JPS6134523Y2 - - Google Patents
Info
- Publication number
- JPS6134523Y2 JPS6134523Y2 JP13668180U JP13668180U JPS6134523Y2 JP S6134523 Y2 JPS6134523 Y2 JP S6134523Y2 JP 13668180 U JP13668180 U JP 13668180U JP 13668180 U JP13668180 U JP 13668180U JP S6134523 Y2 JPS6134523 Y2 JP S6134523Y2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- photographic paper
- layer
- organic substance
- emulsion
- 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.)
- Expired
Links
- 239000000126 substance Substances 0.000 claims description 30
- 125000002091 cationic group Chemical group 0.000 claims description 25
- 239000001023 inorganic pigment Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 description 35
- -1 polyethylene Polymers 0.000 description 32
- 239000004698 Polyethylene Substances 0.000 description 24
- 239000000839 emulsion Substances 0.000 description 24
- 229920000573 polyethylene Polymers 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- 230000000740 bleeding effect Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003851 corona treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 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
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本考案は写真用印画紙に関し、さらに詳しく
は、その裏面に分子量500以上のカチオン性有機
物質と、無機顔料を含む層を設けたことを特徴と
する写真用印画紙に関する。
一般に印画紙は、紙支持体の両面をポリエチレ
ン層で被覆し、一方の面のポリエチレン層上に写
真用乳剤層（以下単に「乳剤層」と言う）が層設
されている。本明細書においては乳剤層が層設さ
れている方の面を「表面」と言い、乳剤層が層設
されていない方の面を「裏面」と言うことにす
る。この印画紙は一般に耐水性印画紙と称され、
現像処理液や、水洗水が紙支持体中に浸透するの
を防止し、現像処理時間を従来のバライタ紙（紙
支持体上に硫酸バリウムの層を設けた印画紙）の
場合よりも極度に短くすることを目的として作ら
れている。
一方、印画紙の裏面に、撮影した日付を入れた
り、文字を書いたり、絵を画いたりまたスタンプ
を押すことが可能になることが希望されており、
裏面に印刷性、描字性、描画性を賦与した印画紙
の出現が持たれていた。またこのような印画紙は
裏面に切手等を貼り付けることも容易で、例えば
ポストカードなどにも使用でき、その用途範囲は
極めて広い。
しかしながら通常印画紙の裏面は上述のように
疎水性のポリエチレン層で被覆されているためそ
のままでは鉛筆、コンテ、万年筆等で文字、絵等
を書くのは困難であり、またスタンプを押しても
ポリエチレン層が吸液性がないため、乾燥が極め
て遅く、たとえ乾燥しても容易に摩擦等によりス
タンプが消えてしまいその目的は達せられない。
ポリエチレン層上に印刷性、描字性、描画性を
附与する最も一般的な方法としては、例えば裏面
側ポリエチレン層上に微細な凹凸を設ける方法が
ある。しかしこの方法によつて得られる描写性、
描画性は極めて不完全で鉛筆、コンテ、万年筆等
では書けず、満足なものとは言えなかつた。
また他の方法としては、裏面のポリエチレン層
上にコロナ放電処理を施したり、あるいは界面活
性剤の層を設ける方法がある。しかしこれらのも
のは油性筆記具には良好な筆記性を示すが、水性
筆記具では殆ど筆記できず満足なものとは言えな
かつた。
更には、実開昭52−169426に開示されているよ
うな裏面ポリエチレン層上に吸湿性を備えた塗料
の層を設ける方法もあるが、この場合確かに鉛
筆、コンテ、ボールペン等による描字性、描画性
は改良される。しかし水性インキを使用して印
刷、描字、描画を行なうと、画像のにじみが激し
く鮮明度が著しく低下してしまう。その結果スタ
ンプで押印した絵や、水性サインペンで書いた字
のデイテールがぼやけてしまい実用に耐えなかつ
た。
また他の方法として、印画紙の裏面に紙をのり
付けしてどのような筆記具でも容易に文字が書け
るようにしているものもある。しかしこの方法に
おいては、印画紙に紙を裏貼りする作業を１枚１
枚人手によつて行なうため、大量生産を行なうこ
とができず、相当の時間と手数を要するために高
価となる問題点があつた。また裏貼りする際に貼
り方を一度失敗すると修復が困難なため、折角の
写真を無駄にする事態がしばしば発生しており、
更に紙を裏貼りすると乾燥後に印画紙自体が反り
返つてしまう等の問題点があつた。
本考案は上記従来の印画紙の欠点を解決するも
のであり、裏面に印刷性、描字性、描画性を賦与
することができ、しかも水性インクのにじみが著
しく改良された印画紙を提供することを目的とす
るものである。
本考案者は、写真用印画紙の裏面ポリエチレン
層上に分子量500以上のカチオン性有機物質と無
機顔料を含む層を設けることにより本考案の目的
を達成した。
ここでカチオン性有機物質とは、水溶液中で電
離して陽イオンとなる基を含む有機物質を言い、
中でも窒素原子を含むカチオン性有機物質が好ま
しい。これにはアミン塩、フオスホニウム塩、ス
ルホニウム塩が含まれる。これらの中ではアミン
塩が最も好ましく更には第４アンモニウム塩が好
ましい。本考案においてカチオン性有機物質は水
性インクのにじみを改良する目的で添加される物
質である。
カチオン性有機物質の具体例としては具体的に
等の界面活性剤、
等のポリアクリルエステル系第３アミン塩
等のポリアクリルエステル系第４アンモニウム塩
等のポリアクリルアミド系第３アミン塩
等のポリエチレンイミン系第２アミン塩
The present invention relates to a photographic paper, and more particularly to a photographic paper characterized in that a layer containing a cationic organic substance having a molecular weight of 500 or more and an inorganic pigment is provided on the back side of the paper. In general, photographic paper has a paper support coated on both sides with polyethylene layers, and a photographic emulsion layer (hereinafter simply referred to as "emulsion layer") is provided on the polyethylene layer on one side. In this specification, the side on which the emulsion layer is formed will be referred to as the "front side," and the side on which the emulsion layer is not formed will be referred to as the "back side." This photographic paper is generally called water-resistant photographic paper.
