was obtained in the same manner as Sample 5 except that the ratio of the two layers in Sample 5 was 4:36.
[0079]
sample Ten
A film having a thickness of 75 μm was obtained in the same manner as Sample 9 above.
[0080]
sample 11
A film having a thickness of 100 μm was obtained in the same manner as Sample 8 above.
[0081]
sample 12
A film having a thickness of 125 μm was obtained in the same manner as Sample 8 above.
[0082]
sample 13
A film having a thickness of 50 μm was obtained in the same manner as in Sample 1 except that the ratio of the thickness of each layer in Sample 1 was set to 3: 2: 1.
[0083]
sample 14
A film having a thickness of 75 μm was obtained in the same manner as Sample 13 above.
[0084]
sample 15
A film having a thickness of 90 μm was obtained in the same manner as Sample 13 above.
[0085]
sample 16
A film having a thickness of 100 μm was obtained in the same manner as Sample 13 above.
[0086]
sample 17
A film having a thickness of 125 μm was obtained in the same manner as Sample 13 above.
[0087]
sample 18
A 50 μm film was obtained in the same manner as Sample 5 except that the ratio of the two layers in Sample 5 was 8:32.
[0088]
sample 19
A film having a thickness of 75 μm was obtained in the same manner as in Sample 18.
[0089]
sample 20
A film having a thickness of 90 μm was obtained in the same manner as Sample 18 above.
[0090]
sample twenty one
A film having a thickness of 100 μm was obtained in the same manner as Sample 18 above.
[0091]
sample twenty two
A 50 μm film was obtained in the same manner as in Sample 5, except that the ratio of the two layers in Sample 5 was 28:12.
[0092]
sample twenty three
A film having a thickness of 75 μm was obtained in the same manner as Sample 22 above.
[0093]
sample twenty four
A film having a thickness of 100 μm was obtained in the same manner as Sample 22 above.
[0094]
sample twenty five
A 50 μm film was obtained in the same manner as in Sample 5, except that the ratio of the two layers in Sample 5 was 12:28.
[0095]
sample 26
A film having a thickness of 75 μm was obtained in the same manner as Sample 25.
[0096]
sample 27
A film having a thickness of 90 μm was obtained in the same manner as in Sample 25.
[0097]
sample 28
A film having a thickness of 100 μm was obtained in the same manner as Sample 25.
[0098]
sample 29
A 50 μm film was obtained in the same manner as Sample 5 except that the ratio of the two layers in Sample 5 was 20:20.
[0099]
sample 30
A film having a thickness of 75 μm was obtained in the same manner as Sample 29 above.
[0100]
sample 31
A film having a thickness of 100 μm was obtained in the same manner as Sample 29 above.
[0101]
sample 32
A film having a thickness of 50 μm was obtained in the same manner as in Sample 1 except that only a copolymerized polyester film in Sample 1 was used.
[0102]
The single layer film had a glass transition temperature (Tg) of 61 ° C.
[0103]
sample 33
A film having a thickness of 75 μm was obtained in the same manner as Sample 32 above.
[0104]
sample 34
A film having a thickness of 90 μm was obtained in the same manner as Sample 32 above.
[0105]
sample 35
A film having a thickness of 100 μm was obtained in the same manner as Sample 32 above.
[0106]
sample 36
A film having a thickness of 125 μm was obtained in the same manner as Sample 32 above.
[0107]
sample 37
A film having a thickness of 50 μm was obtained in the same manner as in Sample 1 except that only a commercially available polyethylene terephthalate (inherent viscosity 0.65) in Sample 1 was used.
[0108]
The single layer film had a glass transition temperature (Tg) of 77 ° C.
[0109]
sample 38
A film having a thickness of 75 μm was obtained in the same manner as Sample 37 above.
[0110]
sample 39
A film having a thickness of 90 μm was obtained in the same manner as Sample 37 above.
[0111]
sample 40
A film having a thickness of 100 μm was obtained in the same manner as Sample 37 above.
[0112]
sample 41
A film having a thickness of 125 μm was obtained in the same manner as Sample 37 above.
[0113]
sample 42
A film having a thickness of 50 μm was obtained in the same manner as in Sample 1 except that the ratio of the thickness of each layer in Sample 1 was 1: 1: 1.
[0114]
sample 43
A film having a thickness of 75 μm was obtained in the same manner as Sample 42 above.
[0115]
sample 44
A film having a thickness of 90 μm was obtained in the same manner as Sample 42 above.
[0116]
sample 45
A film having a thickness of 100 μm was obtained in the same manner as Sample 42 above.
[0117]
sample 46
A film having a thickness of 125 μm was obtained in the same manner as Sample 42 above.
[0118]
(Measurement method of curl value)
▲ 1 ▼ flat plate (curvature 0m^-1) Measurement of curl value over time in the state of standing on
All of the above samples 1 to 46 have almost zero curl immediately after film formation, and the sample without initial curl is cut into a size of 120 mm × 35 mm (120 mm in the longitudinal stretching direction and 35 mm in the lateral stretching direction) and placed on a flat plate. Table 1 shows the curl value (1 / m) measured after standing for 12 months in a room that was allowed to stand and adjusted to a temperature of 23 ° C. and a relative humidity of 55%.
[0119]
However, the standing in this case is a state where no external force is applied to the film other than its own weight.
[0120]
(2) Curvature 100m^-1Measurement of core set curl value when saved with
100m curvature of the same sample as above^-1(Φ20mm) Resin core is placed in the opposite direction to the direction of curling over time, and the end is fixed with tape, then left in a room adjusted to a temperature of 23 ° C and a relative humidity of 55% for 12 months, then released. The curl value (1 / m) was measured and shown in Table 1.
[0121]
(Measurement of shrinkage over time)
The single layer sample was measured for shrinkage with time in the following manner and shown in Table 1. Marks were placed at 100 mm intervals on a film of sample size 120 mm x 35 mm, and the amount of shrinkage was calculated from the dimensional change between the marks after standing for 12 months at a temperature of 23 ° C and a relative humidity of 55%.
[0122]
Curling over time did not occur in a single layer film or a comparative sample film having a symmetrical laminated structure. In addition, all the films of the present invention in which curling with time occurred had concave curls on the side where the copolymerized polyester component having a large shrinkage rate with time was large.
[0123]
R calculated from the above measurements (1) and (2)₀(M^-1) Values are also shown in Table 1.
[0124]
R for single-layer films or films with a symmetrical laminated structure₀Therefore, the winding curvature R of claim 3 does not exist.
[0125]
[Table 1]

