JPS62287243A - Substrate body for silver halide photographic sensitive material having undercoat of excellent sticking property - Google Patents
Substrate body for silver halide photographic sensitive material having undercoat of excellent sticking propertyInfo
- Publication number
- JPS62287243A JPS62287243A JP61130206A JP13020686A JPS62287243A JP S62287243 A JPS62287243 A JP S62287243A JP 61130206 A JP61130206 A JP 61130206A JP 13020686 A JP13020686 A JP 13020686A JP S62287243 A JPS62287243 A JP S62287243A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- gelatin
- support
- undercoat
- undercoat layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title description 8
- 229910052709 silver Inorganic materials 0.000 title 1
- 239000004332 silver Substances 0.000 title 1
- 239000000758 substrate Substances 0.000 title 1
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 108010010803 Gelatin Proteins 0.000 claims abstract description 22
- 229920000159 gelatin Polymers 0.000 claims abstract description 22
- 239000008273 gelatin Substances 0.000 claims abstract description 22
- 235000019322 gelatine Nutrition 0.000 claims abstract description 22
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 22
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 7
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000002253 acid Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 8
- 238000001879 gelation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 55
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- 229920013716 polyethylene resin Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 210000003813 thumb Anatomy 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- DVVZWFCYVJKULS-UHFFFAOYSA-N 2,4-bis(ethenylsulfonylmethyl)pentanediamide Chemical compound C=CS(=O)(=O)CC(C(=O)N)CC(CS(=O)(=O)C=C)C(N)=O DVVZWFCYVJKULS-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
- G03C2001/0471—Isoelectric point of gelatine
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〔産業上の利用分野］
本発明は、接着性のすぐれた下塗り層を有する写真感光
材料支持体に関するものである。更に詳しく述べるなら
ば本発明は、ポリオレフィン樹脂からなる表面層と、そ
の上に形成されかつ、接着性のすぐれた、写真乳剤用下
塗り層とを有する写真感光材料支持体に関するものであ
る。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photographic material support having an undercoat layer with excellent adhesiveness. More specifically, the present invention relates to a support for a photographic light-sensitive material having a surface layer made of a polyolefin resin and an undercoat layer for a photographic emulsion formed thereon and having excellent adhesive properties.
〔従来の技術］
従来一般に、写真感光材料、例えば印画紙の支持体とし
て、原紙からなる支持層と、その少なくとも一面にポリ
オレフィン樹脂をラミネートしたものが使用されている
。ポリオレフィン樹脂層の表面は化学的に不活性である
ため、これに直接写真乳剤を塗布しても、支持体と写真
乳剤層とは充分接着しないという不都合があった。従っ
て、ポリオレフィン樹脂表面層を有する支持体上に写真
乳剤層を塗布する場合には、その表面の接着性を改良す
る為、ポリオレフィン樹脂層の表面を活性化する必要が
あった。従来、この活性化の手段としてはポリオレフィ
ン樹脂層の表面にコロナ放電処理、低温プラズマ処理、
火炎処理、化学薬品処理等が行われてきた。[Prior Art] Conventionally, as a support for photographic light-sensitive materials, such as photographic paper, a support layer consisting of a base paper and a polyolefin resin laminated on at least one surface thereof have been used. Since the surface of the polyolefin resin layer is chemically inert, even if a photographic emulsion is directly coated thereon, there is a disadvantage that the support and the photographic emulsion layer do not adhere sufficiently. Therefore, when coating a photographic emulsion layer on a support having a polyolefin resin surface layer, it is necessary to activate the surface of the polyolefin resin layer in order to improve the adhesion of the surface. Conventionally, methods for this activation include corona discharge treatment, low-temperature plasma treatment, and
Flame treatment, chemical treatment, etc. have been used.