It prevents the development processing solution and washing water from penetrating into the paper support, making the development processing time more extreme than that of conventional baryta paper (photographic paper with a layer of barium sulfate on the paper support). It is designed to be short. On the other hand, it is hoped that it will be possible to write the date of the photograph, write text, draw pictures, or affix a stamp on the back of the photographic paper.
This marked the emergence of photographic paper that had printing, writing, and drawing properties on the back side. Furthermore, it is easy to attach stamps and the like to the back of such photographic paper, and it can be used for postcards, for example, and its range of uses is extremely wide. However, as mentioned above, the back side of photographic paper is usually coated with a hydrophobic polyethylene layer, so it is difficult to write on it with a pencil, conte, fountain pen, etc., and even with a stamp, the polyethylene layer Since it has no liquid absorption properties, it dries very slowly, and even if it does dry, the stamp will easily disappear due to friction, etc., and its purpose will not be achieved. The most common method for imparting printability, writing and drawing properties to a polyethylene layer is, for example, a method of providing fine irregularities on the backside polyethylene layer. However, the descriptive quality obtained by this method,
The drawing quality was extremely imperfect, making it impossible to write with pencils, conte, fountain pens, etc., and it could not be said to be satisfactory. Other methods include performing corona discharge treatment on the polyethylene layer on the back surface or providing a surfactant layer. However, although these materials showed good writing properties with oil-based writing instruments, they could hardly be written on with water-based writing instruments, and could not be said to be satisfactory. Furthermore, there is a method of providing a layer of hygroscopic paint on the back polyethylene layer as disclosed in Japanese Utility Model Application No. 52-169426, but in this case it is certainly difficult to draw with a pencil, conte, ballpoint pen, etc. , the drawing performance is improved. However, when printing, writing, or drawing is performed using water-based ink, the image bleeds severely and the clarity deteriorates significantly. As a result, the details of pictures stamped with stamps and letters written with water-based felt-tip pens became blurred, making them unusable. Another method involves gluing paper to the back of photographic paper so that characters can be easily written on with any writing implement. However, with this method, the work of pasting the back of the paper onto the photographic paper is done one by one.
Since it is carried out by hand, mass production cannot be carried out, and it requires a considerable amount of time and labor, resulting in high costs. In addition, once you make a mistake when pasting the back, it is difficult to repair, so you often end up wasting your hard-earned photos.