[0126]
Example 1
Samples No. 1 to 12 were cut to A2 size (with the longitudinal direction being the longitudinal direction), and the diameter was 90 mm (curvature: 22 m^-1) In a circular cylinder for storing drawings in the opposite direction with respect to the curl over time (invention examples No. 1 to 12). As a comparative example, the same sample was wound in the same direction as the curl over time (Comparative Examples No. 1 to 12).
[0127]
Samples 32, 33, 35, 36, 37, 38, 40, 41, 42, 43, 45, and 46 that do not curl over time were similarly placed in round tubes as comparative examples (Comparative Examples Nos. 13 to 24). ).
[0128]
The round cylinders containing these films were stored for 12 months in an environment of 23 ° C. and 55% humidity with the lid open, and the curl values were measured and shown in Table 2.
[0129]
The curl value was measured by cutting out a piece having a size of 120 mm in the longitudinal direction and 35 mm in the width direction from a substantially central portion of the A2 size film.
[0130]
[Table 2]

[0131]
Example 2
Samples Nos. 1-14, 16 and 17 were cut to A2 size in the same manner as in Example 1, and the diameter was 47 mm (curvature 43 m^-1) In a circular cylinder for storing drawings, respectively, wound in the opposite direction to the curling direction over time (invention examples No. 13 to 28). As a comparative example, the same sample was wound in the same direction as the curl over time (Comparative Examples No. 25 to 40).
[0132]
Samples 32, 33, 35, 36, 37, 38, 40, 41, 42, 43, 45, and 46 that do not curl over time were also placed in round cylinders as comparative examples (Comparative Examples Nos. 41 to 52). ).
[0133]
The circular cylinders containing these films were stored for 12 months in an environment of 23 ° C. and 55% humidity, and their curl values were measured and shown in Table 3.
The method for measuring the curl value is the same as in Example 1.
[0134]
[Table 3]