また、ポリオレフィン表面に対する上記の活性化処理の
効果は、経時的に減衰することが知られているが、これ
を防ぎ、安定した写真乳剤の塗工性を付与するために、
上記の活性化処理直後に、ポリオレフィン表面に親水性
樹脂による被膜、即ち下塗りを施すことが行われてきた
。（例えば、米国特許第２６９８２４１号、同２７６４
５２０号、同２８６４７５５号、同２８６４７５６号、
同３４７５１９３号、英国特許７８８３６５号、同８０
４００５号、同８９１４６９号の各明細書）しかしなが
ら、これらの下塗り層の写真乳剤に対する塗布性、接着
強度および、その接着性の経時的減衰性はなお不満足な
ものであって、一層の向上が望まれていた。In addition, it is known that the effect of the above activation treatment on the polyolefin surface diminishes over time, but in order to prevent this and provide stable photographic emulsion coating properties,
Immediately after the above activation treatment, the surface of the polyolefin has been coated with a hydrophilic resin, ie, undercoated. (For example, U.S. Pat. No. 2,698,241, U.S. Pat. No. 2,764
No. 520, No. 2864755, No. 2864756,
No. 3475193, British Patent No. 788365, No. 80
4005 and 891469) However, the coatability of these undercoat layers to photographic emulsions, the adhesive strength, and the decay properties of the adhesive properties over time are still unsatisfactory, and further improvement is desired. It was rare.
本発明が解決しようとする問題点は、ポリオレフィン樹
脂からなる表面層と、その上に形成された写真乳剤用下
塗り層とを有する写真感光材料支持体において、その下
塗り層の写真乳剤に対する塗布性および接着強度がより
向上しており、かつ接着強度の経時的減衰の少ない支持
体を提供することである。The problem to be solved by the present invention is a photographic light-sensitive material support having a surface layer made of a polyolefin resin and an undercoat layer for a photographic emulsion formed thereon. It is an object of the present invention to provide a support which has improved adhesive strength and whose adhesive strength is less attenuated over time.
〔問題点を解決するための手段・およびその作用〕上記
問題点を解決するための、本発明の写真感光材料支持体
は、支持層と、この支持層の少なくとも１面上に形成さ
れ、かつ活性化処理を施されたポリオレフィン樹脂層と
、この樹脂層上に設けられ、ゼラチンおよび、その硬膜
剤とを含む写真乳剤用下塗り層とを存し、前記下塗り層
の表面における水素イオン濃度が５．２〜６．２の範囲
に保持されており、かつ、前記硬膜剤が、少なくとも１
種のアジリジン化合物を含んでなる、ことを特徴とする
ものである。[Means for solving the problems and their effects] In order to solve the above problems, the photographic light-sensitive material support of the present invention comprises a support layer, formed on at least one surface of the support layer, and It comprises a polyolefin resin layer subjected to activation treatment, and a photographic emulsion undercoat layer provided on this resin layer and containing gelatin and its hardening agent, and the hydrogen ion concentration on the surface of the undercoat layer is 5.2 to 6.2, and the hardener has at least 1
It is characterized in that it comprises a species of aziridine compound.
以下本発明の支持体について説明する。The support of the present invention will be explained below.
本発明の支持体は支持層、ポリオレフィン樹脂層および
写真乳剤用下塗り層からなるものである。The support of the present invention consists of a support layer, a polyolefin resin layer, and an undercoat layer for photographic emulsion.
支持体は紙、合成紙、合成樹脂フィルムなどのシート材
料からなるものである。The support is made of a sheet material such as paper, synthetic paper, or synthetic resin film.
ポリオレフィン樹脂層は、ポリエチレン、ポリプロピレ
ン、ポリエチレン共重合体、およびこれらの２種以上の
混合物からなるものである。支持層の少なくとも１面上
にポリオレフィン樹脂層が形成されているが、この樹脂
層の形成に当り、所望のポリオレフィン樹脂のフィルム
を、支持層に、接着剤を用いて接着してもよいし、所望
のポリオレフィン樹脂を溶融し、これをＴ−ダイを用い
て支持層表面上に押し出し接着する。The polyolefin resin layer is made of polyethylene, polypropylene, polyethylene copolymer, or a mixture of two or more thereof. A polyolefin resin layer is formed on at least one surface of the support layer, and in forming this resin layer, a film of a desired polyolefin resin may be adhered to the support layer using an adhesive, A desired polyolefin resin is melted and extruded onto the surface of the support layer using a T-die to adhere it.
