JP3707819B2 - Support for imaging materials - Google Patents
Support for imaging materials Download PDFInfo
- Publication number
- JP3707819B2 JP3707819B2 JP02802895A JP2802895A JP3707819B2 JP 3707819 B2 JP3707819 B2 JP 3707819B2 JP 02802895 A JP02802895 A JP 02802895A JP 2802895 A JP2802895 A JP 2802895A JP 3707819 B2 JP3707819 B2 JP 3707819B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resin composition
- polyethylene
- polyethylene resin
- support
- 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 - Fee Related
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- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHHXUPJJDHEMGX-UHFFFAOYSA-K azanium;manganese(3+);phosphonato phosphate Chemical compound [NH4+].[Mn+3].[O-]P([O-])(=O)OP([O-])([O-])=O UHHXUPJJDHEMGX-UHFFFAOYSA-K 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- 235000019398 chlorine dioxide Nutrition 0.000 description 1
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- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
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- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
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- VKJQZSSBQZSTIM-UHFFFAOYSA-N hydroxymethanesulfonic acid;sodium Chemical compound [Na].OCS(O)(=O)=O VKJQZSSBQZSTIM-UHFFFAOYSA-N 0.000 description 1
- OOCSVLHOTKHEFZ-UHFFFAOYSA-N icosanamide Chemical compound CCCCCCCCCCCCCCCCCCCC(N)=O OOCSVLHOTKHEFZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
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- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
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- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は紙基体（以下基紙と言うことがある）の両面が樹脂層で被覆された樹脂被覆紙型画像材料用支持体に関するものであり、詳しくは画像形成層を設ける側とは反対側の樹脂層と基紙との接着性の良好な、かつ冷却ロール汚れに起因する問題の発生が無く、高速かつ安定生産できる樹脂被覆紙型画像材料用支持体に関するものである。
【０００２】
【従来の技術】
従来、画像材料用支持体のための基紙面がフィルム形成能ある樹脂で被覆された樹脂被覆紙型支持体はよく知られている。例えば、特公昭55-12584号公報には、基紙がフィルム形成能ある樹脂、好ましくはポリオレフィン樹脂で被覆された写真用支持体についての技術が開示されている。 米国特許第3,501,298 号公報には基紙の両面がポリオレフィン樹脂で被覆された写真用支持体についての技術が開示されている。また、ハロゲン化銀感光材料の迅速写真現像処理方式が適用されて以来、基紙の両面がポリエチレン系樹脂で被覆された写真用支持体が、写真印画紙用として主に実用化されており、必要に応じてその一方の画像形成側の樹脂層中には鮮鋭度を付与するために、通常二酸化チタン顔料を含有している。
【０００３】
また、米国特許第4,774,224 号公報には、樹脂被覆の表面粗さが７. ５マイクロインチ−ＡＡ以下である樹脂被覆紙、特に基紙の表面をポリエチレン樹脂で被覆したポリエチレン樹脂被覆紙を支持体として有する熱転写記録受像要素が提案されている。また、特開昭63-307979 号公報には、樹脂被覆紙を支持体として有するインクジェット記録用シ−トに関する技術が開示されている。
【０００４】
更に、写真層を設ける側とは反対側の基紙面を低密度ポリエチレン樹脂と高密度ポリエチレン樹脂とを含む樹脂組成物で被覆した写真用支持体に関する技術が提案されている。例えば、特公昭44-22904号公報には、密度が０. ９１５〜０. ９２６g/cm3 であり、融解指数が２. ９〜１６g/10分である特定の低密度ポリエチレン樹脂１５〜６５重量％と密度が０. ９６０〜０. ９７５g/cm3 であり、
融解指数が５〜１８g/10分である特定の高密度ポリエチレン樹脂８５〜３５重量％から成る、高速被覆能力があり、かつネックイン及びピンホ−ルの良好なポリエチレン組成物で基紙を被覆した写真用支持体についての開示がある。また、特公昭48-9963 号公報には、低密度ポリエチレン樹脂：高密度ポリエチレン樹脂＝１: １から成る樹脂組成物で基紙を被覆した、カ−ル物性の良好な写真用支持体についての開示がある。更に、特開昭58-95732号公報には、密度が０. ９４５g/cm3 以上であり、メルトインデックスが１５〜４０g/10分である高密度ポリエチレン樹脂４０〜７５重量部と密度が０. ９３０g/cm3 以下であり、メルトインデックスが１〜４０g/10分である低密度ポリエチレン樹脂６０〜２５重量部とから成るポリエチレン樹脂組成物で基紙を被覆した、切断性及びカ−ル物性の良好な写真用支持体についての開示がある。
【０００５】
しかしながら、画像形成層を設ける側とは反対側の基紙面（以下、画像形成層を設ける側の基紙面を表面、その反対側の基紙面を裏面と略すことがある）を被覆する樹脂組成物として、これらの先行技術に開示されたポリエチレン樹脂から成る樹脂組成物を用いても、紙を基質とする樹脂被覆紙型画像材料用支持体を生産する場合には、重大な問題点が発生することが判明した。また、該樹脂被覆紙型画像材料用支持体は、依然として品質的に重大な問題点を有していた。
【０００６】
即ち、第一に、ポリエチレン系樹脂被覆紙は、通常走行する基紙上に溶融押し出し機を用いて、そのスリットダイから溶融したポリエチレン系樹脂組成物をフィルム状に押し出し、流延して被覆し、加圧ロールと冷却ロールとの間で圧着し、冷却後ロールから剥離されるという一連の工程で生産される。しかし、基紙の裏面を被覆する樹脂組成物として、従来公知のポリエチレン樹脂から成る樹脂組成物を用いた場合には、冷却ロール上に冷却ロール汚れと呼称されるポリエチレン系樹脂組成物あるいはその変性物を主成分とする汚れが発生する傾向があった。ポリエチレン系樹脂被覆紙の生産は、操業開始から少なくとも２〜３日、通常は一週間、時には１ヶ月間連続して溶融押し出し機を稼動して行われるが、連続して操業する期間が長くなればなる程、始末が悪いことに、冷却ロール汚れは多く蓄積する傾向があった。
【０００７】
ポリエチレン系樹脂被覆紙の製造中に、冷却ロール汚れが多く発生し始めると冷却ロールからのポリエチレン系樹脂被覆紙の剥離性が悪化して、冷却ロールと樹脂層との粘着性が大きくなって冷却ロール側に樹脂層が取られる傾向が大きくなるために、基紙と樹脂層との接着性が不均一に弱くなったり、ひどい時には基紙と樹脂層とが剥離したりして画像材料用支持体用途のための樹脂被覆紙としては、全く不適当で商品価値のないものになるという問題点があった。また、蓄積した冷却ロール汚れが該樹脂層に附着したまま巻き取られ、画像形成層を設ける側の樹脂層（以下、画像形成層を設ける側を表側、表側に被覆される樹脂層を表樹脂層、その反対側を裏側、裏側に被覆される樹脂層を裏樹脂層と略することがある）面に転写して出現し、それこそ画像材料用支持体用途のための樹脂被覆紙としては、致命的な品質故障を起こすという問題点があった。更に、この冷却ロール汚れの転写の問題は、汚れが一旦樹脂被覆紙製造用のラミネーターのロールや乳剤コーターのロールに転写して、それが再転写して品質故障になるという深刻な問題を引き起こすこともあった。このため、冷却ロール汚れの十分な防止対策を講じる必要があった。
【０００８】
また、画像材料はカールが少なく平坦なものが好ましいものの樹脂被覆紙を支持体として有する画像材料ではバインダーを含む画像形成層側にカールする傾向が強く、特に多層ハロゲン化銀カラー写真印画紙においてはゼラチンを含む多層カラー写真構成層側にカールする傾向が強く、ことに現像処理後のカラー写真プリントにおいては、カールの傾向が顕在化した。このため、樹脂被覆紙型画像材料用支持体の裏樹脂層用の樹脂組成物として、低密度ポリエチレン樹脂と高密度ポリエチレン樹脂とから成る樹脂組成物が、しばしば用いられる。しかしながら、本発明者らの検討の結果、基紙の裏面被覆用の樹脂組成物として、低密度ポリエチレン樹脂と高密度ポリエチレン樹脂とから成る従来公知のポリエチレン樹脂組成物を用いると、それらの相乗作用により冷却ロール汚れが著しく顕在化するという事が判明し、カール物性の改良が極めて制限されるものになっていた。
【０００９】
第二に、基紙の裏面を被覆する樹脂組成物として、従来公知のポリエチレン樹脂から成る樹脂組成物を用いた場合には、樹脂被覆紙型画像材料用支持体の基紙と裏樹脂層との接着性が不十分となる傾向があった。基紙と裏樹脂層の接着性が不十分な樹脂被覆紙型画像材料用支持体は、該支持体を有する画像材料の製造時あるいは画像形成のための処理時に裏樹脂層が剥離して重大な品質故障を起こすという問題点があった。特に、ハロゲン化銀写真材料の場合には、裏樹脂層が剥離していると、現像処理時に現像処理液が基紙に浸透して着色汚染させてしまい、全く品質価値の無いものになるという問題点があった。この基紙と裏樹脂層との接着性の問題は、樹脂被覆紙型画像材料用支持体製造時の基紙の走行速度が速くなればなる程、特に１５０m/分以上で顕在化し、また裏樹脂層の被覆量が薄ければ薄い程、特に３２g/m2以下で顕在化した。
【００１０】
【発明が解決しようとする課題】
従って、本発明の目的は、生産中に冷却ロール汚れの発生が少なく、それ故にロール汚れの転写に起因する問題の発生が無く、かつ画像形成層を設ける側とは反対側の樹脂層と基紙との接着性が良好であり、なおかつ高速かつ安定生産出来る、紙を基質とする樹脂被覆紙型画像材料用支持体を提供することである。本発明のその他の目的は、以下の明細書の記載から明らかとなろう。
【００１１】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、紙を基質として、その一方の画像形成層を設ける側とは反対側の紙基質面がポリエチレン系樹脂を主成分とする樹脂組成物から成る樹脂層で被覆された画像材料用支持体において、該樹脂組成物がメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有し、かつ該樹脂組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎ（ここで、Ｍｗ：重量平均分子量、Ｍｎ：数平均分子量を表す）が４以上であることを特徴とする画像材料用支持体によって、本発明の目的が達成されることを見い出した。
【００１２】
本発明で言うＭｗ／Ｍｎは具体的には以下の如く求める。ウォーターズ社製１５０−Ｃ（カラム：東ソー社製ＧＭＨ−ＸＬ ＨＴ ８mmφ×３cm×３本、溶媒：１、 ２、 ４−トリクロロベンゼン、温度：１３５℃、流量１０ml/ 分）を用いるゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により、ポリエチレン系樹脂を主成分とする樹脂組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ及びＭｎを測定し、Ｍｗ／Ｍｎを算出した。
【００１３】
本発明の目的は、ポリエチレン系樹脂を主成分とする樹脂組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが５. ５以上、特に７. ０以上の樹脂組成物を用いることにより、顕著に達成される事を見い出した。また、本発明の目的は、ポリエチレン系樹脂を主成分とする樹脂組成物（以下、単にポリエチレン系樹脂組成物と略することがある）中のメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂の含有率を全ポリエチレン系樹脂に対して２５重量％以上にすることにより、顕著に達成される事を見い出した。
【００１４】
本発明の実施に用いられるメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂としては、特表平3-502710号公報、特開昭60-35006号公報、特表昭63-501369号公報、特開平3-234717号公報、特開平3-234718号公報等に記載もしくは開示されている如く、ジルコニウム系、チタニウム系又はハフニウム系メタロセンと、好ましくはメチルアルミノキサン等のアルミノキサンとを組み合わせたものを重合触媒として用いて重合製造されたものである。それらのものとしては、エチレンとプロピレン、ブテン−１、ヘキセン−１、オクテン−１、等のα−オレフィンとの共重合体、カルボキシ変性ポリエチレン樹脂等のポリエチレン系樹脂が例示できる。これらのものとしては、各種の密度、メルトフローレート（以下、単にＭＦＲと略す）、分子量、分子量分布のものを使用出来るが、通常、密度が０．８５〜０．９７g/cm３の範囲、ＭＦＲが０．０５〜５００g/10分、好ましくは０．０８〜３００g/10分の範囲のものを単独に或は二種以上混合して使用出来る。
【００１５】
また、本発明の実施に用いられるポリエチレン系樹脂組成物は、メタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有するものであるが、ポリエチレン系樹脂組成物の成形加工性及び基紙と裏樹脂層との接着性、印画紙のカール物性等の性能を一層改良する観点から、高圧法により製造された長鎖分枝を有するポリエチレン系樹脂、メタロセン以外の金属重合触媒を用いて重合製造したポリエチレン系樹脂等を含有せしめるのが有用である。本明細書で言うポリエチレン系樹脂組成物の成形加工性とは、ネックインの程度、溶融樹脂膜の筋の発生の程度、ドローダウン性の程度による膜切れの発生の有無、サージングあるいはドローレゾナンスによる流動の不安定性等の総合的な成形加工性のことをいう。
