JPH0476463B2 - - Google Patents
Info
- Publication number
- JPH0476463B2 JPH0476463B2 JP29104985A JP29104985A JPH0476463B2 JP H0476463 B2 JPH0476463 B2 JP H0476463B2 JP 29104985 A JP29104985 A JP 29104985A JP 29104985 A JP29104985 A JP 29104985A JP H0476463 B2 JPH0476463 B2 JP H0476463B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- resin
- photographic support
- paper
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000004408 titanium dioxide Substances 0.000 claims description 31
- 239000000049 pigment Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 13
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229920013716 polyethylene resin Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims 1
- -1 fatty acid salts Chemical class 0.000 description 12
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006081 fluorescent whitening agent Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229920006319 cationized starch Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- ODPJQZNJZWLTJH-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-d]pyrimidin-5-one Chemical class O=C1N=CC2=NNNC2=N1 ODPJQZNJZWLTJH-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 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
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- OOCSVLHOTKHEFZ-UHFFFAOYSA-N icosanamide Chemical compound CCCCCCCCCCCCCCCCCCCC(N)=O OOCSVLHOTKHEFZ-UHFFFAOYSA-N 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Description
（産業上の利用分野）
本発明は紙又は合成紙基体の少なくとも一方の
面に、二酸化チタンを含む樹脂組成物をフイルム
状に溶融押出塗工した写真用支持体に関するもの
であり、より詳しくは該二酸化チタンがジルコア
ルミネート系カツプリング剤で表面処理されてい
ることを特徴とする写真用支持体に関する。
（従来技術）
写真用支持体の本質的構成については、すでに
公知であり、例えば米国特許第3501298号に開示
されている様に、紙基体の両面を樹脂で被覆し、
乳剤塗布面側の樹脂層には二酸化チタン顔料、青
色顔料、螢光増白剤等を含有させるという方法で
ある。
そもそも顔料をポリオレフイン樹脂に含有せし
める方法としては、予め顔料を樹脂中に高濃度に
含有させた所謂マスターバツチを作成して、それ
らを希釈樹脂で所望の割合に希釈混合して使用す
るか、顔料を樹脂中に最初から所望の組成比だけ
含有させた所謂コンパウンドを作成して使用する
のが通常である。
しかしながら、特にバンバリーミキサー、ニー
ダー等の通常の溶融混練してマスターバツチ或は
コンパウンドを調製する場合には、樹脂中に比較
的粗大な顔料粒子が、微細状態に分散されないで
そのまま分散されてしまう傾向があり、かくして
マスターバツチ或はコンパウンド中には未分散の
顔料粒子が存在する事になる。その結果、紙又は
合成紙基体の少なくとも一方の面が該マスターバ
ツチ或は該コンパウンドを使用して製造された顔
料と樹脂とから成る樹脂組成物で被覆された写真
用支持体の樹脂面上に、微小な異物あるいは微小
な粒であるミクログリツトが発生することにな
る。
写真用支持体にミクログリツトが発生すると重
大な写真的障害を引き起こす。即ちミクログリツ
トの発生した樹脂被覆紙を写真用支持体として有
する印画紙に人物を写した時、顔などの部分にミ
クログリツトが現われるとその商品価値は全くな
くなつてしまう。
さらに、ミクログリツトの発生した写真用支持
体は、隠ぺい力が大巾に低下してしまう。
（発明の目的）
本発明の目的は、ミクログリツトの発生が無
く、隠ぺい力が大巾に向上した写真用支持体を提
供することである。
（発明の構成）
本発明の目的は、紙又は合成紙基体の少なくと
も一方の面が少なくとも二酸化チタン顔料と樹脂
からなる樹脂組成物で被覆された写真用支持体に
於て、該二酸化チタン顔料がその製造工程中に於
てジルコアルミネート系カツプリング剤で被覆処
理されている事を特徴とする写真用支持体により
達成された。
本発明に使用するジルコアルミネート系カツプ
リング剤は商品名CAVCO MODとして上市され