[0135]
Example 3
Samples No. 1 to 12 were slitted to a width of 16 cm, wound into a roll shape on a 3 inch outer diameter core until the outer diameter of the winding reached 6.4 inch, and the end of the film was stopped with tape. However, at this time, both the roll wound in the reverse direction with respect to the curl over time as an example of the present invention and the roll wound in the same direction as a comparative example were simultaneously created (invention examples No. 29 to 40, comparative example No. 53-64).
[0136]
Samples 32, 33, 35, 36, 37, 38, 40, 41, 42, 43, 45, and 46 that did not curl over time were similarly wound in a roll as a comparative example (Comparative Examples No. 65 to 76). .
[0137]
These roll-shaped films were stored for 12 months in an environment of 23 ° C. and humidity of 55%, and the curl values at the core and outside of the roll were measured and shown in Table 4.
[0138]
The curl value was measured by cutting a piece having a size of 120 mm in the longitudinal direction and 35 mm in the width direction.
[0139]
The core set curl value on the outer side of the film No. 29 to 32 of the present invention example is smaller than that on the outer side of the PET single layer (Comparative Example No. 69 to 72). Become bigger. However, the maximum curl value (absolute value) and the average curl value in the entire film length are considerably smaller than those of PET.
[0140]
[Table 4]

[0141]
Example 4
Samples Nos. 1-3, 5-7, 9-11, 13, 14, 16, 18, 19, 21-24 are 120mm x 35mm in size (120mm in the longitudinal direction and 35mm in the lateral direction) Cutting and diameter
30mm (curvature 67m^-1) And the ends were fixed with tape. However, at this time, both the sample wound in the opposite direction to the curl over time as the example of the present invention and the sample wound in the same direction as the comparative example were prepared at the same time (invention example Nos. 41 to 58 and comparative examples No. 77 to 94). ).
[0142]
Samples 32, 33, 35, 37, 38, 40, 42, 43, and 45 that did not curl over time were similarly wound around the core as comparative examples (Comparative Examples No. 95 to 103).
[0143]
These samples were stored for 12 months in an environment of 23 ° C. and 55% humidity, and their curl values were measured and shown in Table 5.
[0144]
[Table 5]

[0145]
Example 5
Samples Nos. 2-3, 6-7, 10-11, 14, 16, 19, 21, 23-24, 26, 28, 30-31 are 120mm x 35mm in size (120mm in the longitudinal direction, transversely stretched) Cut to 35mm in the direction, diameter 20mm (curvature 100m^-1) And the ends were fixed with tape. However, at this time, both the sample wound in the reverse direction with respect to the curl over time as the example of the present invention and the sample wound in the same direction as the comparative example were prepared at the same time (invention examples No. 59 to 74, comparative example No. 104). ~ 119).
[0146]
Samples 33, 35, 38, 40, 43, and 45 that did not curl over time were similarly wound around cores as comparative examples (Comparative Examples Nos. 120 to 125).
[0147]
These samples were stored for 12 months in an environment of 23 ° C. and 55% humidity, and the curl values were measured and shown in Table 6.
[0148]
[Table 6]

[0149]
Example 6
  Samples No.2, 6, 10, 14, 15, 19, 20, 23, 26, 27, 30 are 120mm x 35mm
Photographic negative film spool with a diameter of 10.8mm (curvature 185m) cut to size (120mm in the longitudinal stretching direction and 35mm in the lateral stretching direction)^-1) And the end was fixed with tape. However, at this time, both the one wound in the reverse direction with respect to the curling direction with time as the inventive example and the one wound in the same direction as the comparative example were simultaneously prepared (Invention Examples No. 75 to 85, Comparative Example) No. 126-136).
[0150]
Samples 33, 34, 38, 39, 43, and 44 that were not curled over time were similarly wound on spools as comparative examples (Comparative Examples Nos. 137 to 142).
[0151]
These samples were stored for 12 months in an environment of 23 ° C. and 55% humidity, and their curl values were measured and shown in Table 7.
[0152]
[Table 7]