【００１６】
本発明の実施に用いられるポリエチレン系樹脂組成物としては、該組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４以上のものであるが、樹脂樹脂組成物の成形加工性の点からＭｗ／Ｍｎが５. ５以上のものが好ましく、７. ０以上のものが特に好ましい。
【００１７】
また、本発明の実施に用いられるポリエチレン系樹脂組成物中のメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂の含有率としては、冷却ロール汚れの改良効果及び裏樹脂層と基紙との接着性の改良効果、更には樹脂組成物の成形加工性の観点から、樹脂組成物中の全ポリエチレン系樹脂に対して２５％以上が好ましい。
【００１８】
本発明の実施に用いられるポリエチレン系樹脂組成物中に、メタロセン重合触媒を用いて重合製造したポリエチレン系樹脂と有利に併用して含有せしめられる高圧法により製造された長鎖分枝を有するポリエチレン系樹脂としては、オートクレーブ型反応器、チューブラー型反応器等を用いた、例えば１０００〜３５００気圧下での高圧ラジカル重合法による長鎖分枝を有する各種のポリエチレン系樹脂である。それらの高圧法により製造された長鎖分子を有するポリエチレン系樹脂としては、エチレンの単独重合体、エチレンとプロピレン、ブテン−１、等のα−オレフィンとの共重合体、カルボキシ変性ポリエチレン樹脂等のポリエチレン系樹脂を例示できる。これらのものとしては、各種の密度、ＭＦＲ、分子量、分子量分布のものを使用できるが、通常、密度が０. ８５〜０. ９５g/cm3 の範囲、ＭＦＲが０. １〜５０g/10分、好ましくはＭＦＲが０. ４〜５０g/10分の範囲のものを単独に或は二種以上混合して使用出来る。本明細書で言うカルボキシ変性ポリエチレン樹脂とは、エチレンとマレイン酸、アクリル酸、メタクリル酸等のα、β−不飽和カルボン酸或いは環内に不飽和結合を持つ脂環式カルボン酸等の不飽和カルボン酸または不飽和カルボン酸の無水物、アミド、エステル等の共重合体またはポリエチレンにこれらの不飽和カルボン酸或いは不飽和カルボン酸の無水物、アミド、エステル等をグラフトして変性した樹脂を言う。
【００１９】
本発明の実施に用いられるポリエチレン系樹脂組成物中に、メタロセン重合触媒を用いて重合製造したポリエチレン樹脂と有利に併用して含有せしめられる、メタロセン重合触媒以外の金属重合触媒を用いて重合製造したポリエチレン系樹脂としては、例えば、チーグラー法、フィリップス法等を用いて重合製造した各種のポリエチレン系樹脂をあげることができる。それらのメタロセン重合触媒以外の金属重合触媒を用いて重合製造したポリエチレン系樹脂としては、低密度ポリエチレン樹脂、中密度ポリエチレン樹脂、高密度ポリエチレン樹脂、直鎖状低密度ポリエチレン樹脂、エチレンとプロピレン、ブチレン等のα−オレフィンとの共重合体、あるいはカルボキシ変性ポリエチレン樹脂等及びこれらの混合物であり、各種の密度、ＭＦＲ、分子量、分子量分布のものを使用できるが、通常、密度が０. ８５〜０. ９７g/cm3 の範囲、ＭＦＲが０. ０５〜５００g/10分、好ましくは０. ０８〜３００g/10分の範囲のものを単独に或は二種以上混合して使用出来る。
【００２０】
また、裏樹脂層を多層構成にすることも出来る。裏樹脂層が多層構成の場合、最外層の樹脂組成物として本発明におけるもの、下層の樹脂組成物として従来公知のものを使用するなど別の性質、構成の樹脂組成物を使用することもできる。
【００２１】
本発明における画像材料用支持体の基紙の画像形成層を設ける側の面は、フィルム形成能ある樹脂で被覆される。それらのフィルム形成能ある樹脂としては、ポリオレフィン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂等の熱可塑性樹脂が好ましく、中でも溶融押し出しコーティング性の点からポリオレフィン樹脂が更に好ましく、ポリエチレン系樹脂が特に好ましい。また、特公昭60-17104号公報に記載もしくは例示の電子線硬化樹脂で被覆してもよい。
【００２２】
本発明における画像材料用支持体の裏側の樹脂層の被覆厚さとしては、４〜１００μｍの範囲が有用であるが、６〜５０μｍの範囲が好ましく、９〜３５μｍの範囲が特に好ましい。基紙の表面は、フィルム形成能ある樹脂で被覆されるが、その樹脂はポリエチレン系樹脂が好ましく、その被覆厚さとしては裏側の樹脂と、特にカールバランスを取る範囲で適宜設定するのが好ましく、一般に４〜１００μｍの範囲が有用であるが、好ましくは６〜５０μｍの範囲である。
【００２３】
本発明における画像材料用支持体の基紙面にポリエチレン系樹脂組成物を被覆する方法としては、走行する基紙上に樹脂組成物を溶融押し出し機を用いて、そのスリットダイからフィルム状に流延して被覆する、所謂溶融押し出しコーティング法によって被覆するのが好ましい。その際、溶融フィルムの温度は２８０〜３４０℃であることが好ましい。スリットダイとしては、Ｔ型ダイ、Ｌ型ダイ、フィッシュテイル型ダイのフラットダイが好ましく、スリット開口径は０. １〜２mmであることが望ましい。また、樹脂組成物を基紙にコーティングする前に、基紙にコロナ放電処理、火炎処理等の活性化処理を施すのが好ましい。また、特公昭61-42254号公報に記載の如く、基紙に接する側の溶融樹脂組成物にオゾン含有ガスを吹きつけた後に走行する基紙に樹脂層を被覆してもよい。また、基紙の両面を樹脂層で被覆する場合には、表、裏の樹脂層は逐次、好ましくは連続的に、押し出しコーティングされる、所謂タンデム押し出しコーティング方式で基紙に被覆されるのが好ましく、必要に応じて樹脂層を多層構成にする、多層押し出しコーティング方式で被覆しても良い。また、画像材料用支持体の画像形成層を塗設する側の表樹脂層面は光沢面、特公昭62-19732号公報に記載の微粗面、マット面或は絹目面等に加工することが出来、その反対側の裏樹脂層面は通常無光沢面に加工するのが好ましい。
【００２４】
本発明における画像材料用支持体の表樹脂層中及び必要に応じて裏樹脂層中には、各種の添加剤を含有せしめることが出来る。特公昭60-3430 号公報、特公昭63-11655号公報、特公平1-38291 号公報、特公平1-38292 号公報、特開平1-105245号公報等に記載もしくは例示の二酸化チタン顔料、酸化亜鉛、タルク、炭酸カルシウム等の白色顔料、ステアリン酸アミド、アラキジン酸アミド等の脂肪酸アミド、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸マグネシウム、パルミチン酸亜鉛、ミリスチン酸亜鉛、パルミチン酸カルシウム等の脂肪酸金属塩、特開平1-105245号公報に記載もしくは例示のヒンダードフェノール、ヒンダードアミン、リン系、硫黄系等の各種酸化防止剤、コバルトブルー、群青、セリアンブルー、フタロシアニンブルー等のブルー系の顔料や染料、コバルトバイオレット、ファストバイオレット、マンガンバイオレット等のマゼンタ系の顔料や染料、特開平2-254440号公報に記載もしくは例示の蛍光増白剤、紫外線吸収剤等の各種の添加剤を適宜組み合わせて含有せしめることが出来る。それらの添加剤は、樹脂のマスターバッチあるいはコンパウンドとして含有せしめるのが好ましい。
【００２５】
本発明の実施に用いられる基紙は通常の天然パルプを主成分とする天然パルプ紙が好ましい。また、天然パルプと合成パルプ、合成繊維とからなる混抄紙でもよい。それらの天然パルプとしては、特開昭58-37642号公報、特開昭60-67940号公報、特開昭60-69649号公報、特開昭61-35442号公報等に記載もしくは例示してあるような適切に選択された天然パルプを用いるのが有利である。天然パルプは塩素、次亜塩素酸塩、二酸化塩素漂白の通常の漂白処理並びにアルカリ抽出もしくはアルカリ処理および必要に応じて過酸化水素、酸素などによる酸化漂白処理など、およびそれらの組み合わせ処理を施した針葉樹パルプ、広葉樹パルプ、針葉樹広葉樹混合パルプの木材パルプが有利に用いられ、また、クラフトパルプ、サルファイトパルプ、ソ−ダパルプなどの各種のものを用いることができる。
【００２６】
本発明の実施に好ましく用いられる天然パルプを主成分とする基紙中には、紙料スラリ−調製時に各種の添加剤を含有せしめることができる。サイズ剤として、脂肪酸金属塩あるいは脂肪酸、特公昭62-7534 号公報に記載もしくは例示のアルキルケテンダイマー乳化物あるいはエポキシ化高級脂肪酸アミド、アルケニルまたはアルキルコハク酸無水物乳化物、ロジン誘導体等、乾燥紙力増強剤として、アニオン性、カチオン性あるいは両性のポリアクリルアミド、ポリビニルアルコール、カチオン化澱粉、植物性ガラクトマンナン等、湿潤紙力増強剤として、ポリアミンポリアミドエピクロルヒドリン樹脂等、填料として、クレ−、カオリン、炭酸カルシウム、酸化チタン等、定着剤として、塩化アルミニウム、硫酸バン土等の水溶性アルミニウム塩等、ｐＨ調節剤として、苛性ソ−ダ、炭酸ソ−ダ、硫酸等、その他特開昭63-204251 号公報、特開平1-266537号公報等に記載もしくは例示の着色顔料、着色染料、蛍光増白剤などを適宜組み合せて含有せしめるのが有利である。
【００２７】
また、本発明の実施に好ましく用いられる天然パルプを主成分とする基紙中あるいは基紙上には、各種の水溶性ポリマーもしくは親水性コロイドまたはラテックス、帯電防止剤、添加剤から成る組成物をサイズプレスもしくはタブサイズプレスあるいはブレード塗工、エアーナイフ塗工などの塗工によって含有あるいは塗設せしめることができる。水溶性ポリマーもしくは親水性コロイドとして、特開平1-266537号公報に記載もしくは例示の澱粉系ポリマー、ポリビニルアルコール系ポリマー、ゼラチン系ポリマー、ポリアクリルアミド系ポリマー、セルローズ系ポリマーなど、エマルジョン、ラテックス類として、石油樹脂エマルジョン、特開昭55-4027 号公報、特開平1-180538号公報に記載もしくは例示のエチレンとアクリル酸（又はメタクリル酸）とを少なくとも構成要素とする共重合体のエマルジョンもしくはラテックス、スチレン−ブタジエン系、スチレン−アクリル系、酢酸ビニル−アクリル系、エチレン−酢酸ビニル系、ブタジエン−メチルメタクリレート系共重合体及びそれらのカルボキシ変性共重合体のエマルジョンもしくはラテックス等、帯電防止剤として、塩化ナトリウム、塩化カリウム等のアルカリ金属塩、塩化カルシウム、塩化バリウム等のアルカリ土類金属塩、コロイド状シリカ等のコロイド状金属酸化物、ポリスチレンスルホン酸塩等の有機帯電防止剤など、顔料として、クレー、カオリン、炭酸カルシウム、タルク、硫酸バリウム、酸化チタンなど、ｐＨ調節剤として、塩酸、リン酸、クエン酸、苛性ソーダなど、そのほか前記した着色顔料、着色染料、蛍光増白剤などの添加剤を適宜組み合わせて含有せしめるのが有利である。
【００２８】
本発明の実施に用いられる基紙の厚みに関しては、特に制限はないが、その坪量は２０〜２００g/m2のものが好ましい。
【００２９】
また、本発明の実施に用いられる基紙としては、下記で規定される抄紙方向の膜厚むら指数Ｒｐｙが２５０mV以下にしたものが好ましく、２００mV以下のしたものが更に好ましく、１５０mV以下のものが最も好ましい。ここで言う膜厚むら指数Ｒｐｙとは、２つの球状の触針の間に試料を走行させ、試料の厚み変動を電子マイクロメーターを介し電気信号として測定するフィルム厚み測定器を用い、電子マイクロメーターの感度レンジが±１５μｍ／±３Ｖの条件で、ゼロ点調整後試料の抄紙方向に１. ５m/分の定速で走査することで試料の抄紙方向の厚み変動を測定し、得られた測定信号値を、ＦＦＴアナライザーを用いて、時間窓にハニングウィンドウを使用して高速フーリエ変換して、１２８回の積算の加算平均によるパワースペクトル（単位：mV2 ）を求め、２〜２５Hzの周波数域のパワー値を総和して２／３を掛けた値を１／２乗することにより求められる値（単位：mV）である。
【００３０】
本発明の実施に好ましく用いられる、膜厚むら指数Ｒｐｙが２５０mV以下の原紙を製造する方法としては、具体的には、短繊維で平滑性のでやすい広葉樹パルプを３０重量％以上、好ましくは５０重量％以上用い、叩解機により長繊維分がなるべく少なくなるように叩解する。例えば、パルプの叩解は叩解後のパルプの加重平均繊維長が０. ４〜０. ７５mmになるようにすることが好ましい。ついで、内添薬品を添加した紙料スラリーについて、特開昭58-37642号公報、特開昭61-260240 号公報、特開昭61-284762 号公報等に記載もしくは例示してあるような適切な抄紙方法を採用して長網抄紙機、丸網抄紙機等通常用いられる抄紙機により均一な地合が得られるように抄造し、更に抄造後マシンカレンダー、スーパーカレンダー、熱カレンダー等を用いてカレンダー処理を施し、膜厚むら指数Ｒｐｙが２５０mV以下の基紙を製造することが出来る。
【００３１】
本発明における画像材料用支持体の表樹脂層面上には、コロナ放電処理、火炎処理などの活性化処理を施した後、特開昭61-84643号公報、特開平1-92740 号公報、特開平1-102551号公報、特開平1-166035号公報等に記載もしくは例示のような下引層を塗設することができる。また、本発明における画像材料用支持体の裏樹脂層面上には、コロナ放電処理、火炎処理などの活性化処理を施した後、帯電防止等のために各種のバックコ−ト層を塗設することができる。また、バックコ−ト層には、特公昭52-18020号公報、特公昭57-9059 号公報、特公昭57-53940号公報、特公昭58-56859号公報、特開昭59-214849 号公報、特開昭58-184144 号公報等に記載もしくは例示の無機帯電防止剤、有機帯電防止剤、親水性バインダ−、ラテックス、硬化剤、顔料、界面活性剤等を適宜組み合わせて含有せしめることができる。
【００３２】
本発明における画像材料用支持体は、各種の写真構成層が塗設されてカラ−写真印画紙用、白黒写真印画紙用、写植印画紙用、複写印画紙用、反転写真材料用、銀塩拡散転写法ネガ用及びポジ用、印刷材料用等各種の用途に用いることができる。例えば、塩化銀、臭化銀、塩臭化銀、沃臭化銀、塩沃臭化銀乳剤層を設けることができる。ハロゲン化銀写真乳剤層にカラ−カプラ−を含有せしめて、多層ハロゲン化銀カラ−写真構成層を設けることができる。また、銀塩拡散転写法用写真構成層を設けることができる。それらの写真構成層の結合剤としては、通常のゼラチンの他に、ポリビニルピロリドン、ポリビニルアルコ−ル、多糖類の硫酸エステル化合物などの親水性高分子物質を用いることができる。また、上記の写真構成層には各種の添加剤を含有せしめることができる。例えば、増感色素として、シアニン色素、メロシアニン色素など、化学増感剤として、水溶性金化合物、イオウ化合物など、カブリ防止剤もしくは安定剤として、ヒドロキシ−トリアゾロピリミジン化合物、メルカプト−複素環化合物など、硬膜剤としてホルマリン、ビニルスルフォン化合物、アジリジン化合物など、塗布助剤として、アルキルベンゼンスルフォン酸塩、スルホコハク酸エステル塩など、汚染防止剤として、ジアルキルハイドロキノン化合物など、そのほか蛍光増白剤、鮮鋭度向上色素、帯電防止剤、ｐＨ調製剤、カブらせ剤、更にハロゲン化銀の生成・分散時に水溶性イリジウム、水溶性ロジウム化合物などを適宜組み合わせて含有せしめることができる。