このようにして形成されたポリオレフィン樹脂層の表面
に、接着性向上のために表面活性化処理が施される。こ
の活性化処理の種類には格別の限定はなく、コロナ処理
、低温プラズマ処理、火炎処理、又は化学薬品（例えば
過酸化物含有処理剤）処理のいづれを常法に従って用い
てもよい。The surface of the polyolefin resin layer thus formed is subjected to surface activation treatment to improve adhesion. There is no particular limitation on the type of activation treatment, and any of corona treatment, low-temperature plasma treatment, flame treatment, or chemical treatment (for example, peroxide-containing treatment agent) treatment may be used according to a conventional method.
このようにして形成された活性化ポリオレフィン樹脂層
の表面に下発明の写真乳剤用下塗り層が形成される。The undercoat layer for a photographic emulsion of the present invention is formed on the surface of the activated polyolefin resin layer thus formed.
この下塗り層は、少なくともゼラチンと、その硬膜剤と
を含むものである。ゼラチンには、それと相溶性のある
天然又は合成重合体、例えばアラビヤゴム、カルボキシ
メチルセルロースなどが混合されていてもよい。This undercoat layer contains at least gelatin and a hardening agent. Gelatin may be mixed with natural or synthetic polymers that are compatible therewith, such as gum arabic, carboxymethyl cellulose, and the like.
この混合用天然又は合成重合体のゼラチンに対する混用
比（重量）は、５０ ： ５０以下であることが好まし
い。The mixing ratio (weight) of the natural or synthetic polymer for mixing to gelatin is preferably 50:50 or less.
下塗り層中にはゼラチンを硬膜化するための硬膜剤が含
まれる。本発明の下塗り層においては、硬膜剤は、少な
くとも１種のアジリジン化合物、好ましくは、１分子当
り２個以上のエチレンイミノ基を有するアジリジン化合
物が用いられている。The undercoat layer contains a hardening agent for hardening the gelatin. In the undercoat layer of the present invention, at least one aziridine compound, preferably an aziridine compound having two or more ethyleneimino groups per molecule, is used as the hardening agent.
このようなアジリジン化合物は、例えば下記の化学構造
（１）〜（Ｘ）を有するものから選ばれることが好まし
い。Such an aziridine compound is preferably selected from those having the following chemical structures (1) to (X), for example.
＼−二７
電
Ｚ−二Ｘ
ノー二Ｘ
］記アジリジン化合物のゼラチンに対する添加量よ一般
に、ゼラチン１グラムに対し、Ｉ Ｘ １０−’〜ｌ
Ｘ １０−”モルの範囲で用ることかできるが、１．５
〜３Ｘ１０−’モルの範囲で用いることが好まＪい。\-27 Electron Z-2X No 2X ] The amount of the aziridine compound added to gelatin is generally I
X can be used in the range of 10-” mole, but 1.5
It is preferable to use it in a range of 3×10 −′ moles.
また、本発明の下塗り層には、必要に応じて塗工性改良
の為の界面活性剤、および／又はブロノニング防止用の
微粒子を含んでいてもよい。前者よ、例えば天然物サポ
ニン、合成のアニオン系、フチオン系、ノニオン系界面
活性剤から選ばれ、１者は、例えばコロイダルシリカを
用いることができる。本発明において、下塗り層の表面
は、そつ水素イオン濃度（ｐ Ｈ）を５．２〜６．２の
範囲内に保持される。Further, the undercoat layer of the present invention may contain a surfactant for improving coating properties and/or fine particles for preventing blononing, if necessary. The former is selected from natural saponins, synthetic anionic, phthionic, and nonionic surfactants, and the former is, for example, colloidal silica. In the present invention, the surface of the undercoat layer has a hydrogen ion concentration (pH) maintained within the range of 5.2 to 6.2.