[0153]
From the Examples, it can be seen that when the laminated polymer film is wound in the direction opposite to the direction of curling with time, the core set curl value is greatly reduced as compared with the case of winding in the forward direction.
[0154]
Further, the winding curvature (R) of the laminated polymer film is set to R of the film.₀By making it smaller than the value, the core set curl value becomes smaller than any single layer film of each resin constituting the laminated polymer film.
[0155]
Therefore, according to the present invention, there is provided a method for reducing the core set curl at the time of use of a roll-shaped functional film or a roll-shaped functional film in which a silver halide emulsion layer or the like is coated on the polymer film to a level that does not cause a problem in use. Could be provided.
[0156]
Example 7
Example of support manufacturing for undercoating before heat setting
Support NO.1
To 100 parts by weight of terephthalic acid and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added, and an esterification reaction was performed by a conventional method. The obtained product was mixed with 28 parts by weight of ethylene glycol solution (concentration 35% by weight) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (5 mol% / total acid content), polyethylene glycol (number average molecular weight 3000) 8.1 parts by weight (7% by weight / polymer), 0.05 parts by weight of antimony trioxide, and 0.13 parts by weight of trimethyl phosphate were added. Subsequently, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.
[0157]
This copolymerized polyester (abbreviation M) and commercially available polyethylene terephthalate (abbreviation P) with intrinsic viscosity of 0.65 are vacuum dried at 150 ° C., and then melt extruded at 285 ° C. using three extruders. While being closely attached to the cooling drum, it was rapidly cooled and solidified to obtain a laminated unstretched film. At this time, the extrusion amount of each material was adjusted so that the thickness of each layer was 9: 10: 7.
[0158]
Next, the film was stretched 3.5 times in the vertical direction at 85 ° C.
[0159]
Next, 37 parts by weight of dimethyl terephthalate, 30 parts by weight of dimethyl isophthalate, 10 parts by weight of sodium dimethyl 5-sulfoisophthalate, 52 parts by weight of ethylene glycol, 16 parts by weight of 1,4-cyclohexanedicarboxylic acid, polyethylene glycol (number average) An 8% aqueous solution of a copolyester (inherent viscosity 0.52) obtained by polymerizing 5 parts by weight of a molecular weight of 1,000) is used as an undercoat layer coating solution, and 0.3 g / m in dry weight on both sides of the film after the vertical stretching.²It was applied so as to have an undercoat layer.
[0160]
Next, the film was further stretched 3.5 times in the horizontal direction at 95 ° C. and then heat-set at 210 ° C. to obtain a biaxially stretched film having a thickness of 90 μm.
[0161]
Support NO.2
A laminated unstretched film was obtained in the same manner as the support No. 1, and then a solution of 70 parts by weight of a styrene-butadiene (92-8% by weight) copolymer, 10 parts by weight of a polyethyl acrylate polymer, and 10 parts by weight of gelatin was obtained. 4 g / m in dry weight on both sides of the unstretched film as an undercoat coating solution²It was applied so as to have an undercoat layer.
[0162]
Next, the film was stretched 3.5 times in the vertical direction at 85 ° C., further stretched 3.5 times in the horizontal direction at 95 ° C., and heat-set at 210 ° C. to obtain a biaxially stretched film having a thickness of 90 μm.
[0163]
Support NO.3, 5, 7, 9, 11, 13
The supports prepared in the same manner as NO. 1 except that the lamination ratio, layer configuration, and film thickness were changed as shown in Table 8 below were designated as NO. 3, 5, 7, 9, 11, and 13.
[0164]
Support N0.4, 6, 8, 10, 12, 14
The supports produced in the same manner as in No. 2 except that the lamination ratio, layer structure and film thickness were changed as shown in Table 1 were designated as Nos. 4, 6, 8, 10, 12, and 14. These supports had the property of curling in the longitudinal stretching direction over time.
[0165]
These samples were cut into 3.5 cm × 10 cm so that the longitudinal stretching direction was long, and left on a flat plate at 23 ° C. and 55% for 12 months. Table 8 shows the absolute value (curl value with time) of the difference between the curl amount after being left and the curl amount before being left.
[0166]
[Table 8]