【００３３】
本発明に係る写真材料は、その写真材料に合わせて「写真感光材料と取扱法」（共立出版、宮本五郎著、写真技術講座２）に記載されている様な露光、現像、停止、定着、漂白、安定などの処理を行うことが出来る。また、多層ハロゲン化銀カラー写真材料は、ベンジルアルコール、タリウム塩、フェニドンなどの現像促進剤を含む現像液で処理してもよいし、ベンジルアルコールを実質的に含まない現像液で処理することもできる。
【００３４】
本発明における画像材料用支持体は、各種の熱転写記録受像層が塗設されて各種の熱転写記録受像材料用支持体として用いることができる。それらの熱転写記録受像層に用いられる合成樹脂としては、ポリエステル樹脂、ポリアクリル酸エステル樹脂、ポリカーボネート樹脂、ポリ酢酸ビニル樹脂、ポリビニルブチラール樹脂、スチレンアクリレート樹脂、ビニルトルエンアクリレート樹脂等のエステル結合を有する樹脂、ポリウレタン樹脂等のウレタン結合を有する樹脂、ポリアミド樹脂等のアミド結合を有する樹脂、尿素樹脂等の尿素結合を有する樹脂、その他ポリカプロラクタム樹脂、スチレン系樹脂、ポリ塩化ビニル樹脂、塩化ビニル−酢酸ビニル共重合体樹脂、ポリアクリロニトリル樹脂等を挙げられる。これら樹脂に加えて、これらの混合物もしくは共重合体等も使用できる。
【００３５】
本発明に係わる熱転写記録受像層中には、上記合成樹脂の他に離型剤、顔料等を加えても良い。上記離型剤としては、ポリエチレンワックス、アミドワックス、テフロンパウダー等の固形ワックス類、弗素系、リン酸エステル系界面活性剤、シリコーンオイル類等が挙げられる。これら離型剤の中でシリコーンオイルが最も好ましい。上記シリコーンオイルとしては、油状の物も使用できるが、硬化型のものが好ましい。硬化型のシリコーンオイルとしては、反応硬化型、光硬化型、触媒硬化型等が挙げられるが、反応硬化型のシリコーンオイルが特に好ましい。反応硬化型シリコーンオイルとしては、アミノ変性シリコーンオイル、エポキシ変性シリコーンオイル等が挙げられる。上記反応性シリコーンオイルの添加量は、受像層中に０. １〜２０wt％が好ましい。 上記顔料としては、シリカ、炭酸カルシウム、酸化チタン、酸化亜鉛等の体質顔料が好ましい。また、受像層の厚さとしては、０. ５〜２０μｍが好ましく、２〜１０μｍがさらに好ましい。
【００３６】
本発明における画像材料用支持体は、各種のインク受容層が塗設されて各種のインクジェット記録材料用支持体として用いることができる。それらのインク受容層中にはインクの乾燥性、画像の鮮鋭性等を向上させる目的で各種のバインダーを含有せしめることができる。それらのバインダーの具体例としては、石灰処理ゼラチン、酸処理ゼラチン、酵素処理ゼラチン、ゼラチン誘導体、例えばフタール酸、マレイン酸、フマール酸等の二塩基酸の無水物と反応したゼラチン等の各種のゼラチン、各種ケン化度の通常のポリビニルアルコール、カルボキシ変性、カチオン変性及び両性のポリビニルアルコール及びそれらの誘導体、酸化澱粉、カチオン化澱粉、エーテル化澱粉等の澱粉類、カルボキシメチルセルロ−ス、ヒドロキシエチルセルロース等のセルロ−ス誘導体、ポリビニルピロリドン、ポリビニルピリジウムハライド、ポリアクリル酸ソーダ、アクリル酸メタクリル酸共重合体塩、ポリエチレングリコール、ポリプロピレングリコール、ポリビニルエーテル、アルキルビニルエーテル・無水マレイン酸共重合体、スチレン・無水マレイン酸共重合体及びそれらの塩、ポリエチレンイミン等の合成ポリマー、スチレン・ブタジエン共重合体、メチルメタクリレート・ブタジエン共重合体等の共役ジエン系共重合体ラテックス、ポリ酢酸ビニル、酢酸ビニル・マレイン酸エステル共重合体、酢酸ビニル・アクリル酸エステル共重合体、エチレン・酢酸ビニル共重合体等の酢酸ビニル系重合体ラテックス、アクリル酸エステル重合体、メタクリル酸エステル重合体、エチレン・アクリル酸エステル共重合体、スチレン・アクリル酸エステル共重合体等のアクリル系重合体または共重合体のラテックス、塩化ビニリデン系共重合体ラテックス等或はこれらの各種重合体のカルボキシル基等の官能基含有単量体による官能基変性重合体ラテックス、メラミン樹脂、尿素樹脂等の熱硬化合成樹脂系等の水性接着剤及びポリメチルメタクリレート、ポリウレタン樹脂、不飽和ポリエステル樹脂、塩化ビニル・酢酸ビニルコーポリマー、ポリビニルブチラール、アルキッド樹脂等の合成樹脂系接着剤、特公平3-24906 号公報、特開平3-281383号公報、特願平4-240725号公報に記載もしくは例示のアルミナゾル、シリカゾル等の無機系バインダー等をあげることができ、これらを単独或は併用して含有せしめることができる。
【００３７】
本発明に係わるインクジェット記録材料のインク受容層中には、バインダーの他に各種の添加剤を含有せしめることができる。例えば、界面活性剤として、長鎖アルキルベンゼンスルフォン酸塩、長鎖、好ましくは分枝アルキルスルフォコハク酸エステル塩などのアニオン系界面活性剤、長鎖、好ましくは分岐アルキル基含有フェノールのポリアルキレンオキサイドエーテル、長鎖アルキルアルコールのポリアルキレンオキサイドエーテル等のノニオン系界面活性剤、特公昭47-9303 号公報、米国特許3,589,906 号明細書等に記載のフルオロ化した界面活性剤など、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシランなどのシランカップリング剤、ポリマーの硬膜剤として、活性ハロゲン化合物、ビニルスルフォン化合物、アジリジン化合物、エポキシ化合物、アクリロイル化合物、イソシアネート化合物等の硬膜剤、防腐剤として、特開平1-102551号公報に記載もしくは例示のＰ−ヒドロキシ安息香酸エステル化合物、ベンズイソチアゾロン化合物、イソチアゾロン化合物等、特開昭63-204251 号公報、特開平1-266537号公報等に記載もしくは例示の着色顔料、着色染料、蛍光増白剤など、黄変防止剤としてヒドロキシメタンスルフォン酸ソーダ、Ｐ−トルエンスルフィン酸ソーダ等、紫外線吸収剤として、ヒドロキシ−ジ−アルキルフェニル基を２位に有するベンゾトリアゾール化合物など、酸化防止剤として、特開平1-105245号公報に記載もしくは例示のポリヒンダードフェノール化合物など、鉛筆加筆剤として、澱粉粒、硫酸バリウム、二酸化珪素等の有機または無機の粒子径０. ２〜５μｍの微粒子、特公平4-1337号公報等に記載もしくは例示のオルガノポリシロキサン化合物、ｐＨ調節剤として、苛性ソーダ、炭酸ソーダ、硫酸、塩酸、リン酸、クエン酸など、オクチルアルコール、シリコン系消泡剤などの各種の添加剤を適宜組み合わせて含有せしめることができる。
【００３８】
【実施例】
以下、実施例により本発明を詳しく説明するが、本発明の内容は実施例に限られるものではない。
【００３９】
実施例１〜２及び比較例１〜４
広葉樹漂白クラフトパルプ５０重量％、広葉樹漂白サルファイトパルプ３５重量％及び針葉樹漂白サルファイトパルプ１５重量％から成る混合パルプを繊維長が０. ６mmになるように叩解後、パルプ１００重量部に対して、カチオン化澱粉３重量部、アニオン化ポリアクリルアミド０. ２重量部、アルキルケテンダイマー乳化物（ケテンダイマー分として）０. ４重量部、ポリアミドエピクロルヒドリン樹脂０. ４重量部及び適当量の蛍光増白剤、青色染料、赤色染料を添加して紙料スラリーを調製した。なお、叩解後のパルプの繊維長については、ＪＡＰＡＮ ＴＡＰＰＩ紙パルプ試験方法Ｎｏ, ５２−８９「紙及びパルプ繊維長試験方法」に準拠してカヤーニ社製ＦＳ−１００型機で測定した長さ加重平均繊維長で表す。その後、紙料スラリーを２００m/分で走行している長網抄紙機にのせ適切なタービュレンスを与えつつ紙匹を形成し、ウェットパートで１５〜１００kg/cm の範囲で線圧が調節された３段のウェットプレスを行った後、スムージングロールで処理し、引き続く乾燥パートで３０〜７０kg/cm 範囲で線圧が調節された２段の緊度プレスを行った後、乾燥した。その後、乾燥の途中でカルボキシ変性ポリビニルアルコール４重量部、蛍光増白剤０. ０５重量部、青色染料０. ００２重量部、塩化ナトリウム４重量部及び水９２重量部から成るサイズプレス液を２５g/m2サイズプレスし、最終的に得られる基紙水分が絶乾水分で８重量％になるように乾燥し、７０kg/cm の線圧でマシンカレンダー処理した後温度１５０℃、線圧１５０kg/cm の条件で熱カレンダー処理して坪量１７０g/m2の膜厚むら指数Ｒｐｙが１４０mVである画像材料用支持体の基紙を製造した。
【００４０】
次に、画像形成層を塗設する側とは反対側の基紙面（裏面）をコロナ放電処理した後、該裏面に下記のポリエチレン系樹脂組成物を樹脂温度３２０℃で２５μｍの樹脂厚さに基紙の走行速度２００m/分で溶融押し出しコ−ティングした。この際、冷却ロールとしては、該裏樹脂層面の中心面平均粗さＳＲａが１. ３μｍになるように粗面度を設計した、液体ホーニング法で粗面化された冷却ロールを用いて、冷却水温度１２℃で操業した。
【００４１】
裏樹脂層用のポリエチレン系樹脂組成物（実施例１〜２及び比較例１〜４）は表２に記載の配合のものであり、二種以上併用する樹脂組成物については、混練用押し出し機を用いて予め溶融・混合し、冷却、ペレット化して製造したコンパウンド樹脂組成物として用いた。また、表２に記載の配合のポリエチレン系樹脂組成物を構成するのに用いられたポリエチレン系樹脂は表１に記載のものである。
【００４２】
【表１】
メタロセン重合触媒を用いて重合製造したポリエチレン系樹脂（Ｍ１〜Ｍ１７）として、特表平3-502710号公報に記載の方法に基づいてエチレン／ブラン−１共重合体を製造した。
【００４４】
メタロセン以外の重合触媒を用いて製造したポリエチレン系樹脂（Ｚ１〜Ｚ１２）は、チーグラー法により製造した。
【００４５】
ポリエチレン系樹脂（Ｌ１〜Ｌ３）は、高圧法により製造した。
【００４６】
引き続き、基紙の表面をコロナ放電処理した後、該表面に低密度ポリエチレン樹脂（密度０. ９２０g/cm3 、ＭＦＲ＝８. ５g/10分）４７. ５重量％、含水酸化アルミニウム（対二酸化チタンに対してＡｌ2 Ｏ3 分として０. ７５重量％）で表面処理したアナタ−ゼ型二酸化チタン顔料５０重量％とステアリン酸亜鉛２. ５ 重量％から成る二酸化チタン顔料のマスタ−バッチ２０重量部、低密度ポリエチレン樹脂（密度０. ９２０g/cm3 、ＭＦＲ＝４. ５g ／10分）６５重量部と高密度ポリエチレン樹脂（密度０. ９７０g/cm3 、ＭＦＲ＝７. ０g ／10分）１５重量部から成る樹脂組成物を樹脂温度３２０℃で３２μｍの樹脂厚さに基紙の走行速度２００m/分で溶融押し出しコ−ティングした。なお、表、裏のポリエチレン系樹脂組成物の溶融押し出しコ−ティングは、逐次押し出しコ−ティングが行われる、いわゆるタンデム方式で行われた。その際、該樹脂被覆紙の二酸化チタン顔料を含む樹脂層の表面はグロッシー面に加工した。
【００４７】
更に、樹脂被覆紙の裏樹脂層面にコロナ放電処理後、下記のバックコ−ト塗液をオンマシン塗布した。乾燥重量分として、コロイド状シリカ：スチレン系ラテックス＝１：１から成り、更にポリスチレンスルフォン酸ソーダ０. ０２１g/m2の他適量の塗布助剤等を含むバックコ−ト塗液をラテックス分（固形重量計算で）として０. ２１g/m2になる塗布量で塗設して画像材料用支持体を得た。
【００４８】
以上のようにして画像材料用支持体を製造する時の裏樹脂層用のポリエチレン系樹脂組成物の成形加工性、冷却ロール汚れの発生程度及び画像材料用支持体の基紙と裏樹脂層との接着性の評価方法としては、以下に記載の方法で評価した。
【００４９】
画像材料用支持体製造時の裏樹脂層用のポリエチレン系樹脂組成物の成形加工性の評価方法としては、裏面の樹脂被覆部分の横方向の長さを測定してネックインの程度を評価すると共に、溶融樹脂膜の筋の発生の程度、ドローダウン性の程度による膜切れの発生の有無、サージングあるいはドローレゾナシスによる流動の不安定性等の成形加工性について総合的に評価した。評価基準としては、◎；極めて良好、○；良好、△；やや悪いが実用上問題がない程度、×；悪く実用上問題がある程度、を表す。
【００５０】
裏樹脂層用のポリエチレン系樹脂組成物の溶融押し出し時の冷却ロール汚れの評価方法としては、前記の製造条件下で画像材料製造時に製造開始から６時間後に冷却ロール上の汚れの発生状況を視覚的に判定して評価した。評価基準としては、○；冷却ロール汚れの発生が少なく良好、△；冷却ロール汚れの発生がやや多いが、実用上問題がない程度、×；冷却ロール汚れの発生が多くて、実用上問題がある程度、を表す。
【００５１】
画像材料用支持体の基紙と裏樹脂層との接着性の評価方法としては、各試料を５０℃、６０％ＲＨの恒温恒湿槽に１日間保存した後、試料の基紙層と裏面の樹脂層とに剥離し、剥離した樹脂層に付着した基紙層の面積率を測定することにより、基紙と裏樹脂層との接着性を評価した。評価基準としては、○；面積率が１００％で良好、△；面積率が１００％未満で８０％以上であり、接着性がやや悪いが実用上問題がない程度、×；面積率が８０％未満であり、接着性が悪く実用上問題がある程度、を表す。
【００５２】
得られた結果を表３に表す。
【００５３】
【表２】
【表３】
表３の結果から、ポリエチレン系樹脂組成物からなる裏樹脂層で被覆された画像材料用支持体において、該樹脂組成物がメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有し、かつポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４以上であるポリエチレン系樹脂組成物からなる裏樹脂層で被覆された本発明における画像材料用支持体（実施例１〜２）は、ポリエチレン系樹脂組成物の成形加工性が良好であり、冷却ロール汚れの発生が無く、かつ基紙と裏樹脂層との接着性が良好である、優れた画像材料用支持体であることがよくわかる。特に、裏樹脂層用のポリエチレン系樹脂組成物としては、該組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが、ポリエチレン系樹脂組成物の成形加工性の点から、７. ０以上のものが好ましいこと（実施例１と実施例２との比較）がよくわかる。
【００５６】
一方、本発明外の試料（比較例１〜４）は、それぞれ問題点を有していることがわかる。裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していても、ポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４未満であるポリエチレン系樹脂組成物を用いた場合（比較例１〜３）には、ポリエチレン系樹脂組成物の成形加工性が悪くて問題である。又、従来の高圧法により製造された低密度ポリエチレン系樹脂を主成分とする樹脂組成物を用いた場合（比較例４）には、冷却ロール汚れの発生が悪くて問題であるし、又基紙と裏樹脂層との接着性が弱い傾向がある。
【００５７】
実施例３〜９及び比較例５〜１０
実施例１で用いた裏樹脂層用のポリエチレン系樹脂組成物の代わりに、表１に記載の樹脂で構成した、表４に記載の配合のポリエチレン系樹脂組成物（実施例３〜９及び比較例５〜１０）を用いる以外は実施例１と同様にして実施した。