下塗り層形成に用いられるゼラチンが５．２〜６．２の
範囲内の等電点を有するものである場合は、得られる下
塗り層の表面のｐＨは、５．２〜６．２の・範囲に保持
される。しかし、使用されるゼラチンの等電点がｐＨ５
，２〜６．２の間に入っていないときは、水に可溶の酸
性物質を加えることによってｐＨ調整が行われる。下塗
り層の表面ｐＨが５．２〜６．２の範囲をはずれると得
られる下塗り層の写真乳剤に対する接着性は著しく低下
する。上記酸性物質の具体的例としては、塩酸、硫酸な
どの無機酸、酢酸、プロピオン酸などの有機酸、硫酸水
素ナトリウム、硫酸水素カリウムなどの水溶液が酸性を
示す酸性塩をあげることができる下塗り面のｐＨの測定
は、公知の表面ｐＨ測定法、例えば、共立理研式紙面ｐ
Ｈ試験液によって行うことができる支持体と、写真乳剤
層との接着強度の試験法は、次の通りである。When the gelatin used to form the undercoat layer has an isoelectric point within the range of 5.2 to 6.2, the pH of the surface of the resulting undercoat layer is within the range of 5.2 to 6.2. is maintained. However, the isoelectric point of the gelatin used is pH 5.
, 2 to 6.2, the pH is adjusted by adding a water-soluble acidic substance. If the surface pH of the undercoat layer is outside the range of 5.2 to 6.2, the adhesion of the resulting undercoat layer to the photographic emulsion will be significantly reduced. Specific examples of the above acidic substances include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid and propionic acid, and acid salts whose aqueous solutions are acidic such as sodium hydrogen sulfate and potassium hydrogen sulfate. The pH can be measured using a known surface pH measurement method, such as the Kyoritsu Riken paper p.
The method for testing the adhesive strength between the support and the photographic emulsion layer using H test solution is as follows.
写真乳剤を塗布した支持体を３０〜４０℃に調製したカ
ラー印画紙用発色現像液に浸し、１分後に現像液の中で
、かみそりの刃をもちいて互いに直交するように引っ掻
き傷をつけ、更に２分間浸せき後現像液中で直交した引
っ掻き傷に対し４５度の角度で母指類で摩擦する。この
処理によって、写真乳剤層が傷取上に剥離しないものを
グレード１、完全に剥れてしまうものにグレード１０を
与え、グレード２〜９は、この両極端の間の剥離の程度
に従って与える。本発明により塗設した下引き層を有す
るときのみ、支持体と写真乳剤層との間に最良の接着状
態、即ちグレード１が得られる。The support coated with the photographic emulsion is immersed in a color developer for color photographic paper prepared at 30 to 40°C, and after 1 minute, scratches are made in the developer using a razor blade at right angles to each other. After immersing for an additional 2 minutes, the sample is rubbed with the thumb of the thumb at a 45 degree angle to the perpendicular scratches in the developer. A grade of 1 is given to a case where the photographic emulsion layer does not peel off on scratches due to this treatment, a grade of 10 is given to a case where the photographic emulsion layer completely peels off, and grades of 2 to 9 are given according to the degree of peeling between these two extremes. The best adhesion between the support and the photographic emulsion layer, ie grade 1, is obtained only with a subbing layer applied according to the invention.
下発明の下塗り層の形成に際し、ゼラチンは、水溶液と
して、又は水溶液に水と相溶性を有する有機溶媒を加え
た溶液として用いられる。硬膜剤、例えばアジリジン系
の硬膜剤は水溶液として、又は水と相溶性のある有機溶
媒の溶液として調製され、その適当量を、前述のゼラチ
ン溶液にまぜて用いる。このような有機溶媒の代表的な
ものには、低級アルコール類、アセトンなどが上げられ
る。When forming the undercoat layer of the underinvention, gelatin is used as an aqueous solution or as a solution prepared by adding an organic solvent compatible with water to the aqueous solution. A hardening agent, such as an aziridine-based hardening agent, is prepared as an aqueous solution or as a solution of an organic solvent that is compatible with water, and an appropriate amount thereof is mixed with the gelatin solution described above. Typical examples of such organic solvents include lower alcohols and acetone.