Furthermore, when paper was pasted on the back, there were other problems such as the photographic paper itself curling back after drying. The present invention solves the above-mentioned drawbacks of conventional photographic paper, and provides a photographic paper that can provide printing properties, writing properties, and drawing properties on the back side, and has significantly improved bleeding of water-based ink. The purpose is to The present inventor achieved the object of the present invention by providing a layer containing a cationic organic substance having a molecular weight of 500 or more and an inorganic pigment on the back polyethylene layer of photographic paper. Here, the cationic organic substance refers to an organic substance containing a group that becomes a cation when ionized in an aqueous solution.
Among these, cationic organic substances containing nitrogen atoms are preferred. This includes amine salts, phosphonium salts, and sulfonium salts. Among these, amine salts are most preferred, and quaternary ammonium salts are even more preferred. In the present invention, the cationic organic substance is a substance added for the purpose of improving the bleeding of aqueous ink. Specific examples of cationic organic substances include surfactants such as polyacrylic ester-based tertiary amine salts such as Polyacrylic ester quaternary ammonium salts such as polyacrylamide-based tertiary amine salts such as Polyethyleneimine secondary amine salts such as
【式】 等のビニルピリジン系第４アンモニウム塩【formula】 Vinylpyridine quaternary ammonium salts such as
【式】 等のポリスチレン系第４アンモニウム塩 等のポリアクリル共重合体系第３アミン塩 等のスチレン共重合体系第４アンモニウム塩Polystyrene quaternary ammonium salts such as [Formula] polyacrylic copolymer-based tertiary amine salts such as Styrene copolymer quaternary ammonium salts such as
【式】
で示されるポリビニルピロリドン０グアニジン基
を含む
などが含まれる。これらの中ではポリアクリルエ
ステル系第４アンモニウム塩、ポリスチレン系第
４アンモニウム塩が好ましく、更にはポリアクリ
ルエステル系第チアンモニウム塩が特に好まし
い。
該カチオン水性有機物質の分子量は500以上が
好ましく、更に3000以上が、更には8000以上が好
ましい。分子量が500以下ならば後述するように
カチオン性有機物質に含まれる塩基性基が、水性
インク中の酸性基とイオン結合しても、分子量が
小さいために移動度が大きく、スタンプインクの
にじみを防止することは困難である。
本考案に用いられる無機顔料はカチオン性有機
物質と共にポリエチレン表面に適用され、筆記
性、インクの吸収性を与えるもので、アルカリ土
金属の炭酸塩、硫酸塩、微紛珪酸、合成珪酸塩の
シリカ類、珪酸カルシウム、アルミナ、アルミナ
水和物、酸化チタン、タルク、クレイ等である。
印画紙の裏面に、カチオン性有機物質と無機顔
料を含む層を設ける方法は、特に制約されない
が、カチオン性有機物質と無機顔料を含む液を塗
布する方法が、最も一般的である。
裏面の層の中に含まれるカチオン性有機物質の
量は、カチオン性有機物質の種類、分子量によつ
て異なるため、一概に規定できないが、塗布層全
体に対して、カチオン性有機物質固型分で１乃至
50重量％、好ましくは５乃至40重量％、更に好ま
しくは10乃至30重量％が良い。１重量％以下では
水性インクのにじみ防止効果が小さいし、50重量
％以上では液の粘度が著しく向上し塗布適性が悪
化する。また添加するカチオン性有機物質は、一
種類に限るものではなく２種類以上を添加しても
良い。この場合もカチオン性有機物質の全量が上
述した範囲内であれば本考案の目的は達せられ
る。
また裏面の層の中に含まれる無機顔料の量は、
無機顔料の種類によつて異なるため一概には規定
できないが、塗布層全体に対して10乃至90重量
％、好ましくは20乃至85重量％更に好ましくは40
乃至80重量％が良い。10重量％以下では筆記性、
インクの吸収性が劣るし、90重量％以上では液粘
度が極端に高くなり塗布が著しく困難になる。ま
た添加する無機顔料は一種類に限るものではなく
２種類以上を添加しても良い。この場合も無機顔
料の全量が上述した範囲内であれば本考案の目的
は達せられる。
またカチオン性有機物質と無機顔料から成る液
に塗膜形成を容易にする物質としてエチレン酢酸
ビニル共重合体エマルジヨン、アクリル系（エス
テル）エマルジヨン、酢酸ビニルエマルジヨン、
スチレン・ブタジエン共重合体エマルジヨン、ポ
リ塩化ビニルエマルジヨン、クロロプレンゴムエ