[0167]
Comparative support example
A film prepared in the same manner as the support 1 except that the composition ratio was 1/1/1 was determined as support NO.15.
[0168]
A film prepared in the same manner as the support 1 except that only the copolyester (M) is used is referred to as support NO.16.
[0169]
The curl values of these two supports over time were less than 2 in absolute value.
[0170]
Further, the difference between the shrinkage rate with time of 1 year at 23 ° C. and the shrinkage rate with time of support No. 16 was about 0.3% in the film obtained by forming the above polyethylene terephthalate resin in the same manner as the support 1.
[0171]
Example of support manufacturing for undercoating after heat setting
Except for not undercoating before heat setting, 0.5 g of the water-soluble polymer compound shown below was dissolved in 5 cc of water on both sides of the polyester film after biaxial stretching heat setting as in the case of support NO.3. This solution was mixed and dissolved in a 95 cc methanol solution containing 4 g of resorcin.²It was applied at 50 mg per unit and dried at 100 ° C. for 2 minutes. This support is designated as N0.17.
[0172]
A support body that has been biaxially stretched and heat-fixed in the same manner as the support body No. 16 except that the subbing process before heat setting is not performed, and then subjected to the subbing process in the same manner as NO.
[0173]
The following backing layer and emulsion layer were coated to prepare a color negative silver halide photographic light-sensitive material. Incidentally, the polyester support whose curl value continuously curls in one direction with time has an emulsion layer provided on the curled and convex side.
[0174]
<Measurement of curl amount>
The silver halide photographic light-sensitive material thus prepared was cut to a width of 3.5 cm so that the longitudinal stretching direction of the support was long, cut to a length of 10 cm, and the winding end was fixed with a tape with a core of 10.8 mm in diameter. It was left for 12 months at 23 ° C and 55%. After standing, the tape was peeled off, the curl value was measured, and the amount was curled up. The obtained values are shown in Table 9.
[0175]
[Table 9]