こうして得られた溶液を、活性化処理後のポリオレフィ
ン樹脂層表面に塗布する。下塗り層の乾燥塗布量は０゜
０２〜１ ｇ／ｍの範囲でもちいられるが、０．０５〜
０．１５ｇ／ｍが特に好ましい。The solution thus obtained is applied to the surface of the polyolefin resin layer after the activation treatment. The dry coating amount of the undercoat layer can be used in the range of 0.02 to 1 g/m, but it is 0.05 to 1 g/m.
Particularly preferred is 0.15 g/m.
〔実施例］
以下、実施例に基づいて、本発明を更に詳細に説明する
。[Example] Hereinafter, the present invention will be described in more detail based on Examples.
−１１〜３および １１〜５
各実施例および比較例において１７０ ｇ ／ｒｒｌの
写真用原紙からなる支持層の裏面には密度０．９４ ｇ
／ｍ′のポリエチレン樹脂を、また支持層の表面には
前述のポリエチレン樹脂にアナターゼ型酸化チタンを、
ポリエチレン樹脂の１０重量％加え良く分散したものを
、おのおの２８ｇ／ｍの塗布量になるようにＴダイ型押
し出し、ラミネート法によってラミネートした。このポ
リエチレン被覆紙の乳剤塗布側表面をコロナ放電法によ
り、処理後の表面が、４５〜４６ ｄｙｎｅ／ ｃｍの
ヌレ指数を示すように活性化処理した。この処理表面の
ヌレ指数は、ＪＩＳに−６７６８に従って測定した。活
性化処理後のポリエチレン樹脂層表面に、下記組成の下
塗り液患１〜７の各々をバーコーティングにより乾燥塗
布量が０．１ｇ／ｍとなるように塗布し、下塗り層とし
た。下塗り層は、乾燥後、４０℃、相対湿度５０％の雰
囲気下で１７時間放置し条件調整した。-11-3 and 11-5 In each Example and Comparative Example, the back side of the support layer made of 170 g/rrl photographic base paper had a density of 0.94 g.
/m' of polyethylene resin, and on the surface of the support layer, anatase type titanium oxide was added to the above-mentioned polyethylene resin.
A well-dispersed mixture of 10% by weight of polyethylene resin was extruded using a T-die to a coating weight of 28 g/m, and laminated by a lamination method. The emulsion-coated surface of this polyethylene-coated paper was activated by a corona discharge method so that the treated surface exhibited a wetting index of 45 to 46 dyne/cm. The wetting index of this treated surface was measured according to JIS-6768. On the surface of the polyethylene resin layer after the activation treatment, each of the undercoat liquids Nos. 1 to 7 having the following composition was applied by bar coating so that the dry coating amount was 0.1 g/m to form an undercoat layer. After drying, the undercoat layer was left in an atmosphere of 40° C. and 50% relative humidity for 17 hours to adjust the conditions.
また比較のために、活性化したポリエチレン樹脂層のみ
を有し、下塗り層を有していない支持体（比較例５）を
調製した。For comparison, a support (Comparative Example 5) having only an activated polyethylene resin layer and no undercoat layer was prepared.