マルジヨン、エチレン・アクリル酸共重合体、エ
チレン・無水マレイン酸共重合体、ブタジエン・
無水マレイン酸共重合体ポリビニルアルコール、
デンプン、カルボキシメチルセルロースなどの高
分子物質の水溶液やエマルジヨンを必要に応じて
添加しても良い。また塗布性を改良する。
物質として、乾燥過程中に蒸発して塗膜には残
らないエチルアルコール、ブチルアルコールなど
のアルコール類、石油スピリツト、燈油、キシレ
ンなどの炭化水素類、酢酸エチル、酢酸ブチルな
どのエステル類、アセトン、メチルエチルケト
ン、シクロヘキサノンなどのケトン類、ジエチレ
ングリコール、ブチルセロソルブなどのエーテル
類、トリクロルエチレン、塩化メチレンなどのク
ロル化合物などを加えても構わない。
カチオン性有機物質と無機顔料とを含む液は、
印画紙を製造するどの工程で塗布しても良い。例
えば乳剤塗布前でも良いし、乳剤塗設後露光前、
露光、現像処理後でも良い。しかし乳剤塗設前お
よび乳剤塗設後露光前の場合には現像時に、現像
処理液中にカチオン性物質の一部が溶出する可能
性があるので、露光、現像処理後に塗布する方が
好ましい。
またポリエチレン層と該層との接着強度を向上
させるために、ポリエチレン表面にコロナ放電処
理やグロー放電処理を施しても良い。
該液の塗布には汎用の方法が使用できる。即ち
バーコート、デイツプコート、グラビアコート等
が一般的である。塗布層厚みは、乾膜１μ以上
が、更には３μ以上が好ましい。１μ以下では水
性インクなどの乾燥速度が著しく悪化するので好
ましくない。
本考案を実施することにより以下に記す多くの
利点が得られる。
(1) 水性インクのにじみがなく、且つ乾燥が速
い、裏面に印刷性のある印画紙を製造し得る。
(2) 鉛筆をはじめあらゆる筆記用具で自由且つ鮮
明に文字等を書くことができる。
(3) 印画紙の裏面に塗料を塗布するのみでよいの
で、オートマチツクな作業により、大量生産が
可能となり、従つて安価に製作し得る。
(4) 紙を裏貼りする方式に比し作業自体に失敗が
なく写真を無駄にしてしまうようなことがな
い。
(5) 紙を裏貼りする方式に比し印画紙が反り返る
ようなことがない。
次に、図面を参照してさらに本考案を説明す
る。
第１図に示すように通常の印画紙は紙支持体１
の両面にポリエチレン層２，３が層設されてい
る。紙支持体表面のポリエチレン層２の上にカラ
ーまたは白黒用の写真乳剤層４が層設されるが、
このポリエチレン層２には酸化チタン等の光反射
物質が含まれているのが普通である。なお、ポリ
エチレン層２と乳剤層４の間には両者の密着を改
良する為に下塗り層を設けても良い。
第２図は本考案に係る写真用印画紙の断面図を
示し、裏面のポリエチレン層３上にカチオン性有
機物質と無機顔料を含む層５を設けたものであ
る。
第３図は本考案の実施態様を示す斜視図で、カ
チオン性有機物質と無機顔料を含む層５上に、郵
便切手６を貼り付けポストカードにした実施例で
ある。このようにすることによつて写真の絵葉書
を容易に作ることができる。
以下実施例に基づいて本考案の内容をさらに詳
細に説明するが、実施例中で示す水性インクのに
じみ度合は次に記す方法で測定されたものであ
る。写真用印画紙の裏面に水性インク（商品名：
シヤチハタゾルスタンプ台 緑）をスタンプを使
用して幅１mmの線になるように押し、水性インク
が完全に乾燥した後の線の幅（mm）を測定する。
比較例 １
写真用印画紙の裏面ポリエチレン表面に深さ10
μの微細な凹凸を付けマツト加工した。
比較例 ２
写真用印画紙の裏面ポリエチレン表面に、コロ
ナ放電処理を施し、更に酸化チタン35重量部、エ
チレン・酢酸ビニル共重合体エマルジヨン55重量
部、水10重量部から成る液を乾膜で５μになるよ
うに塗布し乾燥した。
比較例 ３
写真用印画紙の裏面ポリエチレン表面に、コロ
ナ放電処理を施し、更に酸化チタン35重量部、エ
チレン・酢酸ビニル共重合体エマルジヨン55重量
部、[Formula] Polyvinylpyrrolidone containing 0 guanidine groups etc. are included. Among these, polyacrylic ester-based quaternary ammonium salts and polystyrene-based quaternary ammonium salts are preferred, and polyacrylic ester-based quaternary ammonium salts are particularly preferred. The molecular weight of the cationic aqueous organic substance is preferably 500 or more, more preferably 3,000 or more, and even more preferably 8,000 or more. If the molecular weight is 500 or less, even if the basic groups contained in the cationic organic substance ionically bond with the acidic groups in the water-based ink, as will be described later, the mobility is large due to the small molecular weight, and the stamp ink will not bleed. It is difficult to prevent. The inorganic pigment used in this invention is applied to the surface of polyethylene together with a cationic organic substance to provide writing properties and ink absorption. calcium silicate, alumina, alumina hydrate, titanium oxide, talc, clay, etc. The method for providing a layer containing a cationic organic substance and an inorganic pigment on the back side of photographic paper is not particularly limited, but the most common method is to apply a liquid containing a cationic organic substance and an inorganic pigment. The amount of cationic organic substance contained in the back layer cannot be determined unconditionally because it varies depending on the type and molecular weight of the cationic organic substance, but the amount of cationic organic substance solid content in the entire coating layer is from 1 to