ており、これを利用出来る。
本発明のジルコアルミネート系カツプリング剤
を酸化チタン顔料の粒子表面に被覆処理するに
は、１二酸化チタン製造工程中でそれが水スラリ
ー状態の時にジルコアルミネート系カツプリング
剤を添加し被覆処理する方法。２二酸化チタン顔
料をマイクロナイザー或はジエツトミル等の流体
エネルギー粉砕機で粉砕する際にジルコアルミネ
ート系カツプリング剤を添加する方法。３ヘンシ
エルミキサー、スーパーミキサー等の高剪断力混
合機を用いてジルコアルミネート系カツプリング
剤と混合して、二酸化チタン顔料表面に被覆する
方法。４ジルコアルミネート系カツプリング剤溶
液中に酸化チタン顔料を浸漬させてから溶媒を蒸
発乾燥させる方法等があり、その他結果として二
酸化チタン表面に均一に処理されていれば良い
が、特に上記２及び３の方法が好ましい。
本発明のジルコアルミネート系カツプリング剤
の被覆処理量は、二酸化チタンに対して0.01〜５
重量％（固形分計算）が好ましい。処理量が0.01
％未満では二酸化チタンの分散性が低下し、かつ
ミクログリツトが多量に発生する。又、５重量％
以上にしても５重量％処理品に比べて特に良い効
果が発現する訳ではなく、逆にマスターバツチ製
造時に滑りが発生し、混練性の悪化とミクログリ
ツトの増加を伴なう。
本発明で使用する二酸化チタンはルチル型、ア
ナターゼ型何れのものも使用出来、また二酸化チ
タン表面を含水金属酸化物例えば含水酸化アルミ
ニウム、含水酸化鉄等で表面が部分的に被覆され
ていても良い。特にジルコアルミネート系カツプ
リング在処理に先だつて、含水酸化アルミニウム
で二酸化チタンに対して0.2〜1.2重量％（Al2O3
換算）表面処理した二酸化チタンを用いるとさら
に効果的である。又、本発明で使用する二酸化チ
タンの粒子径は特に規制はなく、通常市販されて
いる0.1〜1μｍ程度の粒子径で良いが、好ましく
は0.15〜0.35程度の粒子径が使用される。本発明
に於て使用される二酸化チタンを得る為の含水酸
化アルミニウムによる表面処理方法は、例えば特
公昭47−17620号に記載の方法で行なえばよい。
二酸化チタン顔料のポリオレフイン樹脂への添
加量は、ポルオレフイン樹脂組成物に対し、５重
量％以下であると、写真用支持体として隠ぺい力
が不十分であり、一方30重量％以上では流動性が
低下して好ましくなく、特に好ましくは、５〜20
重量％の範囲である。
本発明に於けるポリオレフインとしては、低密
度ポレエチレン、中密度ポリエチレン、高密度ポ
リエチレンの各種の密度及び溶融粘度指数のもの
を、単独或は、それらを混合して使用できる。
本発明に於けるポリオレフイン樹脂組成物中に
は、二酸化チタンの他に更に酸化亜鉛、タルク、
炭酸カルシウムなどの白色顔料、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、
２，６−ジ−tert−ブチル−４−メチルフエノー
ル等の酸化防止剤、群青、ベンガラ等の着色顔
料、螢光増白剤を加えても良い。
本発明に於けるポリオレフイン樹脂被覆紙は、
通常走行する紙又は合成紙基体（以下単に基紙と
言う）上にポリオレフイン樹脂組成物をスリツト
ダイからフイルム状に溶融押出塗工して製造され
る。その際、溶融押出温度は200℃乃至350℃であ
ることが好ましい。スリツトダイとしては、Ｔ型
ダイ、Ｌ型ダイ、フイツシユテイル型ダイが好ま
しく、スリツト開口径は0.1乃至１mmであること
が望ましい。又、樹脂組成物を基紙に塗工する前
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。樹脂被覆紙の樹脂層の
厚さとしては、特に制限はないが、一般に５ミク
ロン乃至50ミクロン程度の厚さに押出塗工したも
のが有利である。又、基紙の両面が樹脂によつて
被覆された通常のポリオレフイン樹脂被覆紙に於
ては、二酸化チタンを含む樹脂表面（乳剤塗布
面）は、その用途に応じて光沢面、マツト面、絹
目面等を有し、裏面は通常無光沢面であり、表面
或は必要に応じて表裏両面にもコロナ放電処理、
火炎処理等の活性化処理を施すことができる。
本発明の実施に用いられる基紙は通常の天然パ
ルプ、紙、合成繊維紙、或は合成樹脂フイルムを
凝紙化した所謂合成紙の何れでも良いが、針葉樹
パルプ、広葉樹パルプ、針葉樹広葉樹混合パルプ
の木材パルプを主成分とする天然パルプ紙が有利
に用いられる。又、基紙の厚味に関しては特に制
限はないが、表面の平滑性の良い基紙が好まし
く、その坪量は50ｇ／m2〜250ｇ／m2が好ましい。
本発明の実施に有利に用いられる天然パルプを
主成分とする基紙には、各種の高分子化合物、添
加剤を含有せしめることが出来る。例えば、乾燥
紙力増強剤としてカチオン化澱粉、カチオン化ポ
リアクリルアミド、アニオン化ポリアクリルアミ
ド、カリボキシ変性ポリビニルアルコール、ゼラ
チン等、サイズ剤として、脂肪酸塩、ロジン誘導
体、ジアルキルケテンダイマー乳化物、石油樹脂
エマルジョン、スチレン−無水マレイン酸共重合
体アルキルエステルのアンモニウム塩等、顔料と
して、クレー、カオリン、炭酸カルシウム、硫酸
バリウム、二酸化チタン等、湿潤紙力増強剤とし
て、メラミン樹脂、尿素樹脂、エポキシ化ポリア
ミド樹脂等、定着剤として硫酸アルミニウム、塩
化アルミニウム等の多価金属塩、カチオン化澱粉
等のカチオン性ポリマー等、PH調節剤として、苛
性ソーダ、炭酸ソーダ、塩酸等、無機電解質とし
て、食塩、芒硝等、そのほか染料、螢光増白剤、
ラテツクス等を適宜組み合わせて含有せしめるこ
とが出来る。
本発明に係る写真用支持体には各種のハロゲン
化銀写真乳剤層を設けることが出来る。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。又、ハロゲン化
銀写真乳剤層にカラーカプラーを含有せしめて、
多層ハロゲン化銀写真構成層を設けることが出来
る。それらのハロゲン化銀乳剤層の結合剤として