論 組 隘１（例１）
ゼラチン（等電点ｐＨ６，０） １０ｇアジリジ
ン化合物（１） ０．６５ｇ純水
５００ｇ
と１） ン 、 １ｔ２（＋２）ゼラチン（等
電点ｐＨ６，０） Ｌｏｇアジリジン化合物（Ｖ
ｌ） ０．６５ｇ純水 ４９５
ｇ
エチルアルコール Ｌｏｇ塗 パ １
嵐３（＋３）
ゼラチン（等電点ｐＨ９，０） １０ｇアジリジ
ン化合物（１） ０．６５ｇ純水
５００ｇ
下徐 ン組成患４ （較 １）
ゼラチン（等電点ｐＨ６，０） １０ｇ純水
５００ｇ
ンタｉミ ン 、 さｈ５ （＋ ２
）ゼラチン（等電点ｐＨ９，０） １０ｇアジ
リジン化合物（１） ０．６５ｇ純水
５００ｇ
諭 ン さに１６ （六 ３ ）ゼラチン
（等電点ｐＨ６゜Ｏ） １０ｇアジリジン化合物
（Ｉ） ０．６５ｇ純水 ５０
０ｇ
啼 ’、１１ｈ７（較 １４）
ゼラチン（等電点ｐＨ６，０） １０ｇ純水
５００ｇ
上記の各支持体の表面側に印画紙用写真乳剤を、バーコ
ーティングにより乾燥塗工量が９ ｇ／ｎ（になるよう
に塗布した。印画紙用写真乳剤は写真工業出版社刊（昭
和５１年）「特殊写真処理の実際」８３ページ記載の方
法により調製し、これに硬膜剤として写真乳剤中のゼラ
チン１ｇに対し２Ｘ１．０−’モルの１．２−ビス（２
−ビニルスルホニルエチル）ピペリジンを添加した。得
られた印画紙を、乳剤層乾燥後、温度５５℃、相対湿度
７０％の雰囲気下で２４時間あるいは７２時間放置し、
前述の試験法により支持体と写真乳剤層の接着強度を測
定した。その結果を第１表に示す。Theory Group 1 (Example 1) Gelatin (isoelectric point pH 6,0) 10g aziridine compound (1) 0.65g pure water
500g and 1), 1t2(+2) gelatin (isoelectric point pH 6,0) Log aziridine compound (V
l) 0.65g pure water 495
g Ethyl alcohol Log coating 1
Arashi 3 (+3) Gelatin (isoelectric point pH 9,0) 10g Aziridine compound (1) 0.65g pure water
500g lower composition Example 4 (Comparison 1) Gelatin (isoelectric point pH 6,0) 10g pure water
500g weight, 500g (+2
) Gelatin (isoelectric point pH 9,0) 10g Aziridine compound (1) 0.65g pure water
500g 16 (6 3) gelatin (isoelectric point pH 6°O) 10g aziridine compound (I) 0.65g pure water 50
0g, 11h7 (comparison 14) Gelatin (isoelectric point pH 6,0) 10g pure water
500 g A photographic emulsion for photographic paper was coated on the surface side of each of the above supports by bar coating so that the dry coating amount was 9 g/n. 1.2-bis(2
-vinylsulfonylethyl)piperidine was added. After drying the emulsion layer, the obtained photographic paper is left for 24 or 72 hours in an atmosphere at a temperature of 55° C. and a relative humidity of 70%.
The adhesive strength between the support and the photographic emulsion layer was measured using the test method described above. The results are shown in Table 1.
第１表
注（＊）：メチレンービス（β−ビニルスルホニルプロ
ピオンアミド）
〔発明の効果〕
第１表からも明らかであるように、本発明の写真乳剤下
塗り層を有する写真感光材料支持体は、写真乳剤層に対
してすぐれた接着強度を有している。Table 1 Note (*): Methylenebis(β-vinylsulfonylpropionamide) [Effects of the Invention] As is clear from Table 1, the photographic light-sensitive material support having the photographic emulsion undercoat layer of the present invention It has excellent adhesive strength to the emulsion layer.