The amount is preferably 50% by weight, preferably 5 to 40% by weight, and more preferably 10 to 30% by weight. If it is less than 1% by weight, the effect of preventing the aqueous ink from bleeding is small, and if it is more than 50% by weight, the viscosity of the liquid will increase significantly and the coating suitability will deteriorate. Further, the cationic organic substance to be added is not limited to one type, but two or more types may be added. In this case as well, the object of the present invention can be achieved as long as the total amount of the cationic organic substance is within the above-mentioned range. Also, the amount of inorganic pigment contained in the back layer is
Although it cannot be specified as it varies depending on the type of inorganic pigment, it is 10 to 90% by weight, preferably 20 to 85% by weight, more preferably 40% by weight based on the entire coating layer.
80% by weight is preferable. Writability is poor at 10% by weight or less,
Ink absorption is poor, and if it exceeds 90% by weight, the liquid viscosity becomes extremely high, making coating extremely difficult. Further, the number of inorganic pigments to be added is not limited to one type, but two or more types may be added. In this case as well, the object of the present invention can be achieved as long as the total amount of the inorganic pigment is within the above-mentioned range. In addition, ethylene vinyl acetate copolymer emulsion, acrylic (ester) emulsion, vinyl acetate emulsion,
Styrene/butadiene copolymer emulsion, polyvinyl chloride emulsion, chloroprene rubber emulsion, ethylene/acrylic acid copolymer, ethylene/maleic anhydride copolymer, butadiene/
maleic anhydride copolymer polyvinyl alcohol,
An aqueous solution or emulsion of a polymeric substance such as starch or carboxymethylcellulose may be added as necessary. It also improves coating properties. Substances include alcohols such as ethyl alcohol and butyl alcohol that evaporate during the drying process and do not remain on the coating film, hydrocarbons such as petroleum spirits, kerosene, and xylene, esters such as ethyl acetate and butyl acetate, acetone, Ketones such as methyl ethyl ketone and cyclohexanone, ethers such as diethylene glycol and butyl cellosolve, and chloro compounds such as trichlorethylene and methylene chloride may be added. A liquid containing a cationic organic substance and an inorganic pigment is
It may be applied at any step of manufacturing photographic paper. For example, it can be done before emulsion coating, or after emulsion coating and before exposure.