【００５８】
得られた結果を表５に表す。
【００５９】
【表４】
【表５】
表５の結果から、ポリエチレン系樹脂組成物からなる裏樹脂層で被覆された画像材料用支持体において、該樹脂組成物がメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有し、かつポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４以上であるポリエチレン系樹脂組成物からなる裏樹脂層で被覆された本発明における画像材料用支持体（実施例３〜９）は、ポリエチレン系樹脂組成物の成形加工性が良好であり、冷却ロール汚れの発生が無くて、かつ基紙と裏樹脂層との接着性が良好である、優れた画像材料用支持体であることがよくわかる。特に、裏樹脂層用のポリエチレン系樹脂組成物中のメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂の含有量としては、冷却ロール汚れ及び基紙と裏樹脂層との接着性の改良効果の点から、裏樹脂層用のポリエチレン系樹脂組成物中の全ポリエチレン系樹脂に対して２５重量％以上が好ましいこと（実施例３〜８と実施例９との比較）がよくわかる。又、裏樹脂層用のポリエチレン系樹脂組成物としては、該組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが、ポリエチレン系樹脂組成物の成形加工性の点から、５. ５以上のものが好ましく、７. ０以上のものが特に好ましいこと（実施例３並びに実施例７〜８と実施例５と実施例４並びに実施例６との比較）がよくわかる。
【００６２】
一方、本発明外の試料（比較例５〜１０）は、それぞれ問題点を有していることがわかる。裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していても、ポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４未満であるポリエチレン系樹脂組成物を用いた場合（比較例５〜９）には、ポリエチレン系樹脂組成物の成形加工性が悪くて問題であるし、又裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していない場合（比較例１０）には、冷却ロール汚れが悪くて問題である。
【００６３】
実施例１０〜１５及び比較例１１〜１６
実施例１で用いた裏樹脂層用のポリエチレン系樹脂組成物の代わりに。表１に記載の樹脂で構成した、表６に記載の配合のポリエチレン系樹脂組成物（実施例１０〜１５及び比較例１１〜１６）を用いる以外は実施例１と同様にして実施した。
【００６４】
得られた結果を表７に表す。
【００６５】
【表６】
【表７】
なお、画像材料用支持体のカ−ル物性の評価方法としては、以下のようにして行った。まず、画像材料用支持体の二酸化チタン顔料を含む表側の樹脂面にコロナ放電処理後黄色発色カプラ−を含む青感乳剤層、色混り防止剤を含む中間層、マゼンタ発色カプラ−を含む緑感乳剤層、紫外線吸収剤を含む紫外線吸収層、シアン発色カプラ−を含む赤感乳剤層及び保護層を設けてゼラチンの総量が８g/m2であるカラ−印画紙を作成した。各色感乳剤層は硝酸銀で０. ６g/m2に相当する塩臭化銀を含み、更にハロゲン化銀の生成、分散及び成膜に必要なゼラチンの他、適量のカブリ防止剤、増感色素、塗布助剤、硬膜剤、増粘剤及び適量のフィルタ−染料等を含む。次に、作成したカラ−印画紙を３５℃、常湿で５日間保存した後、カラ−発色現像後２０℃、５０％ＲＨにおける８. ２cm×１１. ７cmの大きさのカラ−プリントのカ−ルの状態を評価した。評価基準としては、○；カールが少なく、カ−ル物性が良好、△；カ−ルがあるが、実用上問題がない程度、を表す。
【００６８】
表７の結果から、ポリエチレン系樹脂組成物からなる裏樹脂層で被覆された画像材料用支持体において、該樹脂組成物がメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有し、かつポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４以上であるポリエチレン系樹脂組成物からなる裏樹脂層で被覆された本発明における画像材料用支持体（実施例１０〜１５）は、ポリエチレン系樹脂組成物の成形加工性が良好であり、冷却ロール汚れの発生が無くて、かつ基紙と裏樹脂層との接着性が良好である、優れた画像材料用支持体であることがよくわかる。特に、裏樹脂層用のポリエチレン系樹脂組成物中のメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂の含有量としては、冷却ロール汚れ及び基紙と裏樹脂層との接着性の改良効果の点から、裏樹脂層用のポリエチレン系樹脂組成物中の全ポリエチレン系樹脂に対して２５重量％以上が好ましいこと（実施例１０〜１３と実施例１４との比較）がよくわかる。又、裏樹脂層用のポリエチレン系樹脂組成物としては、該組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが、ポリエチレン系樹脂組成物の成形加工性の点から、７. ０以上のものが特に好ましいこと（実施例１０〜１４と実施例１５との比較）がよくわかる。また、裏樹脂層用のポリエチレン系樹脂組成物中の全ポリエチレン系樹脂に対して３０重量％以上の高密度ポリエチレン系樹脂を該組成物中に含有せしめることにより、カール物性が改良されて好ましいこと（実施例１０〜１１並びに実施例１３〜１４と実施例１２並びに実施例１５との比較）がよくわかる。
【００６９】
一方、本発明外の試料（比較例１１〜１６）は、それぞれ問題点を有していることがわかる。裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していても、ポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４未満であるポリエチレン系樹脂組成物を用いた場合（比較例１１及び比較例１５〜１６）には、ポリエチレン系樹脂組成物の成形加工性が悪くて問題であるし、又裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していない場合（比較例１２〜１４）には、冷却ロール汚れが悪くて問題であるし、基紙と裏樹脂層との接着性が弱い傾向がある。
【００７０】
実施例１６〜１９及び比較例１７〜１９
実施例１で用いた裏樹脂層用のポリエチレン系樹脂組成物の代わりに、表１に記載の樹脂で構成した、表８に記載の配合のポリエチレン系樹脂組成物（実施例１６〜１９及び比較例１７〜１９）を用いる以外は実施例１と同様に実施した。
【００７１】
得られた結果を表９に表す。
【００７２】
【表８】
【表９】
表９の結果から、ポリエチレン系樹脂組成物からなる裏樹脂層で被覆された画像材料用支持体において、該樹脂組成物がメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有し、かつポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４以上であるポリエチレン系樹脂組成物からなる裏樹脂層で被覆された本発明における画像材料用支持体（実施例１６〜１９）は、ポリエチレン系樹脂組成物の成形加工性が良好であり、冷却ロール汚れの発生が無くて、かつ基紙と裏樹脂層との接着性が良好である、優れた画像材料用支持体であることがよくわかる。又、裏樹脂層用のポリエチレン系樹脂組成物としては、該組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが、ポリエチレン系樹脂組成物の成形加工性の点から、５. ５以上のものが好ましく、７. ０以上のものが特に好ましいこと（実施例１７〜１８と実施例１６と実施例１９との比較）がよくわかる。
【００７５】
一方、本発明外の試料（比較例１７〜１９）は、それぞれ問題点を有していることがわかる。裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していても、ポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４未満であるポリエチレン系樹脂組成物を用いた場合（比較例１８〜１９）には、ポリエチレン系樹脂組成物の成形加工性が悪くて問題であるし、又裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していない場合（比較例１７）には、冷却ロール汚れが悪くて問題であるし、基紙と裏樹脂層との接着性が弱い傾向がある。
【００７６】
実施例２０〜３３及び比較例２０〜２３
実施例１で用いた裏樹脂層用のポリエチレン系樹脂組成物の代わりに、表１０に記載の樹脂で構成した、表１１に記載の配合のポリエチレン系樹脂組成物（実施例２０〜３３及び比較例２０〜２３）を用いる以外は実施例１と同様に実施した。なお、カール物性の評価は、実施例１０と同様にして行った。
【００７７】
得られた結果を表１２に表す。
【００７８】
【表１０】
【表１１】
【表１２】
表１２の結果から、ポリエチレン系樹脂組成物からなる裏樹脂層で被覆された画像材料用支持体において、該樹脂組成物がメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有し、かつポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４以上であるポリエチレン系樹脂組成物からなる裏樹脂層で被覆された本発明における画像材料用支持体（実施例２０〜３３）は、ポリエチレン系樹脂組成物の成形加工性が良好であり、冷却ロール汚れの発生が無くて、かつ基紙と裏樹脂層との接着性が良好である、優れた画像材料用支持体であることがよくわかる。特に、裏樹脂層用のポリエチレン系樹脂組成物としては、該組成物中のポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが、ポリエチレン系樹脂組成物の成形加工性の点から、５. ５以上のものが好ましく、７. ０以上のものが特に好ましいこと（実施例２９〜３３と実施例２０並びに実施例２３〜２７と実施例２１〜２２並びに実施例２８との比較）がよくわかる。また、裏樹脂層用のポリエチレン系樹脂組成物中の全ポリエチレン系樹脂に対して３０重量％以上の高密度ポリエチレン系樹脂を該組成物中に含有せしめることにより、カール物性が改良されて好ましいこと（実施例２３〜２７並びに実施例２９〜３３と実施例２０〜２２並びに実施例２８との比較）がよくわかる。
【００８２】
一方、本発明外の試料（比較例２０〜２３）は、それぞれ問題点を有していることがわかる。裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していても、ポリエチレン系樹脂成分のトータルとしてのＭｗ／Ｍｎが４未満であるポリエチレン系樹脂組成物を用いた場合（比較例２０〜２１）には、ポリエチレン系樹脂組成物の成形加工性が悪くて問題であるし、又裏樹脂層用の樹脂組成物中にメタロセン重合触媒を用いて重合製造したポリエチレン系樹脂を含有していない場合（比較例２２〜２３）には、冷却ロール汚れが悪くて問題であるし、基紙と裏樹脂層との接着性が弱い傾向があったり、悪くなったりして問題である。
【００８３】
【発明の効果】
本発明により、生産中に冷却ロール汚れの発生が少なく、それ故に冷却ロール汚れの転写に起因する問題の発生が無く、かつ裏樹脂層と基紙との接着性が良好であり、更に高速かつ安定生産できる、紙を基質とする優れた樹脂被覆紙型画像材料用支持体を提供できる。[0001]
[Industrial application fields]
The present invention relates to a support for a resin-coated paper type image material in which both sides of a paper substrate (hereinafter sometimes referred to as a base paper) are coated with a resin layer, and more specifically, the side opposite to the side on which an image forming layer is provided. The present invention relates to a support for a resin-coated paper-type image material, which has good adhesion between the resin layer and the base paper and does not cause problems due to dirt on the cooling roll and can be stably produced at high speed.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a resin-coated paper type support in which a base paper surface for a support for image materials is coated with a resin capable of forming a film is well known. For example, Japanese Patent Publication No. 55-12584 discloses a technique relating to a photographic support in which the base paper is coated with a film-forming resin, preferably a polyolefin resin. U.S. Pat. No. 3,501,298 discloses a technique for a photographic support in which both surfaces of a base paper are coated with a polyolefin resin. In addition, since the rapid photographic development processing method for silver halide photosensitive materials has been applied, photographic supports in which both sides of the base paper are coated with a polyethylene resin have been mainly put into practical use for photographic printing paper, If necessary, the image forming resin layer usually contains a titanium dioxide pigment in order to impart sharpness.