[0176]
As is clear from Table 9, the support that curls over time is less likely to curl.
[0177]
Further, when Example 3 of the present invention is compared with Comparative Example 17 and Comparative Example 16 and Comparative Example 18 are compared, the effect of subbing before the end of crystal orientation is particularly remarkable in a support that curls with time.
[0178]
In addition, any sample had no problem with the curling recovery property after the development processing.
[0179]
<Backing layer>
First layer;
Gelatin 4.5mg
Sodium-di-(-2-ethylhexyl) -sulfosuccinate 1.0mg
Sodium tripolyphosphate 76mg
Citric acid 16mg
Carboxyalkyl dextran sulfate 49mg
Vinylsulfone type hardener 30mg
Second layer (outermost layer);
Gelatin 1.5g
Polymer beads
(Average particle size: 3μm, polymethyl methacrylate) 24mg
Vinylsulfone type hardener 45mg
30 mg of a mixture of compound SB-1 and compound SB-2
Compound SB-1 100mg
<Emulsion layer>
First layer: Antihalation layer (HC)
Black colloidal silver 0.15g
UV absorber (UV-1) 0.20g
Compound (CC-1) 0.02g
High boiling point solvent (Oil-1) 0.20g
High boiling point solvent (Oil-2) 0.20g
Gelatin 1.6g
Second layer; intermediate layer (IL-1)
Gelatin 1.3g
Third layer: Low-sensitivity red-sensitive emulsion layer (RL)
Silver iodobromide emulsion
(Average particle size 0.3 μm, average iodine content 2.0 mol%) 0.4 g
Silver iodobromide emulsion
(Average particle size 0.4μm, average iodine content 8.0mol%) 0.3g
Sensitizing dye (S-1) 3.2 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-2) 3.2 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-3) 0.2 × 10^-Four(Mol / silver 1 mol)
Cyan coupler (C-1) 0.50g
Cyan coupler (C-2) 0.13g
Colored Cyan Coupler (CC-1) 0.07g
DIR compound (D-1) 0.006g
DIR compound (D-2) 0.01g
High boiling point solvent (Oil-1) 0.55g
Gelatin 1.0g
Fourth layer: High-sensitivity red-sensitive emulsion layer (RH)
Silver iodobromide emulsion
(Average particle size 0.7μm, average iodine content 7.5mol%) 0.9g
Sensitizing dye (S-1) 1.7 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-2) 1.6 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-3) 0.1 × 10^-Four(Mol / silver 1 mol)
Cyan coupler (C-2) 0.23g
Colored Cyan Coupler (CC-1) 0.03g
DIR compound (D-2) 0.02g
High boiling point solvent (Oil-1) 0.25g
Gelatin 1.0g
5th layer: Intermediate layer (IL-2)
Gelatin 0.8g
Sixth layer: Low-sensitivity green-sensitive emulsion layer (GL)
Silver iodobromide emulsion
(Average particle size 0.4μm, average iodine content 8.0mol%) 0.6g
Silver iodobromide emulsion
(Average particle size 0.3μm, average iodine content 2.0mol%) 0.2g
Sensitizing dye (S-4) 6.7 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-5) 0.8 × 10^-Four(Mol / silver 1 mol)
Magenta coupler (M-1) 0.17g
Magenta coupler (M-2) 0.43g
Colored magenta coupler (CM-1) 0.10g
DIR compound (D-3) 0.02g
High boiling point solvent (Oil-2) 0.7g
Gelatin 1.0g
Seventh layer: High-sensitivity green-sensitive emulsion layer (GH)
Silver iodobromide emulsion
(Average particle size 0.7μm, average iodine content 7.5mol%) 0.9g
Sensitizing dye (S-6) 1.1 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-7) 2.0 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-8) 0.3 × 10^-Four(Mol / silver 1 mol)
Magenta coupler (M-1) 0.30g
Magenta coupler (M-2) 0.13g
Colored magenta coupler (CM-1) 0.04g
DIR compound (D-3) 0.004g
High boiling point solvent (Oil-2) 0.35g
Gelatin 1.0g
8th layer: Yellow filter layer (YC)
Yellow colloidal silver 0.1g
Additive (HS-1) 0.07g
Additive (HS-2) 0.07g
Additive (SC-1) 0.12g
High boiling point solvent (Oil-2) 0.15g
Gelatin 1.0g
Ninth layer: Low-sensitivity blue-sensitive emulsion layer (BL)
Silver iodobromide emulsion
(Average particle size 0.3μm, average iodine content 2.0mol%) 0.25g
Silver iodobromide emulsion
(Average particle size 0.4μm, average iodine content 8.0mol%) 0.25g
Sensitizing dye (S-9) 5.8 × 10^-Four(Mol / silver 1 mol)
Yellow coupler (Y-1) 0.6g
Yellow coupler (Y-2) 0.32g
DIR Compound (D-1) 0.003g
DIR compound (D-2) 0.006g
High boiling point solvent (Oil-2) 0.18g
Gelatin 1.3g
10th layer: High sensitivity blue-sensitive emulsion layer (BH)
Silver iodobromide emulsion
(Average particle size 0.8μm, average iodine content 8.5mol%) 0.5g
Sensitizing dye (S-10) 3 × 10^-Four(Mol / silver 1 mol)
Sensitizing dye (S-11) 1.2 × 10^-Four(Mol / silver 1 mol)
Yellow coupler (Y-1) 0.18g
0.10g of yellow coupler (Y-2)
High boiling point solvent (Oil-2) 0.05g
Gelatin 2.0g
11th layer; 1st protective layer (PRO-1)
Silver iodobromide (average grain size 0.08μm) 0.3g
UV absorber (UV-1) 0.07g
UV absorber (UV-2) 0.08g
Additive (HS-1) 0.2g
Additive (HS-2) 0.1g
High boiling point solvent (Oil-1) 0.07g
High boiling point solvent (Oil-3) 0.07g
Gelatin 0.8g
12th layer; 2nd protective layer (PRO-2)
Compound (Compound A) 0.04g
Compound (Compound B) 0.004g
Polymethylmethacrylate (average particle size: 3μm) 0.02g
Methyl methacrylate: Ethyl methacrylate: Methacrylic acid
= 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g
Gelatin 0.7g
-Preparation of silver iodobromide emulsion-
The silver iodobromide emulsion used in the 10th layer was prepared by the following method.
[0180]
A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.
[0181]
A solution <G-1> having the following composition was maintained at a temperature of 70 ° C., pAg 7.8, and pH 7.0, and 0.34 mol of the seed emulsion was added while stirring well.
[0182]
(Formation of internal high iodine phase-core phase)
Thereafter, the solution <H-1> having the following composition and the solution <S-1> having the following composition are maintained at a flow rate of 1: 1 while maintaining an accelerated flow rate (the flow rate at the end is 3.6 times the initial flow rate). Added over 86 minutes.
[0183]
(Formation of external low iodine phase-shell phase)
Subsequently, while maintaining pAg10.1 and pH6.0, <H-2> and <S-2> were accelerated at a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate). It took 65 minutes to add.
[0184]
The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the formation of the particles, it was washed with water by a conventional flocculation method, and then gelatin was added and redispersed. At 40 ° C., pH and pAg were adjusted to 5.8 and 8.06, respectively.
[0185]
The obtained emulsion was a monodispersed emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution range of 12.4%, and a silver iodide content of 8.5 mol%.
[0186]
<G-1> Solution
Ossein gelatin 100.0g
10% by weight methanol solution of the following compound-I 25.0ml
28% ammonia solution 440.0ml
56% acetic acid aqueous solution 660.0ml
Finish with water 5000.0ml
* Compound I: Polypropyleneoxy, polyethyleneoxy, dioxalic acid, sodium.
[0187]
<H-1> Solution
Ossein gelatin 82.4g
Potassium bromide 151.6g
Potassium iodide 90.6g
Finish with water 1030.5ml
<S-1> Solution
Silver nitrate 309.2g
28% aqueous ammonia equivalent
Finish with water 1030.5ml
28% aqueous ammonia equivalent
Finish with water 1030.5ml
<H-2> solution
Ossein gelatin 302.1g
Potassium bromide 770.0g
Potassium iodide 33.2g
Finish with water 3776.8ml
<S-2> Solution
Silver nitrate 1133.0g
28% aqueous ammonia equivalent
Finish with water 3776.8ml
For silver iodobromide emulsions used in emulsion layers other than the tenth layer, the average grain size, temperature, pAg, pH, flow rate, addition time, and halide composition of the seed crystal were changed in the same manner. The above emulsions having different average grain sizes and different silver iodide contents were prepared.
[0188]
All were core / shell type monodispersed emulsions having a distribution range of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to produce a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. 1-phenyl-5-mercaptotetrazole was added.
[0189]
In addition, the above-described photosensitive material further includes compounds Su-1, Su-2, a viscosity modifier, a hardener H-1, H-2, a stabilizer ST-1, an antifoggant AF-1, AF-2. (Weight average molecular weight 10,000 and 1,100,000), dye AI-1, AI-2 and compound DI-1 (9.4 mg / m²).
[0190]
-Film development processing-
[0191]
[Table 10]