Claims (1)
れ、かつ、活性化処理を施されたポリオレフィン樹脂層
と、この樹脂層上に設けられ、ゼラチン、および、その
硬膜剤とを含む、写真乳剤用下塗り層とを有し、 前記下塗り層の表面における水素イオン濃度が５．２〜
６．２の範囲に保持されており、かつ前記硬膜剤が少な
くとも１種のアジリジン化合物を含んでなる、 ことを特徴とする写真感光材料用支持体。 ２、前記ゼラチンが５．２〜６．２の範囲内にある等電
点を有するものから選ばれる、特許請求の範囲第１項記
載の支持体。 ３、前記ゼラチンが６．２より高い等電点を有し、前記
下塗り層の水素イオン濃度が、酸性物質の添付により５
．２〜６．２の範囲内に調整されている、特許請求の範
囲第１項記載の支持体。 ４、前記酸性物質が、水溶性無機酸、有機酸および酸性
塩から選ばれる、特許請求の範囲第３項記載の支持体。 ５、前記アジリジン系硬膜剤の、ゼラチン１ｇに対する
添加量が１×１０＾−＾５〜１×１０＾−＾３モルであ
る、特許請求の範囲第１項記載の支持体。 ６、前記下塗り層の乾燥重量が０．０２〜１ｇ／ｍ＾２
の範囲内にある、特許請求の範囲第１項記載の支持体。[Scope of Claims] 1. a support layer, a polyolefin resin layer formed on at least one surface of the support layer and subjected to an activation treatment, gelatin provided on the resin layer, and and a photographic emulsion undercoat layer containing the hardening agent, and the hydrogen ion concentration on the surface of the undercoat layer is 5.2 to 5.2.
6.2, and the hardening agent contains at least one aziridine compound. 2. The support according to claim 1, wherein the gelatin is selected from those having an isoelectric point within the range of 5.2 to 6.2. 3. The gelatin has an isoelectric point higher than 6.2, and the hydrogen ion concentration of the undercoat layer is increased to 5.
．． The support according to claim 1, which is adjusted within the range of 2 to 6.2. 4. The support according to claim 3, wherein the acidic substance is selected from water-soluble inorganic acids, organic acids, and acid salts. 5. The support according to claim 1, wherein the amount of the aziridine hardener added to 1 g of gelatin is 1 x 10^-^5 to 1 x 10^-^3 mol. 6. The dry weight of the undercoat layer is 0.02 to 1 g/m^2
A support according to claim 1, which falls within the scope of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61130206A JPS62287243A (en) | 1986-06-06 | 1986-06-06 | Substrate body for silver halide photographic sensitive material having undercoat of excellent sticking property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61130206A JPS62287243A (en) | 1986-06-06 | 1986-06-06 | Substrate body for silver halide photographic sensitive material having undercoat of excellent sticking property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62287243A true JPS62287243A (en) | 1987-12-14 |
Family
ID=15028627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61130206A Pending JPS62287243A (en) | 1986-06-06 | 1986-06-06 | Substrate body for silver halide photographic sensitive material having undercoat of excellent sticking property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62287243A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4827132A (en) * | 1971-08-10 | 1973-04-10 | ||
| JPS4917522A (en) * | 1972-06-14 | 1974-02-16 | ||
| JPS541612A (en) * | 1977-04-27 | 1979-01-08 | Du Pont | Undercoat composition |
| JPS5654623A (en) * | 1979-10-05 | 1981-05-14 | Alps Electric Co Ltd | Core of magnetic head and its manufacture |
| JPS6052421A (en) * | 1983-08-31 | 1985-03-25 | Iseki & Co Ltd | Grain taking-out device in grain drier |
-
1986
- 1986-06-06 JP JP61130206A patent/JPS62287243A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4827132A (en) * | 1971-08-10 | 1973-04-10 | ||
| JPS4917522A (en) * | 1972-06-14 | 1974-02-16 | ||
| JPS541612A (en) * | 1977-04-27 | 1979-01-08 | Du Pont | Undercoat composition |
| JPS5654623A (en) * | 1979-10-05 | 1981-05-14 | Alps Electric Co Ltd | Core of magnetic head and its manufacture |
| JPS6052421A (en) * | 1983-08-31 | 1985-03-25 | Iseki & Co Ltd | Grain taking-out device in grain drier |
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