[0003]
US Pat. No. 4,774,224 discloses a resin-coated paper having a resin-coated surface roughness of 7.5 microinches-AA or less, particularly a polyethylene resin-coated paper in which the surface of the base paper is coated with a polyethylene resin. A thermal transfer recording image receiving element has been proposed. Japanese Patent Application Laid-Open No. 63-307979 discloses a technique relating to an ink jet recording sheet having a resin-coated paper as a support.
[0004]
Further, a technique relating to a photographic support in which the surface of the base paper opposite to the side on which the photographic layer is provided is coated with a resin composition containing a low density polyethylene resin and a high density polyethylene resin has been proposed. For example, Japanese Patent Publication No. 44-22904 discloses a density of 0.915 to 0.926 g / cm. Three A specific low density polyethylene resin having a melting index of 2.9 to 16 g / 10 min and a density of 0.960 to 0.975 g / cm. Three And
The base paper was coated with a polyethylene composition having a high-speed coating capability and a good neck-in and pinhole composition comprising 85 to 35% by weight of a specific high-density polyethylene resin having a melt index of 5 to 18 g / 10 min. There is a disclosure of a photographic support. Japanese Patent Publication No. 48-9963 discloses a photographic support having good curl properties, in which a base paper is coated with a resin composition comprising low density polyethylene resin: high density polyethylene resin = 1: 1. There is disclosure. Further, JP-A-58-95732 discloses a density of 0.945 g / cm. Three The density is 0.930 g / cm with 40 to 75 parts by weight of high density polyethylene resin having a melt index of 15 to 40 g / 10 min. Three For photographic materials having good cutting properties and curl properties, wherein the base paper is coated with a polyethylene resin composition comprising 60 to 25 parts by weight of a low density polyethylene resin having a melt index of 1 to 40 g / 10 min. There is disclosure about the support.
[0005]
However, a resin composition that covers the base paper surface opposite to the side on which the image forming layer is provided (hereinafter, the base paper surface on the side on which the image forming layer is provided may be abbreviated as the front surface, and the base paper surface on the opposite side may be abbreviated as the back surface). As described above, even when the resin composition comprising the polyethylene resin disclosed in these prior arts is used, a serious problem occurs when producing a support for resin-coated paper-type image material using paper as a substrate. It has been found. Further, the support for resin-coated paper type image material still has a serious problem in quality.
[0006]
That is, first, the polyethylene-based resin-coated paper is obtained by extruding a molten polyethylene-based resin composition from its slit die into a film on a base paper that normally travels, and casting and coating it. It is produced in a series of processes in which it is pressure-bonded between a pressure roll and a cooling roll and peeled off from the roll after cooling. However, when a resin composition made of a conventionally known polyethylene resin is used as the resin composition for coating the back surface of the base paper, the polyethylene resin composition referred to as cooling roll dirt on the cooling roll or its modification There was a tendency for stains consisting mainly of objects to occur. Production of polyethylene-based resin-coated paper is carried out by operating the melt extruder for at least 2-3 days from the start of operation, usually for a week, sometimes for a month, but the continuous operation period can be extended. The worse the cleaning, the more chill roll dirt tended to accumulate.
[0007]
During the production of polyethylene resin-coated paper, if a lot of cooling roll dirt begins to occur, the peelability of the polyethylene resin-coated paper from the cooling roll deteriorates, and the adhesiveness between the cooling roll and the resin layer increases and cooling Since the tendency of the resin layer to be removed on the roll side increases, the adhesion between the base paper and the resin layer becomes unevenly weak, or in severe cases, the base paper and the resin layer may peel off and support for image materials As a resin-coated paper for body use, there is a problem that it is completely inappropriate and has no commercial value. Further, the accumulated cooling roll dirt is wound up while adhering to the resin layer, and the resin layer on the side on which the image forming layer is provided (hereinafter, the side on which the image forming layer is provided is the front side, and the resin layer coated on the front side is the surface resin. Layer, the opposite side is the back side, and the resin layer coated on the back side may be abbreviated as the back resin layer), which is the resin-coated paper for use as a support for imaging materials There was a problem of causing a fatal quality failure. Furthermore, this transfer problem of the cooling roll stain causes a serious problem that the stain is once transferred to a laminator roll or an emulsion coater roll for producing a resin-coated paper, which is retransferred to cause a quality failure. There was also. For this reason, it is necessary to take sufficient measures to prevent the cooling roll from being soiled.
[0008]
In addition, although image materials having less curling and flat materials are preferable, image materials having resin-coated paper as a support have a strong tendency to curl to the image forming layer side containing a binder, particularly in multilayer silver halide color photographic printing paper. There is a strong tendency to curl to the side of the multilayer color photographic composition layer containing gelatin, and in particular, the tendency of curling has become apparent in color photographic prints after development processing. For this reason, a resin composition comprising a low density polyethylene resin and a high density polyethylene resin is often used as the resin composition for the back resin layer of the support for resin-coated paper-type image material. However, as a result of the study by the present inventors, when a conventionally known polyethylene resin composition comprising a low-density polyethylene resin and a high-density polyethylene resin is used as the resin composition for coating the back surface of the base paper, their synergistic effect is obtained. As a result, it was found that the contamination of the cooling rolls was remarkably manifested, and the improvement of the curl properties was extremely limited.
[0009]
Secondly, when a resin composition made of a conventionally known polyethylene resin is used as the resin composition for coating the back surface of the base paper, the base paper and the back resin layer of the support for resin-coated paper-type image materials are used. There was a tendency that the adhesiveness of was insufficient. A support for resin-coated paper-type image material with insufficient adhesion between the base paper and the back resin layer is critical because the back resin layer peels off during the production of the image material having the support or during processing for image formation. There was a problem of causing a quality failure. In particular, in the case of a silver halide photographic material, if the back resin layer is peeled off, the developing solution penetrates into the base paper and causes color contamination during the developing process, and it is said that there is no quality value at all. There was a problem. This problem of adhesion between the base paper and the back resin layer becomes more apparent at a speed of 150 m / min or more as the running speed of the base paper increases during the production of the support for resin-coated paper type image material. The thinner the resin layer coverage, the more specifically 32g / m 2 It became apparent below.
[0010]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to reduce the occurrence of cooling roll stains during production, and hence no problems due to transfer of roll stains, and the resin layer and base on the side opposite to the side on which the image forming layer is provided. An object of the present invention is to provide a support for resin-coated paper-type image material using paper as a substrate, which has good adhesiveness to paper and can be stably produced at high speed. Other objects of the present invention will become clear from the description of the following specification.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a paper as a substrate and a paper substrate surface opposite to the side on which one of the image forming layers is provided is a resin composition containing a polyethylene resin as a main component. In a support for image materials coated with a resin layer comprising a product, the resin composition contains a polyethylene resin produced by polymerization using a metallocene polymerization catalyst, and the total of the polyethylene resin components in the resin composition Mw / Mn (where Mw: weight average molecular weight, Mn: number average molecular weight) is 4 or more, the object of the present invention is achieved by a support for imaging materials, characterized in that I found it.
[0012]
Specifically, Mw / Mn referred to in the present invention is determined as follows. Gel permeation chromatography using 150-C manufactured by Waters (column: GMH-XL HT manufactured by Tosoh Corporation 8 mmφ × 3 cm × 3, solvent: 1, 2, 4-trichlorobenzene, temperature: 135 ° C., flow rate 10 ml / min) Mw and Mn as a total of the polyethylene resin component in the resin composition containing polyethylene resin as a main component were measured by a graphic (GPC) method, and Mw / Mn was calculated.
[0013]
An object of the present invention is to use a resin composition having a total Mw / Mn of 5.5 or more, particularly 7.0 or more as a total of polyethylene resin components in a resin composition containing a polyethylene resin as a main component, I found that it was achieved significantly. Another object of the present invention is to provide a polyethylene resin produced by polymerization using a metallocene polymerization catalyst in a resin composition containing a polyethylene resin as a main component (hereinafter sometimes simply referred to as a polyethylene resin composition). It was found that the content was significantly achieved by setting the content to 25% by weight or more based on the total polyethylene resin.
[0014]
Examples of the polyethylene resin polymerized and produced using the metallocene polymerization catalyst used in the practice of the present invention include Japanese Patent Publication No. 3-502710, Japanese Patent Laid-Open No. 60-3506, Japanese Patent Publication No. 63-501369, A polymerization catalyst comprising a combination of a zirconium-based, titanium-based or hafnium-based metallocene and preferably an aluminoxane such as methylaluminoxane as described or disclosed in Kaihei 3-234717, JP-A-3-234718, etc. Used as a polymerization product. As those things , D Examples thereof include copolymers of ethylene and α-olefins such as propylene, butene-1, hexene-1 and octene-1, and polyethylene resins such as carboxy-modified polyethylene resins. As these, those having various densities, melt flow rates (hereinafter simply referred to as MFR), molecular weight, and molecular weight distribution can be used, but usually the density is 0.85 to 0.97 g / cm. 3 In the range of 0.05 to 500 g / 10 min, preferably 0.08 to 300 g / 10 min, can be used alone or in admixture of two or more.
[0015]
The polyethylene resin composition used in the practice of the present invention contains a polyethylene resin polymerized and produced using a metallocene polymerization catalyst. From the viewpoint of further improving performance such as adhesion to the resin layer and curling properties of the photographic paper, it was produced by polymerization using a polyethylene polymerization resin having a long chain branch produced by a high-pressure method and a metal polymerization catalyst other than metallocene. It is useful to include a polyethylene resin or the like. The molding processability of the polyethylene-based resin composition referred to in the present specification refers to the degree of neck-in, the degree of generation of streaks in the molten resin film, the presence or absence of film breakage due to the degree of drawdown, surging or draw resonance. Comprehensive processability such as flow instability.
[0016]
The polyethylene resin composition used in the practice of the present invention has a total Mw / Mn of 4 or more of the polyethylene resin components in the composition, but the molding processability of the resin resin composition To Mw / Mn of 5.5 or more is preferable, and 7.0 or more is particularly preferable.