[0192]
In Table 10, the replenishment amount is 1 m of photosensitive material.²It is a hit value.
[0193]
Color developing solutions, bleaching solutions, fixing solutions, stabilizers and replenishers thereof were prepared as follows.
[0194]
<Color developer>
800ml water
Potassium carbonate 30g
Sodium bicarbonate 2.5g
Potassium sulfite 3.0g
Sodium bromide 1.3g
Potassium iodide 1.2mg
Hydroxylamine sulfate 2.5g
Sodium chloride 0.6g
4-Amino-3-methyl-N-ethyl-N-
(Β-Hydroxyethyl) aniline sulfate 4.5g
Diethylenetriaminepentaacetic acid 3.0g
Potassium hydroxide 1.2g
Water was added to 1 liter, and the pH was adjusted to 10.06 using potassium hydroxide or 20% sulfuric acid.
[0195]
<Color development replenisher>
800ml water
Potassium carbonate 35g
Sodium bicarbonate 3g
Potassium sulfite 5g
Sodium bromide 0.4g
Hydroxylamine sulfate 3.1g
4-Amino-3-methyl-N-ethyl-N-
(Β-Hydroxyethyl) aniline sulfate 6.3g
Potassium hydroxide 2g
Diethylenetriaminepentaacetic acid 3.0g
Water was added to 1 liter, and the pH was adjusted to 10.18 using potassium hydroxide or 20% sulfuric acid.
[0196]
<Bleaching solution>
700ml of water
1,3-diaminopropanetetraacetic acid iron (III) ammonium ・ 125g
Ethylenediaminetetraacetic acid 2g
Sodium nitrate 40g
150g ammonium bromide
Glacial acetic acid 40g
Water was added to 1 liter, and the pH was adjusted to 4.4 using aqueous ammonia or glacial acetic acid.
[0197]
<Bleaching replenisher>
700ml of water
1,3-diaminopropanetetraacetic acid iron (III) ammonium ・ 175g
Ethylenediaminetetraacetic acid 2g
Sodium nitrate 50g
Ammonium bromide 200g
Glacial acetic acid 56g
After adjusting the pH to 4.0 using aqueous ammonia or glacial acetic acid, water was added to make 1 liter.
[0198]
<Fixing solution>
800ml water
120g ammonium thiocyanate
150g ammonium thiosulfate
Sodium sulfite 15g
Ethylenediaminetetraacetic acid 2g
After adjusting the pH to 6.2 using ammonia water or glacial acetic acid, water was added to make 1 liter.
[0199]
<Fixing replenisher>
800ml water
150g ammonium thiocyanate
180g ammonium thiosulfate
Sodium sulfite 20g
Ethylenediaminetetraacetic acid 2g
After adjusting the pH to 6.5 with aqueous ammonium or glacial acetic acid, water was added to make 1 liter.
[0200]
<Stabilizer and stable replenisher>
900ml water
The compound represented by the following (Chemical Formula 2) 2.0 g
Dimethylolurea 0.5g
Hexamethylenetetramine 0.2g
1,2-benzisothiazolin-3-one 0.1g
Siloxane (UCC: L-77) 0.1g
Ammonia water 0.5ml
After adding water to make 1 liter, it was adjusted to pH 8.5 using ammonia water or 50% sulfuric acid.
[0201]
[Chemical formula 2]