は、通常のゼラチンの他に、ポリビニルピロリド
ン、ポリビニルアルコール、多糖類の硝酸エステ
ル化合物等の親水性高分子物質を用いることが出
来る。又、上記のハロゲン化銀乳剤層には各種の
添加剤を含有せしめることが出来る。例えば、増
感色素として、シアニン色素、メロシアニン色素
等、化学増感剤として水溶性金化合物、イオウ化
合物等、カブリ防止剤若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−複素環化合物等、硬膜剤として、ホルマリ
ン、ビニルスルフオン化合物、アジリジン化合物
等、塗布助剤として、ベンゼンスルフオン酸塩、
スルフオコハク酸エステル塩等、汚染防止剤とし
て、ジアルキルハイドロキノン化合物等、紫外線
吸収剤として、ベンゾトリアゾール化合物等、そ
のほか螢光増白剤、鮮鋭度向上色素、帯電防止
剤、PH調節剤、更にハロゲン化銀の生成・分散時
に水溶性イリジウム、ロジウム化合物等を適宜組
み合わせて含有せしめることが出来る。
（発明の実施例）
次に本発明をさらに具体的に説明する為に、実
施例を述べる。
実施例
低密度ポリエチレン（MI＝５、密度0.918）50
重量部と第１表記載のジルコアルミネート系カツ
プリング剤で表面処理した二酸化チタン50重量部
をバンバリーミキサーを用いて150℃で混練し、
二酸化チタンマスターバツチを得た。このマスタ
ーバツチ26重量部と稀釈樹脂として低密度ポリエ
チレン（MI＝４、密度0.920）50重量部及び高密
度ポリエチレン（MI＝６、密度0.960）24重量部
を乾式混合し、坪量105ｇ／m2のポリエステルフ
イルムに溶融押出機を用いて塗工速度80ｍ／分、
溶融温度320℃、塗工量30ｇ／m2で溶融押出塗工
した。この溶融押出機は押出口径65mmのスクリユ
ー式押出機と750mm幅のＴダイを有している。又、
キヤストされた冷却ロール平面は平滑で、ハード
クロムメツキ処理がなされているものを使用し
た。
比較例
低密度ポリエチレン（MI＝5.0、密度0.918）50
重量部と無処理二酸化チタン50重量部及びステア
リン酸亜鉛をバンバリーミキサーを用いて150℃
で混練し、二酸化チタンマスターバツチを得た。
このマスターバツチを実施例と同様の比率同様の
方法で稀釈し、溶融押出塗布した。
第１表不透明度は、ハンター白色度計を用いて
測定した（Ｇフイルター使用）結果を示す。数値
が大い程、隠ぺい力は高い。又、夫々の試料につ
きポリエチレン樹脂面上に発生したミクログリツ
トの個数を視覚的に計数した結果も示す。
第１表の結果より、何れのジルコアルミネート
系カツプリング剤で処理した二酸化チタンを用い
ても、無処理及びステアリン酸亜鉛混練品よりも
不透明度、ミクログリツト共良好であることがわ
かる。
(Industrial Application Field) The present invention relates to a photographic support in which a resin composition containing titanium dioxide is melt-extruded and coated on at least one side of a paper or synthetic paper substrate in the form of a film. The present invention relates to a photographic support characterized in that the titanium dioxide is surface-treated with a zircoaluminate coupling agent. (Prior Art) The essential structure of a photographic support is already known; for example, as disclosed in U.S. Pat. No. 3,501,298, both sides of a paper base are coated with a resin,
In this method, a titanium dioxide pigment, a blue pigment, a fluorescent whitening agent, etc. are contained in the resin layer on the emulsion-coated side. In the first place, the method of incorporating pigments into polyolefin resin is to create a so-called master batch in which pigments are contained in the resin at a high concentration in advance, and then dilute and mix them with a diluent resin to the desired ratio. It is usual to prepare and use a so-called compound in which a desired composition ratio is contained in a resin from the beginning. However, especially when preparing a masterbatch or compound by ordinary melt-kneading using a Banbury mixer, kneader, etc., relatively coarse pigment particles tend to be dispersed as they are without being dispersed in a fine