[0017]
In addition, the content of the polyethylene resin produced by polymerization using the metallocene polymerization catalyst in the polyethylene resin composition used in the practice of the present invention includes the effect of improving the cooling roll stain and the adhesion between the back resin layer and the base paper. From the viewpoint of improving the properties, and further from the viewpoint of the moldability of the resin composition, it is preferably 25% or more based on the total polyethylene resin in the resin composition.
[0018]
A polyethylene-based resin having a long-chain branch produced by a high-pressure method that is advantageously used in combination with a polyethylene-based resin produced by polymerization using a metallocene polymerization catalyst in the polyethylene-based resin composition used in the practice of the present invention. Examples of the resin include various polyethylene-based resins having long chain branching by high-pressure radical polymerization using, for example, 1000 to 3500 atm using an autoclave reactor, a tubular reactor, or the like. Examples of polyethylene resins having long-chain molecules produced by these high-pressure methods include ethylene homopolymers, copolymers of ethylene and propylene, butene-1, etc., and carboxy-modified polyethylene resins. A polyethylene-type resin can be illustrated. As these, those having various densities, MFR, molecular weight, and molecular weight distribution can be used, but usually the density is from 0.85 to 0.95 g / cm. Three In the range of 0.1 to 50 g / 10 min, preferably MFR in the range of 0.4 to 50 g / 10 min, can be used alone or in admixture of two or more. The carboxy-modified polyethylene resin referred to in the present specification is an unsaturated group such as ethylene and α, β-unsaturated carboxylic acid such as maleic acid, acrylic acid or methacrylic acid or alicyclic carboxylic acid having an unsaturated bond in the ring. This refers to resins modified by grafting these unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides, amides, esters, etc. onto carboxylic acid or unsaturated carboxylic acid anhydrides, amides, esters, etc. copolymers or polyethylene. .
[0019]
Polymerized and produced using a metal polymerization catalyst other than the metallocene polymerization catalyst, which is advantageously used in combination with a polyethylene resin produced by polymerization using a metallocene polymerization catalyst in the polyethylene resin composition used in the practice of the present invention. Examples of the polyethylene resin include various polyethylene resins produced by polymerization using a Ziegler method, a Philips method, or the like. Polyethylene resins produced by polymerization using metal polymerization catalysts other than those metallocene polymerization catalysts include low density polyethylene resins, medium density polyethylene resins, high density polyethylene resins, linear low density polyethylene resins, ethylene and propylene, butylene. A copolymer with an α-olefin such as carboxy-modified polyethylene resin, and a mixture thereof, and those having various densities, MFR, molecular weight, and molecular weight distribution can be used. Usually, the density is 0.85-0. 97g / cm Three In the range of 0.05 to 500 g / 10 min, preferably 0.08 to 300 g / 10 min, can be used alone or in admixture of two or more.
[0020]
Moreover, the back resin layer can also have a multilayer structure. When the back resin layer has a multi-layer structure, a resin composition having another property or structure such as that used in the present invention as the outermost resin composition or a conventionally known resin composition as the lower resin composition can be used. .
[0021]
In the present invention, the surface on which the image forming layer of the base paper of the image material support is provided is coated with a film-forming resin. As these resins capable of forming a film, thermoplastic resins such as polyolefin resins, polycarbonate resins, polyester resins, and polyamide resins are preferable. Among them, polyolefin resins are more preferable from the viewpoint of melt extrusion coating properties, and polyethylene resins are particularly preferable. Further, it may be coated with an electron beam curable resin described or exemplified in JP-B-60-17104.
[0022]
The coating thickness of the resin layer on the back side of the image material support in the present invention is useful in the range of 4 to 100 μm, preferably in the range of 6 to 50 μm, and particularly preferably in the range of 9 to 35 μm. The surface of the base paper is coated with a resin capable of forming a film, but the resin is preferably a polyethylene resin, and the coating thickness is preferably set as appropriate within the range of curling balance with the resin on the back side. In general, the range of 4 to 100 μm is useful, but the range of 6 to 50 μm is preferable.
[0023]
As a method for coating the polyethylene resin composition on the base paper surface of the image material support in the present invention, the resin composition is cast on the traveling base paper from the slit die into a film shape using a melt extruder. It is preferable to coat by a so-called melt extrusion coating method. In that case, it is preferable that the temperature of a molten film is 280-340 degreeC. As the slit die, a flat die such as a T die, an L die, or a fishtail die is preferable, and the slit opening diameter is preferably 0.1 to 2 mm. Moreover, it is preferable to subject the base paper to activation treatment such as corona discharge treatment and flame treatment before coating the resin composition on the base paper. Further, as described in JP-B-61-42254, a resin layer may be coated on the base paper that travels after the ozone-containing gas is sprayed on the molten resin composition on the side in contact with the base paper. When both surfaces of the base paper are coated with a resin layer, the front and back resin layers are extrusion coated sequentially, preferably continuously, so that the base paper is coated by a so-called tandem extrusion coating method. Preferably, the resin layer may be coated by a multilayer extrusion coating method in which the resin layer has a multilayer structure as necessary. Further, the surface resin layer side of the image material support on which the image forming layer is to be coated is processed into a glossy surface, a fine rough surface described in JP-B-62-19732, a matte surface, or a silky surface. It is preferable that the opposite side of the back resin layer is usually processed into a matte surface.
[0024]
Various additives can be contained in the front resin layer of the support for image material in the present invention and, if necessary, in the back resin layer. Japanese Patent Publication No. 60-3430, Japanese Patent Publication No. 63-11655, Japanese Patent Publication No. 1-38291, Japanese Patent Publication No. 1-38292, Japanese Patent Application Laid-Open No. 1-105245, etc. White pigments such as zinc, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, calcium palmitate Fatty acid metal salts, hindered phenols, hindered amines, phosphorus-based, sulfur-based and other various antioxidants described or exemplified in JP-A-1-105245, blue-based compounds such as cobalt blue, ultramarine blue, ceria blue, and phthalocyanine blue Pigments and dyes, cobalt violet, fast violet, manganese violet The magenta pigments and dyes, fluorescent whitening agents described or exemplified in JP-A-2-254440, various additives as appropriate combination can be incorporated such as an ultraviolet absorber. These additives are preferably contained as a resin masterbatch or compound.
[0025]
The base paper used in the practice of the present invention is preferably natural pulp paper mainly composed of normal natural pulp. Moreover, the mixed paper which consists of a natural pulp, a synthetic pulp, and a synthetic fiber may be sufficient. These natural pulps are described or exemplified in JP-A-58-37642, JP-A-60-67940, JP-A-60-69649, JP-A-61-35442, etc. It is advantageous to use such appropriately selected natural pulp. Natural pulp was subjected to normal bleaching treatment of chlorine, hypochlorite, chlorine dioxide bleaching and alkali extraction or alkali treatment, and if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and combinations thereof Wood pulp of softwood pulp, hardwood pulp, softwood hardwood mixed pulp is advantageously used, and various kinds such as kraft pulp, sulfite pulp and soda pulp can be used.
[0026]
Various additives can be incorporated into the base paper mainly composed of natural pulp, which is preferably used in the practice of the present invention, at the time of preparing the paper slurry. As sizing agent, fatty acid metal salt or fatty acid, alkyl ketene dimer emulsion described or exemplified in JP-B-62-7534, epoxidized higher fatty acid amide, alkenyl or alkyl succinic anhydride emulsion, rosin derivative, etc., dry paper As force enhancer, anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc., as wet paper strength enhancer, polyamine polyamide epichlorohydrin resin, etc., as filler, clay, kaolin, Calcium carbonate, titanium oxide, etc., fixing agent, water-soluble aluminum salts such as aluminum chloride, vanadium sulfate, etc., pH regulator, caustic soda, soda carbonate, sulfuric acid, etc. Other JP-A 63-204251 No. 1, JP-A 1-266537, etc. Pigments, coloring dyes, that allowed to contain appropriately combining a fluorescent whitening agent is advantageous.
[0027]
In addition, a composition composed of various water-soluble polymers or hydrophilic colloids or latexes, antistatic agents, and additives is sized in or on a base paper mainly composed of natural pulp preferably used in the practice of the present invention. It can be contained or coated by press, tab size press, blade coating, air knife coating or the like. As water-soluble polymers or hydrophilic colloids, starch-based polymers, polyvinyl alcohol-based polymers, gelatin-based polymers, polyacrylamide-based polymers, cellulose-based polymers, etc. described or exemplified in JP-A No. 1-266537, as emulsions and latexes, Petroleum resin emulsion, emulsion or latex of copolymer comprising at least ethylene and acrylic acid (or methacrylic acid) as described or exemplified in JP-A-55-4027 and JP-A-1-80538, styrene -Emulsion or latex of butadiene-based, styrene-acrylic-based, vinyl acetate-acrylic-based, ethylene-vinyl acetate-based, butadiene-methyl methacrylate-based copolymers and their carboxy-modified copolymers, and sodium chloride as an antistatic agent Alkali metal salts such as potassium chloride, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, organic antistatic agents such as polystyrene sulfonate, etc., pigments such as clay and kaolin , Calcium carbonate, talc, barium sulfate, titanium oxide, etc., as a pH regulator, hydrochloric acid, phosphoric acid, citric acid, caustic soda, etc., and other appropriate additives such as the above-mentioned coloring pigments, coloring dyes, fluorescent whitening agents, etc. The inclusion is advantageous.
[0028]
Although there is no restriction | limiting in particular regarding the thickness of the base paper used for implementation of this invention, The basic weight is 20-200 g / m. 2 Are preferred.
[0029]
In addition, as the base paper used in the practice of the present invention, the paper thickness non-uniformity index Rpy defined below is preferably 250 mV or less, more preferably 200 mV or less, and 150 mV or less. Most preferred. The film thickness nonuniformity index Rpy referred to here is an electronic micrometer using a film thickness measuring instrument that moves a sample between two spherical styluses and measures the thickness variation of the sample as an electrical signal via the electronic micrometer. Under the condition that the sensitivity range is ± 15μm / ± 3V, the thickness variation in the papermaking direction of the sample is measured by scanning at a constant speed of 1.5m / min in the papermaking direction of the sample after zero adjustment. The signal value is subjected to fast Fourier transform using a Hanning window as a time window using an FFT analyzer, and a power spectrum (unit: mV) obtained by adding and averaging 128 times. 2 ), And the value obtained by summing the power values in the frequency range of 2 to 25 Hz and multiplying by 2/3 (1/2).
[0030]
As a method for producing a base paper having a film thickness nonuniformity index Rpy of 250 mV or less, which is preferably used in the practice of the present invention, specifically, hardwood pulp which is easy to be smooth with short fibers is 30% by weight or more, preferably 50% by weight. % Or more, and beaten with a beater so that the amount of long fibers is as small as possible. For example, it is preferable to beat the pulp so that the weighted average fiber length of the pulp after beating is 0.4 to 0.75 mm. Next, the paper slurry to which the internally added chemicals are added is appropriate as described or exemplified in JP-A-58-37642, JP-A-61-260240, JP-A-61-284762, etc. Paper making method so that a uniform texture can be obtained with a conventional paper machine such as a long paper machine or a round paper machine, and further using a machine calendar, super calendar, thermal calendar, etc. By applying a calendar process, a base paper having a film thickness nonuniformity index Rpy of 250 mV or less can be produced.
[0031]
The surface resin layer surface of the image material support in the present invention is subjected to activation treatment such as corona discharge treatment and flame treatment, and then disclosed in JP-A-61-84643 and JP-A-1-92740. An undercoat layer as described or exemplified in Kaihei 1-102551, JP-A-1-66035, etc. can be applied. In addition, on the back resin layer surface of the image material support in the present invention, after activation treatment such as corona discharge treatment and flame treatment, various back coat layers are coated for antistatic purposes. be able to. In addition, the back coat layer includes JP-B-52-18020, JP-B-57-9059, JP-B-57-53940, JP-B-58-56859, JP-A-59-214849, Inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants, and the like described or exemplified in JP-A No. 58-184144 can be contained in appropriate combinations.
[0032]
The support for image material in the present invention is coated with various photographic composition layers, for color photographic paper, for black and white photographic paper, for phototypesetting paper, for copy photographic paper, for reversal photographic material, silver salt It can be used for various applications such as diffusion transfer method negative, positive and printing materials. For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion layer can be provided. Multilayer silver halide color photographic constituent layers can be provided by incorporating color couplers in the silver halide photographic emulsion layers. Further, a photographic constituent layer for silver salt diffusion transfer method can be provided. As binders for these photographic constituent layers, hydrophilic polymer substances such as polyvinylpyrrolidone, polyvinyl alcohol, and polysaccharide sulfate compounds can be used in addition to ordinary gelatin. The photographic composition layer can contain various additives. Examples include sensitizing dyes such as cyanine dyes and merocyanine dyes, chemical sensitizers such as water-soluble gold compounds and sulfur compounds, antifoggants or stabilizers such as hydroxy-triazolopyrimidine compounds and mercapto-heterocyclic compounds. Formalin, vinyl sulphone compounds, aziridine compounds as hardening agents, alkylbenzene sulphonate and sulfosuccinic acid ester salts as coating aids, dialkyl hydroquinone compounds as antifouling agents, other fluorescent whitening agents, improved sharpness A dye, an antistatic agent, a pH adjusting agent, a fogging agent, and a water-soluble iridium, a water-soluble rhodium compound, and the like can be contained in appropriate combinations during the formation and dispersion of silver halide.