[0202]
The structures of the respective compounds used for forming the silver halide photographic light-sensitive material according to the present invention are shown below.
[0203]
[Chemical Formula 3]

[0204]
[Formula 4]

[0205]
[Chemical formula 5]

[0206]
[Chemical 6]

[0207]
[Chemical 7]

[0208]
[Chemical 8]

[0209]
[Chemical 9]

[0210]
Embedded image

[0211]
Embedded image

[0212]
Embedded image

[0213]
Embedded image

[0214]
Embedded image

[0215]
Embedded image

[0216]
Embedded image

[0217]
【The invention's effect】
According to the present invention, the core set curl when using a polymer film stored in a roll or a functional film in which a silver halide emulsion layer is coated on the polymer film is reduced to such an extent that it does not cause a problem in use. A rolled film can be provided. Further, it is possible to provide a silver halide photographic light-sensitive material which is difficult to curl and can be easily curled by development processing.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing a curled state of a film.

Claims (3)

A curl value in the longitudinal direction of the film (reciprocal of the radius of curvature) when at least two layers of resins having different shrinkage amounts with time are laminated asymmetrically with respect to the center plane with respect to both sides of the film. ) Changes in one direction over time, and is cut into a 3.5cm x 12cm strip so that the direction of curl change is in the longitudinal direction. Leave it on a flat plate at 23 ° C and 55 % for 12 months. roll film, characterized in that the time curl value is the absolute value of the difference between the curl values a Ru film 2～250M ^-1 der, is wound into a roll in the curl direction opposite to the direction of the film . The roll film according to claim 1, wherein the winding curvature (R) is within a range represented by the following formula.
0 <R (m ^-1 ) <R ₀ R ₀ = 900a / (400-9b + 9a)
a: Curling value with time when the film was stored on a flat plate at 23 ° C. and 55% RH for one year b: The film was wound at a winding diameter (φ20 mm) with a curvature of 100 m ⁻¹ Increase in curl value when stored at 23 ° C and 55% RH for 1 year A roll-shaped silver halide photographic light-sensitive material having at least one silver halide emulsion layer on at least one side of a polyester support, wherein the support comprises at least two layers of resins having different shrinkage over time. The support is laminated asymmetrically with respect to the center plane, and the support is cut into a 3.5 cm × 12 cm strip so that the curl value changes in one direction over time and the direction in which the curl change occurs is the longitudinal direction. 23 ° C., and 12 months standing on a plate with 55% under the conditions, temporal curl value left is the absolute value of the difference between before and after the curl value has a 2～250M ^-1 der Ru characteristics, and, of the support A rolled silver halide photographic light-sensitive material, which is rolled in the direction opposite to the curl direction of a support having a hydrophilic colloid layer coated with an undercoating resin before completion of oriented crystal.

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