state. Therefore, there will be undispersed pigment particles in the masterbatch or compound. As a result, on the resin side of the photographic support, at least one side of the paper or synthetic paper substrate is coated with a resin composition comprising a pigment and a resin produced using the masterbatch or the compound, Microgrit, which is minute foreign matter or minute particles, will be generated. The occurrence of microgrit in photographic supports causes serious photographic defects. That is, when a person is photographed on a photographic paper using a resin-coated paper containing microgrit as a photographic support, if microgrit appears in areas such as the face, the photograph's commercial value is completely lost. Furthermore, photographic supports in which microgrit is generated have a greatly reduced hiding power. (Object of the Invention) An object of the present invention is to provide a photographic support that does not generate microgrit and has greatly improved hiding power. (Structure of the Invention) An object of the present invention is to provide a photographic support in which at least one side of a paper or synthetic paper substrate is coated with a resin composition comprising at least a titanium dioxide pigment and a resin. This was achieved by using a photographic support characterized by being coated with a zircoaluminate coupling agent during the manufacturing process. The zircoaluminate coupling agent used in the present invention is commercially available under the trade name CAVCO MOD, and can be used. In order to coat the surface of titanium oxide pigment particles with the zircoaluminate coupling agent of the present invention, the zircoaluminate coupling agent is added to the titanium dioxide pigment when it is in a water slurry state during the titanium dioxide production process. . A method of adding a zircoaluminate coupling agent when grinding titanium dioxide pigment with a fluid energy grinder such as a micronizer or a jet mill. 3. A method of coating the surface of titanium dioxide pigment by mixing it with a zircoaluminate coupling agent using a high shear mixer such as a Henschel mixer or a super mixer. 4. There are methods such as immersing the titanium oxide pigment in a zircoaluminate coupling agent solution and then evaporating the solvent to dry it, and other methods as long as the titanium dioxide surface is uniformly treated, but in particular, 2 and 3 above. The method is preferred. The coating amount of the zircoaluminate coupling agent of the present invention is 0.01 to 5% based on titanium dioxide.