[0033]
The photographic material according to the present invention can be exposed, developed, stopped, fixed, as described in “Photosensitive materials and handling methods” (Kyoritsu Shuppan, written by Goro Miyamoto, Photographic Technology Course 2) according to the photographic material. Processing such as bleaching and stabilization can be performed. The multilayer silver halide color photographic material may be processed with a developer containing a development accelerator such as benzyl alcohol, thallium salt or phenidone, or may be processed with a developer substantially free of benzyl alcohol. it can.
[0034]
The support for image material in the present invention can be used as a support for various thermal transfer recording image receiving materials by coating various thermal transfer recording image receiving layers. Synthetic resins used in those thermal transfer recording image receiving layers include polyester resins, polyacrylate resins, polycarbonate resins, polyvinyl acetate resins, polyvinyl butyral resins, styrene acrylate resins, vinyl toluene acrylate resins, and other resins having ester bonds. Resin having urethane bond such as polyurethane resin, resin having amide bond such as polyamide resin, resin having urea bond such as urea resin, other polycaprolactam resin, styrene resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate Examples include copolymer resins and polyacrylonitrile resins. In addition to these resins, mixtures or copolymers thereof can also be used.
[0035]
In the thermal transfer recording image-receiving layer according to the present invention, a release agent, a pigment or the like may be added in addition to the above synthetic resin. Examples of the mold release agent include solid waxes such as polyethylene wax, amide wax, and Teflon powder, fluorine-based surfactants, phosphate ester-based surfactants, and silicone oils. Of these release agents, silicone oil is most preferred. As the silicone oil, an oily material can be used, but a curable type is preferable. Examples of the curable silicone oil include a reactive curable type, a photo curable type, and a catalyst curable type, and a reactive curable type silicone oil is particularly preferable. Examples of the reaction curable silicone oil include amino-modified silicone oil and epoxy-modified silicone oil. The amount of the reactive silicone oil added is preferably 0.1 to 20 wt% in the image receiving layer. As the pigment, extender pigments such as silica, calcium carbonate, titanium oxide, and zinc oxide are preferable. Further, the thickness of the image receiving layer is preferably 0.5 to 20 μm, and more preferably 2 to 10 μm.
[0036]
The support for image material in the present invention can be used as a support for various ink jet recording materials by coating various ink receiving layers. These ink-receiving layers can contain various binders for the purpose of improving the drying property of the ink, the sharpness of the image, and the like. Specific examples of such binders include various types of gelatin such as lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives such as gelatin reacted with dibasic acid anhydrides such as phthalic acid, maleic acid, and fumaric acid. Ordinary polyvinyl alcohols of various saponification degrees, carboxy-modified, cation-modified and amphoteric polyvinyl alcohol and derivatives thereof, starches such as oxidized starch, cationized starch, etherified starch, carboxymethyl cellulose, hydroxyethyl cellulose, etc. Cellulose derivatives, polyvinylpyrrolidone, polyvinylpyridium halide, polyacrylic acid soda, acrylic acid / methacrylic acid copolymer salt, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether / maleic anhydride Polymers, styrene / maleic anhydride copolymers and their salts, synthetic polymers such as polyethyleneimine, conjugated diene copolymer latexes such as styrene / butadiene copolymers and methyl methacrylate / butadiene copolymers, polyvinyl acetate , Vinyl acetate / maleic acid ester copolymer, vinyl acetate / acrylic acid ester copolymer, vinyl acetate polymer latex such as ethylene / vinyl acetate copolymer, acrylic acid ester polymer, methacrylic acid ester polymer, ethylene・ Acrylic ester copolymers, acrylic polymers such as styrene / acrylic ester copolymers or latex of copolymers, vinylidene chloride copolymer latex, etc., or functionalities such as carboxyl groups of these various polymers Functional group-modified polymer latex and group Water-based adhesives such as thermosetting synthetic resins such as vinyl resins and urea resins, and synthetic resin adhesives such as polymethyl methacrylate, polyurethane resins, unsaturated polyester resins, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, alkyd resins, etc. In addition, inorganic binders such as alumina sol and silica sol described or exemplified in Japanese Patent Publication No. 3-24906, Japanese Patent Application Laid-Open No. 3-281383, Japanese Patent Application No. 4-40725 can be mentioned, and these can be used alone or in combination. It can be used in combination.
[0037]
The ink receiving layer of the ink jet recording material according to the present invention can contain various additives in addition to the binder. For example, as a surfactant, an anionic surfactant such as a long chain alkylbenzene sulfonate, a long chain, preferably a branched alkylsulfosuccinate, a polyalkylene oxide of a long chain, preferably a branched alkyl group-containing phenol Nonionic surfactants such as ethers and polyalkylene oxide ethers of long-chain alkyl alcohols, fluorinated surfactants described in Japanese Patent Publication No. 47-9303, US Pat. No. 3,589,906, etc. Silane coupling agents such as ethoxysilane and N-β (aminoethyl) γ-aminopropyltrimethoxysilane, polymer hardeners, active halogen compounds, vinyl sulfone compounds, aziridine compounds, epoxy compounds, acryloyl compounds, isocyanate compounds Hardeners such as Examples of the agent include those described in JP-A-1-102551 or exemplified P-hydroxybenzoate compounds, benzisothiazolone compounds, isothiazolone compounds, etc., JP-A 63-204251, JP-A 1-266537, etc. Or, examples of colored pigments, colored dyes, fluorescent whitening agents, hydroxymethane sulfonic acid sodium soda, P-toluene sulfinic acid soda, etc. as yellowing inhibitors, hydroxy-di-alkylphenyl groups in the 2-position as ultraviolet absorbers Benzotriazole compound having an antioxidant, polyhindered phenol compound described or exemplified in JP-A-1-105245, pencil writing agent, organic particles or inorganic particles such as starch granules, barium sulfate, silicon dioxide Fine particles having a diameter of 0.2 to 5 μm, an organopolysiloxane described or exemplified in Japanese Examined Patent Publication No. 4-1337 Various additives such as octyl alcohol, silicon-based antifoaming agent, etc. can be appropriately combined and contained as sodium compounds and pH adjusters, such as caustic soda, sodium carbonate, sulfuric acid, hydrochloric acid, phosphoric acid and citric acid.
[0038]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example.
[0039]
Examples 1-2 and Comparative Examples 1-4
A mixed pulp comprising 50% by weight of hardwood bleached kraft pulp, 35% by weight of hardwood bleached sulfite pulp and 15% by weight of softwood bleached sulfite pulp is beaten so that the fiber length is 0.6 mm, and then 100 parts by weight of pulp. 3 parts by weight of cationized starch, 0.2 part by weight of anionized polyacrylamide, 0.4 part by weight of an alkyl ketene dimer emulsion (as ketene dimer), 0.4 part by weight of polyamide epichlorohydrin resin and an appropriate amount of fluorescent whitening An agent, a blue dye, and a red dye were added to prepare a paper slurry. In addition, about the fiber length of the pulp after beating | pulling, the length weight measured with the Kayani FS-100 type machine based on JAPAN TAPPI paper pulp test method No, 52-89 "paper and pulp fiber length test method" Expressed as average fiber length. Thereafter, a paper web was formed on a long paper machine running the paper stock slurry at 200 m / min while giving an appropriate turbulence, and the linear pressure was adjusted in the range of 15-100 kg / cm 2 in the wet part. After performing a three-stage wet press, it was treated with a smoothing roll, followed by a two-stage tension press in which the linear pressure was adjusted in the range of 30 to 70 kg / cm 2 in the subsequent drying part, and then dried. Then, during drying, a size press solution consisting of 4 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of optical brightener, 0.002 parts by weight of blue dye, 4 parts by weight of sodium chloride and 92 parts by weight of water was 25 g / m 2 Size-pressed, dried so that the final base paper moisture is 8% by weight with absolutely dry moisture, machine calender treatment at a linear pressure of 70 kg / cm, conditions of temperature 150 ° C. and linear pressure 150 kg / cm 2 With a calender treatment and basis weight 170g / m 2 A base paper for an image material support having a film thickness unevenness index Rpy of 140 mV was produced.
[0040]
Next, the base paper surface (back surface) opposite to the side on which the image forming layer is applied is subjected to corona discharge treatment, and the following polyethylene resin composition is applied to the back surface at a resin temperature of 320 ° C. to a resin thickness of 25 μm. Melt extrusion coating was performed at a running speed of the base paper of 200 m / min. At this time, as a cooling roll, a cooling roll roughened by a liquid honing method, in which the roughness is designed so that the center surface average roughness SRa of the back resin layer surface is 1.3 μm, cooling is performed. Operation was at a water temperature of 12 ° C.
[0041]
The polyethylene resin compositions for the back resin layer (Examples 1 and 2 and Comparative Examples 1 to 4) are those shown in Table 2. For resin compositions to be used in combination of two or more, an extruder for kneading Was used as a compound resin composition produced by melting and mixing in advance, cooling and pelletizing. In addition, the polyethylene resin used to constitute the polyethylene resin composition having the formulation shown in Table 2 is that shown in Table 1.
[0042]
[Table 1]
As polyethylene resins (M1 to M17) produced by polymerization using a metallocene polymerization catalyst, an ethylene / Bran-1 copolymer was produced based on the method described in JP-T-3-502710.
[0044]
Polyethylene resins (Z1 to Z12) produced using a polymerization catalyst other than metallocene were produced by the Ziegler method.
[0045]
Polyethylene resins (L1 to L3) were produced by a high pressure method.
[0046]
Subsequently, after the surface of the base paper was subjected to corona discharge treatment, a low density polyethylene resin (density 0.920 g / cm) was applied to the surface. Three , MFR = 8.5 g / 10 min) 47.5% by weight, hydrous aluminum oxide (Al to titanium dioxide) 2 O Three 20 parts by weight of a master batch of titanium dioxide pigment composed of 50% by weight of anatase-type titanium dioxide pigment and 2.5% by weight of zinc stearate surface-treated with 0.75% by weight as a minute, low-density polyethylene resin (density) 0.920 g / cm Three MFR = 4.5 g / 10 min) 65 parts by weight and high density polyethylene resin (density 0.970 g / cm) Three , MFR = 7.0 g / 10 min) A resin composition comprising 15 parts by weight was melt extruded at a resin temperature of 320 ° C. and a resin thickness of 32 μm at a running speed of the base paper of 200 m / min. The melt extrusion coating of the front and back polyethylene resin compositions was performed by a so-called tandem method in which extrusion coating was performed sequentially. At that time, the surface of the resin layer containing the titanium dioxide pigment of the resin-coated paper was processed into a glossy surface.
[0047]
Further, after the corona discharge treatment on the back resin layer surface of the resin-coated paper, the following back coat coating solution was applied on-machine. As dry weight, it was composed of colloidal silica: styrene-based latex = 1: 1, and sodium polystyrene sulfonate 0.021 g / m. 2 The back coat coating solution containing a suitable amount of coating aid, etc. as a latex component (calculated by solid weight) is 0.21 g / m. 2 An image material support was obtained by coating with the coating amount of
[0048]
As described above, the moldability of the polyethylene resin composition for the back resin layer when producing the support for the image material, the degree of occurrence of the cooling roll stain, and the base paper and the back resin layer of the support for the image material As an evaluation method of the adhesiveness, evaluation was performed by the method described below.
[0049]
As a method for evaluating the molding processability of the polyethylene resin composition for the back resin layer at the time of producing the support for the image material, the lateral length of the resin coating portion on the back surface is measured to evaluate the degree of neck-in. At the same time, comprehensive evaluation was made on molding processability such as the degree of streaks of the molten resin film, the presence or absence of film breakage due to the degree of drawdown, and the instability of flow due to surging or draw resonance. As evaluation criteria, ◎: very good, ○: good, Δ: a little bad but no practical problem, x: bad practical problem to some extent.
[0050]
As a method for evaluating the cooling roll stain at the time of melt-extrusion of the polyethylene resin composition for the back resin layer, the state of occurrence of the stain on the cooling roll was visually observed 6 hours after the start of production when the image material was produced under the above production conditions. Judgment was made and evaluated. The evaluation criteria are as follows: ○: Cooling roll dirt is small and good, Δ: Cooling roll dirt is slightly high, but there is no practical problem, ×: Cooling roll dirt is frequently generated, and there is a practical problem Represents to some extent.
[0051]
As a method for evaluating the adhesion between the base paper of the image material support and the back resin layer, each sample was stored in a constant temperature and humidity chamber at 50 ° C. and 60% RH for 1 day, and then the base paper layer and the back surface of the sample. The adhesion between the base paper and the back resin layer was evaluated by measuring the area ratio of the base paper layer attached to the peeled resin layer. The evaluation criteria are as follows: ○: Area ratio is 100%, good, Δ: Area ratio is less than 100%, 80% or more, adhesion is slightly bad but practically no problem, x: Area ratio is 80% This indicates that the adhesiveness is poor and there are some practical problems.
[0052]
The obtained results are shown in Table 3.