It may be used after exposure and development. However, if the emulsion is applied before emulsion coating or after emulsion coating and before exposure, there is a possibility that a part of the cationic substance will be eluted into the developing solution during development, so it is preferable to apply the coating after exposure and development. Further, in order to improve the adhesive strength between the polyethylene layers, the polyethylene surface may be subjected to corona discharge treatment or glow discharge treatment. A general-purpose method can be used to apply the liquid. That is, bar coats, dip coats, gravure coats, etc. are common. The dry film thickness of the coating layer is preferably 1 μm or more, more preferably 3 μm or more. If it is less than 1 μm, the drying speed of water-based ink etc. will be significantly deteriorated, which is not preferable. Implementation of the present invention provides many advantages as described below. (1) It is possible to produce photographic paper that does not bleed water-based ink, dries quickly, and has printability on the back side. (2) Be able to write freely and clearly with any writing instrument including a pencil. (3) Since it is only necessary to apply paint to the back side of the photographic paper, mass production is possible through automatic operation, and it can therefore be manufactured at low cost. (4) Compared to the method of backing paper, there are no errors in the work itself, and there is no risk of wasting photos. (5) Compared to the method of backing paper, there is no chance of the photographic paper warping. Next, the present invention will be further explained with reference to the drawings. As shown in Figure 1, ordinary photographic paper has a paper support 1.
Polyethylene layers 2 and 3 are provided on both sides. A color or black and white photographic emulsion layer 4 is provided on the polyethylene layer 2 on the surface of the paper support.
This polyethylene layer 2 usually contains a light-reflecting substance such as titanium oxide. Note that an undercoat layer may be provided between the polyethylene layer 2 and the emulsion layer 4 in order to improve the adhesion between the two. FIG. 2 shows a sectional view of a photographic paper according to the present invention, in which a layer 5 containing a cationic organic substance and an inorganic pigment is provided on a polyethylene layer 3 on the back side. FIG. 3 is a perspective view showing an embodiment of the present invention, in which a postage stamp 6 is pasted on a layer 5 containing a cationic organic substance and an inorganic pigment to form a postcard. By doing this, you can easily create picture postcards of photos. The content of the present invention will be explained in more detail below based on Examples, and the degree of bleeding of aqueous ink shown in Examples was measured by the method described below. Water-based ink (product name:
Use a stamp on the Shachihatazol stamp pad (green) to make a 1 mm wide line and measure the width (mm) of the line after the water-based ink has completely dried. Comparative example 1 A depth of 10 mm on the back polyethylene surface of photographic paper
It was matte processed with microscopic irregularities of μ. Comparative Example 2 The back polyethylene surface of photographic paper was subjected to corona discharge treatment, and a solution consisting of 35 parts by weight of titanium oxide, 55 parts by weight of ethylene/vinyl acetate copolymer emulsion, and 10 parts by weight of water was applied with a dry film to 5 μm. I applied it and let it dry. Comparative Example 3 The back polyethylene surface of photographic paper was subjected to corona discharge treatment, and 35 parts by weight of titanium oxide, 55 parts by weight of ethylene/vinyl acetate copolymer emulsion,
【式】
（分子量320）８重量部、水２重量部から成る液を
乾燥で５μになるように塗布し乾燥した。
実施例 １
写真用印画紙の裏面ポリエチレン表面に、コロ
ナ放電処理を施し、更に酸化チタン35重量部、エ
チレン・酢酸ビニル共重合体エマルジヨン55重量
部、
（分子量576）８重量部、水２重量部から成る液を
乾膜で５μになるように塗布し乾燥した。
実施例 ２
写真用印画紙の裏面ポリエチレン表面に、コロ
ナ放電処理を施し、更に酸化チタン35重量部、エ
チレン・酢酸ビニル共重合体エマルジヨン55重量