Weight % (solids calculation) is preferred. Processing amount is 0.01
If the amount is less than %, the dispersibility of titanium dioxide decreases and a large amount of microgrit is generated. Also, 5% by weight
Even with the above treatment, no particularly good effect is obtained compared to the 5% by weight treated product; on the contrary, slipping occurs during masterbatch production, which is accompanied by deterioration in kneading properties and an increase in microgrit. The titanium dioxide used in the present invention can be either rutile type or anatase type, and the surface of the titanium dioxide may be partially coated with a hydrous metal oxide such as hydrous aluminum oxide, hydrous iron oxide, etc. . In particular, prior to treatment with zircoaluminate couplings, 0.2 to 1.2% by weight of hydrous aluminum oxide (Al 2 O 3
It is even more effective to use surface-treated titanium dioxide. Further, the particle size of titanium dioxide used in the present invention is not particularly limited, and may be a commercially available particle size of about 0.1 to 1 μm, but preferably a particle size of about 0.15 to 0.35 is used. The surface treatment method with hydrous aluminum oxide for obtaining titanium dioxide used in the present invention may be carried out, for example, by the method described in Japanese Patent Publication No. 17620/1983. If the amount of titanium dioxide pigment added to the polyolefin resin is less than 5% by weight based on the polyolefin resin composition, the hiding power will be insufficient as a photographic support, while if it is more than 30% by weight, the fluidity will be poor. It is undesirable because it decreases, particularly preferably from 5 to 20
% by weight. As the polyolefin in the present invention, low-density polyethylene, medium-density polyethylene, and high-density polyethylene with various densities and melt viscosity indexes can be used alone or in combination. In addition to titanium dioxide, the polyolefin resin composition of the present invention further contains zinc oxide, talc,
White pigments such as calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide,
Antioxidants such as 2,6-di-tert-butyl-4-methylphenol, coloring pigments such as ultramarine blue and red iron oxide, and fluorescent whitening agents may be added. The polyolefin resin coated paper in the present invention is
It is usually produced by melt-extruding a polyolefin resin composition onto a paper or synthetic paper substrate (hereinafter simply referred to as base paper) that runs through a slit die in the form of a film. At that time, the melt extrusion temperature is preferably 200°C to 350°C. The slit die is preferably a T-shaped die, an L-shaped die, or a fishtail die, and the slit opening diameter is preferably 0.1 to 1 mm. Further, before coating the resin composition on the base paper, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment or a flame treatment. There is no particular limit to the thickness of the resin layer of the resin-coated paper, but it is generally advantageous to extrude coat it to a thickness of about 5 microns to 50 microns. In addition, in ordinary polyolefin resin-coated paper in which both sides of the base paper are coated with resin, the resin surface containing titanium dioxide (emulsion coated surface) can be glossy, matte, or silky depending on the application. The back side is usually matte, and if necessary, corona discharge treatment is applied to both the front and back sides.