[0053]
[Table 2]
[Table 3]
From the results of Table 3, in the support for image material coated with a back resin layer comprising a polyethylene resin composition, the resin composition contains a polyethylene resin produced by polymerization using a metallocene polymerization catalyst, and polyethylene The support for image materials in the present invention (Examples 1 and 2) coated with a back resin layer made of a polyethylene resin composition having a total Mw / Mn of 4 or more as a total of the resin resin components is a polyethylene resin composition It can be clearly seen that this is an excellent support for imaging materials, in which the molding processability of the product is good, the cooling roll is not smeared, and the adhesion between the base paper and the back resin layer is good. In particular, as the polyethylene resin composition for the back resin layer, Mw / Mn as a total of the polyethylene resin components in the composition is 7.0 or more from the viewpoint of moldability of the polyethylene resin composition. It is well understood that the above are preferable (comparison between Example 1 and Example 2).
[0056]
On the other hand, it can be seen that the samples outside of the present invention (Comparative Examples 1 to 4) each have problems. Polyethylene resin composition in which Mw / Mn as a total of polyethylene resin components is less than 4 even if the resin composition for the back resin layer contains a polyethylene resin polymerized using a metallocene polymerization catalyst In the case of using (Comparative Examples 1 to 3), the molding processability of the polyethylene resin composition is poor, which is a problem. In addition, when a resin composition mainly composed of a low-density polyethylene resin produced by a conventional high-pressure method is used (Comparative Example 4), there is a problem in that the cooling roll stain is badly generated. There is a tendency that the adhesion between the paper and the back resin layer is weak.
[0057]
Examples 3-9 and Comparative Examples 5-10
Instead of the polyethylene resin composition for the back resin layer used in Example 1, a polyethylene resin composition having the composition shown in Table 4 and composed of the resin shown in Table 1 (Examples 3 to 9 and comparison) The same procedure as in Example 1 was carried out except that Examples 5 to 10) were used.
[0058]
The obtained results are shown in Table 5.
[0059]
[Table 4]
[Table 5]
From the results of Table 5, in the support for image material coated with a back resin layer comprising a polyethylene resin composition, the resin composition contains a polyethylene resin produced by polymerization using a metallocene polymerization catalyst, and polyethylene The support for image materials in the present invention (Examples 3 to 9) coated with a back resin layer made of a polyethylene resin composition having a total Mw / Mn of 4 or more as a total of the resin resin components is a polyethylene resin composition It can be clearly seen that this is an excellent support for imaging materials in which the molding processability of the product is good, the cooling roll is not smudged, and the adhesion between the base paper and the back resin layer is good. In particular, the content of the polyethylene resin polymerized and produced using the metallocene polymerization catalyst in the polyethylene resin composition for the back resin layer is the effect of improving the cooling roll dirt and the adhesion between the base paper and the back resin layer. From the point, it is well understood that the content is preferably 25% by weight or more based on the total polyethylene resin in the polyethylene resin composition for the back resin layer (comparison between Examples 3 to 8 and Example 9). In addition, as the polyethylene resin composition for the back resin layer, Mw / Mn as a total of the polyethylene resin components in the composition is 5.5 or more from the viewpoint of moldability of the polyethylene resin composition. It is well understood that those of 7.0 or more are particularly preferred (comparison between Example 3 and Examples 7 to 8, Example 5, Example 4 and Example 6).
[0062]
On the other hand, it can be seen that the samples outside of the present invention (Comparative Examples 5 to 10) each have problems. Polyethylene resin composition in which Mw / Mn as a total of polyethylene resin components is less than 4 even if the resin composition for the back resin layer contains a polyethylene resin polymerized using a metallocene polymerization catalyst (Comparative Examples 5 to 9) is a problem due to poor molding processability of the polyethylene resin composition, and polymerization production using a metallocene polymerization catalyst in the resin composition for the back resin layer When it does not contain the polyethylene-based resin (Comparative Example 10), the cooling roll stains are bad, which is a problem.
[0063]
Examples 10-15 and Comparative Examples 11-16
Instead of the polyethylene resin composition for the back resin layer used in Example 1. It implemented similarly to Example 1 except using the polyethylene-type resin composition (Examples 10-15 and Comparative Examples 11-16) of the mixing | blending of Table 6 comprised with resin of Table 1. FIG.
[0064]
Table 7 shows the obtained results.
[0065]
[Table 6]
[Table 7]
In addition, as a method for evaluating the physical properties of the support of the image material support, it was performed as follows. First, a blue-sensitive emulsion layer containing a yellow coloring coupler after corona discharge treatment, a green layer containing a color mixing inhibitor, and a green containing a magenta coloring coupler on the front side resin surface containing the titanium dioxide pigment of the support for the image material. Emulsion-sensitive emulsion layer, UV-absorbing layer containing UV-absorbing agent, red-sensitive emulsion layer containing cyan color coupler and protective layer are provided, and the total amount of gelatin is 8g / m 2 A color photographic paper was produced. Each color-sensitive emulsion layer is 0.6 g / m in silver nitrate. 2 In addition to gelatin necessary for the formation, dispersion and film formation of silver halide, an appropriate amount of antifoggant, sensitizing dye, coating aid, hardener, thickener and Contains appropriate amount of filter-dye and the like. Next, the prepared color photographic paper was stored at 35 ° C. and normal humidity for 5 days, and after color color development, a color print cover having a size of 8.2 cm × 11.7 cm at 20 ° C. and 50% RH was used. -The state of the ru was evaluated. As evaluation criteria, ◯ represents less curl and good curl properties, and Δ represents curl, but there is no practical problem.
[0068]
From the results of Table 7, in the image material support coated with a back resin layer comprising a polyethylene resin composition, the resin composition contains a polyethylene resin polymerized and produced using a metallocene polymerization catalyst, and polyethylene The support for image materials in the present invention (Examples 10 to 15) coated with a back resin layer made of a polyethylene resin composition having a total Mw / Mn of 4 or more as a total of the resin resin components is a polyethylene resin composition It can be clearly seen that this is an excellent support for imaging materials in which the molding processability of the product is good, the cooling roll is not smudged, and the adhesion between the base paper and the back resin layer is good. In particular, the content of the polyethylene resin polymerized and produced using the metallocene polymerization catalyst in the polyethylene resin composition for the back resin layer is the effect of improving the cooling roll dirt and the adhesion between the base paper and the back resin layer. From the point, it is well understood that the content is preferably 25% by weight or more based on the total polyethylene resin in the polyethylene resin composition for the back resin layer (comparison between Examples 10-13 and Example 14). Further, as the polyethylene resin composition for the back resin layer, Mw / Mn as a total of the polyethylene resin components in the composition is 7.0 or more from the viewpoint of the moldability of the polyethylene resin composition. It can be clearly seen that those are particularly preferable (comparison between Examples 10 to 14 and Example 15). In addition, the curl properties are preferably improved by adding 30% by weight or more of high-density polyethylene resin to the total polyethylene resin in the polyethylene resin composition for the back resin layer. (Comparison between Examples 10 to 11 and Examples 13 to 14, Example 12 and Example 15) is well understood.
[0069]
On the other hand, it can be seen that the samples outside of the present invention (Comparative Examples 11 to 16) each have problems. Polyethylene resin composition in which Mw / Mn as a total of polyethylene resin components is less than 4 even if the resin composition for the back resin layer contains a polyethylene resin polymerized using a metallocene polymerization catalyst (Comparative Example 11 and Comparative Examples 15 to 16) is a problem because the moldability of the polyethylene resin composition is poor, and a metallocene polymerization catalyst is added to the resin composition for the back resin layer. When it does not contain the polyethylene-based resin produced by polymerization (Comparative Examples 12 to 14), the cooling roll stain is bad and there is a problem, and the adhesion between the base paper and the back resin layer tends to be weak. .
[0070]
Examples 16-19 and Comparative Examples 17-19
Instead of the polyethylene resin composition for the back resin layer used in Example 1, a polyethylene resin composition having the composition shown in Table 8 and composed of the resin shown in Table 1 (Examples 16 to 19 and comparison) The same procedure as in Example 1 was carried out except that Examples 17 to 19) were used.
[0071]
The obtained results are shown in Table 9.
[0072]
[Table 8]
[Table 9]
From the results of Table 9, in the image material support coated with the back resin layer comprising the polyethylene resin composition, the resin composition contains a polyethylene resin produced by polymerization using a metallocene polymerization catalyst, and polyethylene The support for image materials in the present invention (Examples 16 to 19) coated with a back resin layer composed of a polyethylene resin composition having a total Mw / Mn of 4 or more as a total of the resin resin components is a polyethylene resin composition. It can be clearly seen that this is an excellent support for imaging materials in which the molding processability of the product is good, the cooling roll is not smudged, and the adhesion between the base paper and the back resin layer is good. In addition, as the polyethylene resin composition for the back resin layer, Mw / Mn as a total of the polyethylene resin components in the composition is 5.5 or more from the viewpoint of moldability of the polyethylene resin composition. It is well understood that those of 7.0 or more are particularly preferred (comparison between Examples 17 to 18, Example 16 and Example 19).
[0075]
On the other hand, it can be seen that the samples outside of the present invention (Comparative Examples 17 to 19) have problems. Polyethylene resin composition in which Mw / Mn as a total of polyethylene resin components is less than 4 even if the resin composition for the back resin layer contains a polyethylene resin polymerized using a metallocene polymerization catalyst (Comparative Examples 18 to 19) is a problem due to the poor molding processability of the polyethylene-based resin composition, and polymerization production using a metallocene polymerization catalyst in the resin composition for the back resin layer When the polyethylene resin is not contained (Comparative Example 17), there is a problem that the cooling roll is dirty, and the adhesion between the base paper and the back resin layer tends to be weak.
[0076]
Examples 20-33 and Comparative Examples 20-23
Instead of the polyethylene resin composition for the back resin layer used in Example 1, the polyethylene resin composition having the composition shown in Table 11 and composed of the resin shown in Table 10 (Examples 20 to 33 and comparison) Example 20 was carried out in the same manner as in Example 1 except that 20) was used. The curl properties were evaluated in the same manner as in Example 10.
[0077]
The obtained results are shown in Table 12.
[0078]
[Table 10]
[Table 11]
[Table 12]
From the results of Table 12, in the image material support coated with the back resin layer comprising the polyethylene resin composition, the resin composition contains a polyethylene resin polymerized and produced using a metallocene polymerization catalyst, and polyethylene. The support for image materials in the present invention (Examples 20 to 33) coated with a back resin layer comprising a polyethylene resin composition having a total Mw / Mn of 4 or more as the total of the resin resin components is a polyethylene resin composition It can be clearly seen that this is an excellent support for imaging materials in which the molding processability of the product is good, the cooling roll is not smudged, and the adhesion between the base paper and the back resin layer is good. In particular, as the polyethylene resin composition for the back resin layer, Mw / Mn as a total of the polyethylene resin components in the composition is 5.5 or more from the viewpoint of moldability of the polyethylene resin composition. It is well understood that those of 7.0 or more are particularly preferred (comparison between Examples 29 to 33 and Example 20, and Examples 23 to 27, Examples 21 to 22, and Example 28). In addition, the curl properties are preferably improved by adding 30% by weight or more of high-density polyethylene resin to the total polyethylene resin in the polyethylene resin composition for the back resin layer. (Comparison between Examples 23 to 27 and Examples 29 to 33 and Examples 20 to 22 and Example 28) is well understood.
[0082]
On the other hand, it can be seen that the samples outside of the present invention (Comparative Examples 20 to 23) each have problems. Polyethylene resin composition in which Mw / Mn as a total of polyethylene resin components is less than 4 even if the resin composition for the back resin layer contains a polyethylene resin polymerized using a metallocene polymerization catalyst (Comparative Examples 20 to 21) is a problem due to poor molding processability of the polyethylene resin composition, and polymerization production using a metallocene polymerization catalyst in the resin composition for the back resin layer In the case where the polyethylene resin is not contained (Comparative Examples 22 to 23), there is a problem that the cooling roll dirt is bad and the adhesion between the base paper and the back resin layer tends to be weak or worse. It is a problem.
[0083]
【The invention's effect】
According to the present invention, there is little occurrence of cooling roll stains during production, and therefore there is no occurrence of problems due to transfer of cooling roll stains, and the adhesiveness between the back resin layer and the base paper is good, and the speed is high. An excellent support for resin-coated paper-type imaging material using paper as a substrate, which can be stably produced, can be provided.
Claims (6)
Priority Applications (1)
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| JP02802895A JP3707819B2 (en) | 1995-02-16 | 1995-02-16 | Support for imaging materials |
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| JP02802895A JP3707819B2 (en) | 1995-02-16 | 1995-02-16 | Support for imaging materials |
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| JPH08220690A JPH08220690A (en) | 1996-08-30 |
| JP3707819B2 true JP3707819B2 (en) | 2005-10-19 |
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| JP02802895A Expired - Fee Related JP3707819B2 (en) | 1995-02-16 | 1995-02-16 | Support for imaging materials |
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|---|---|---|---|---|
| DE69217075T2 (en) * | 1991-04-05 | 1997-05-15 | Eastman Chem Co | METHOD FOR HIGH-SPEED EXTRUSION COATING AT LOW TEMPERATURE AND SUITABLE POLYETHYLENE COMPOSITIONS THEREFOR WITH HEAT-SENSITIVE ADDITIVES |
| JPH0566519A (en) * | 1991-09-05 | 1993-03-19 | Oji Paper Co Ltd | Supporting body for photographic printing paper |
| JPH0651450A (en) * | 1992-03-27 | 1994-02-25 | Fuji Photo Film Co Ltd | Photosensitive material paper and its production |
-
1995
- 1995-02-16 JP JP02802895A patent/JP3707819B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08220690A (en) | 1996-08-30 |
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