部、[Formula] A solution consisting of 8 parts by weight (molecular weight 320) and 2 parts by weight of water was applied to a drying thickness of 5 μm and dried. Example 1 The back polyethylene surface of photographic paper was subjected to corona discharge treatment, and 35 parts by weight of titanium oxide, 55 parts by weight of ethylene/vinyl acetate copolymer emulsion, A solution consisting of 8 parts by weight (molecular weight 576) and 2 parts by weight of water was applied with a dry film to a thickness of 5 μm and dried. Example 2 The back polyethylene surface of photographic paper was subjected to corona discharge treatment, and 35 parts by weight of titanium oxide, 55 parts by weight of ethylene/vinyl acetate copolymer emulsion,
【式】
（平均分子量8904）８重量部、水２重量部から成
る液を乾膜で５μになるように塗布し乾燥した。
実施例 ３
写真用印画紙の裏面ポリエチレン表面に、コロ
ナ放電処理を施し、更に酸化チタン35重量部、エ
チレン・酢酸ビニル共重合体エマルジヨン55重量
部、
（平均分子量28400）８重量部、水２重量部から成
る液を乾膜で５μになるように塗布し乾燥した。
比較例１，２，３実施例１，２，３で作成した
写真用印画紙裏面の鉛筆、ボールペンによる描字
性、水性インクによる乾燥性、にじみ度合の評価
を行なつた所次表に示す結果が得られた。つまり
比較例１では鉛筆による描字性、水性インクの乾
燥性が著しく劣り、比較例２では水性インクのに
じみが極端に悪い。一方分子量が500未満のカチ
オン性有機物質を添加した比較例３ではいく分水
性インクのにじみが改良されているが、十分では
ない。これに対し分子量が500以上のカチオン性
有機物質を添加した実施例１，２，３ではいずれ
も水性インクのにじみが著しく減少している。ま
たその他の特性も満足されるものである。
したがつて分子量500以上のカチオン性有機物
質を添加することにより水性インクのにじみを改
良できることが示された。[Formula] A solution consisting of 8 parts by weight (average molecular weight 8904) and 2 parts by weight of water was applied with a dry film to a thickness of 5 μm and dried. Example 3 The back polyethylene surface of photographic paper was subjected to corona discharge treatment, and 35 parts by weight of titanium oxide, 55 parts by weight of ethylene/vinyl acetate copolymer emulsion, A solution consisting of 8 parts by weight (average molecular weight 28400) and 2 parts by weight of water was applied with a dry film to a thickness of 5 μm and dried. Comparative Examples 1, 2, and 3 The back side of the photographic paper prepared in Examples 1, 2, and 3 was evaluated for writing performance with a pencil or ballpoint pen, drying performance with water-based ink, and degree of bleeding, as shown in the following table. The results were obtained. That is, in Comparative Example 1, the drawing performance with a pencil and the drying property of the water-based ink were extremely poor, and in Comparative Example 2, the bleeding of the water-based ink was extremely poor. On the other hand, in Comparative Example 3 in which a cationic organic substance having a molecular weight of less than 500 was added, the bleeding of the water-separating ink was improved somewhat, but it was not sufficient. On the other hand, in Examples 1, 2, and 3 in which a cationic organic substance having a molecular weight of 500 or more was added, the bleeding of the aqueous ink was significantly reduced. In addition, other characteristics are also satisfied. Therefore, it has been shown that the bleeding of aqueous ink can be improved by adding a cationic organic substance having a molecular weight of 500 or more.
図面は本考案に係る写真用印画紙を説明する図
面であり、第１図は通常の写真用印画紙の断面図
を第２図は本考案に係る写真用印画紙の断面図を
示し、第３図は本考案の一実施態様であるポスト
カードを示す斜視図である。
１……支持体、２および３……ポリエチレン
層、４……写真乳剤層、５……カチオン性有機物
質と無機顔料を含む層、６……郵便切手。
The drawings are diagrams for explaining the photographic paper according to the present invention, and FIG. 1 shows a cross-sectional view of ordinary photographic photographic paper, and FIG. FIG. 3 is a perspective view showing a postcard which is an embodiment of the present invention. 1... Support, 2 and 3... Polyethylene layer, 4... Photographic emulsion layer, 5... Layer containing a cationic organic substance and inorganic pigment, 6... Postage stamp.
Claims (1)
と無機顔料を含む層を設けたことを特徴とする写
真用印画紙。 Photographic paper characterized by having a layer containing a cationic organic substance with a molecular weight of 500 or more and an inorganic pigment on the back side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13668180U JPS6134523Y2 (en) | 1980-09-26 | 1980-09-26 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13668180U JPS6134523Y2 (en) | 1980-09-26 | 1980-09-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5760140U JPS5760140U (en) | 1982-04-09 |
| JPS6134523Y2 true JPS6134523Y2 (en) | 1986-10-07 |
Family
ID=29496784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13668180U Expired JPS6134523Y2 (en) | 1980-09-26 | 1980-09-26 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6134523Y2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60238828A (en) * | 1984-05-11 | 1985-11-27 | Fuji Photo Film Co Ltd | Photographic printing paper base |
-
1980
- 1980-09-26 JP JP13668180U patent/JPS6134523Y2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5760140U (en) | 1982-04-09 |
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