Activation treatment such as flame treatment can be performed. The base paper used in the practice of the present invention may be ordinary natural pulp, paper, synthetic fiber paper, or so-called synthetic paper made of agglomerated synthetic resin film, but may include softwood pulp, hardwood pulp, and mixed softwood and hardwood pulp. Natural pulp paper based on wood pulp is advantageously used. There are no particular restrictions on the thickness of the base paper, but a base paper with good surface smoothness is preferred, and its basis weight is preferably 50 g/m 2 to 250 g/m 2 . The base paper mainly composed of natural pulp, which is advantageously used in the practice of the present invention, can contain various polymeric compounds and additives. For example, dry paper strength enhancers such as cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxyl-modified polyvinyl alcohol, gelatin, etc., and sizing agents such as fatty acid salts, rosin derivatives, dialkyl ketene dimer emulsions, petroleum resin emulsions, Ammonium salt of styrene-maleic anhydride copolymer alkyl ester, etc. Pigments include clay, kaolin, calcium carbonate, barium sulfate, titanium dioxide, etc. Wet paper strength enhancers include melamine resin, urea resin, epoxidized polyamide resin, etc. , polyvalent metal salts such as aluminum sulfate and aluminum chloride, cationic polymers such as cationized starch as fixing agents, caustic soda, soda carbonate, hydrochloric acid, etc. as pH regulators, salt, mirabilite, etc. as inorganic electrolytes, and other dyes. , fluorescent whitening agent,
Latex and the like can be contained in an appropriate combination. The photographic support according to the present invention can be provided with various silver halide photographic emulsion layers. for example,
A silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion layer can be provided. Also, by incorporating a color coupler into the silver halide photographic emulsion layer,
Multilayer silver halide photographic constituent layers can be provided. As the binder for these silver halide emulsion layers, in addition to ordinary gelatin, hydrophilic polymeric substances such as polyvinylpyrrolidone, polyvinyl alcohol, and polysaccharide nitrate ester compounds can be used. Further, the above-mentioned silver halide emulsion layer can contain various additives. For example, as sensitizing dyes, cyanine dyes, merocyanine dyes, etc.; as chemical sensitizers, water-soluble gold compounds, sulfur compounds, etc.; as antifoggants or stabilizers, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc.; As a hardening agent, formalin, vinyl sulfone compound, aziridine compound, etc. As a coating aid, benzene sulfonate,
Sulfosuccinic acid ester salts, etc. as anti-staining agents, dialkylhydroquinone compounds, etc. as ultraviolet absorbers, benzotriazole compounds, etc., as well as fluorescent whitening agents, sharpness-improving dyes, antistatic agents, PH regulators, and silver halides. At the time of production and dispersion, a suitable combination of water-soluble iridium, rhodium compounds, etc. can be included. (Examples of the Invention) Next, examples will be described in order to explain the present invention more specifically. Example Low density polyethylene (MI=5, density 0.918) 50
Parts by weight and 50 parts by weight of titanium dioxide surface-treated with a zircoaluminate coupling agent listed in Table 1 were kneaded at 150°C using a Banbury mixer.
A titanium dioxide masterbatch was obtained. 26 parts by weight of this masterbatch was dry mixed with 50 parts by weight of low-density polyethylene (MI=4, density 0.920) and 24 parts by weight of high-density polyethylene (MI=6, density 0.960) as diluent resins, and a basis weight of 105 g/m 2 was obtained. Coating speed 80 m/min on polyester film using a melt extruder,
Melt extrusion coating was carried out at a melt temperature of 320°C and a coating weight of 30 g/m 2 . This melt extruder has a screw type extruder with an extrusion opening diameter of 65 mm and a T-die with a width of 750 mm. or,
The cast cooling roll had a smooth flat surface and was hard chrome plated. Comparative example Low density polyethylene (MI=5.0, density 0.918) 50
Part by weight, 50 parts by weight of untreated titanium dioxide and zinc stearate at 150°C using a Banbury mixer.
A titanium dioxide masterbatch was obtained.
This masterbatch was diluted in the same manner and in the same proportions as in the Examples and melt extrusion coated. The opacity in Table 1 shows the results measured using a Hunter whiteness meter (using a G filter). The higher the number, the higher the concealment power. Also shown are the results of visually counting the number of microgrits generated on the polyethylene resin surface for each sample. From the results in Table 1, it can be seen that no matter which titanium dioxide treated with a zircoaluminate coupling agent is used, both the opacity and the microgrit are better than the untreated product and the zinc stearate kneaded product.
【表】
中二酸化チタンに噴霧して処理した。
[Table] Treated by spraying onto medium titanium dioxide.
Claims (1)
酸化チタン顔料と樹脂からなる樹脂組成物で被覆
された写真用支持体に於て、該二酸化チタン顔料
が、その製造工程中にジルコアルミネート系カツ
プリング剤で被覆処理されていることを特徴とす
る写真用支持体。 ２ ジルコアルミネート系カツプリング剤の処理
量が、二酸化チタンに対して0.01〜５重量％（固
形分計算）である特許請求の範囲第１項記載の写
真用支持体。 ３ 二酸化チタンがジルコアルミネート系カツプ
リング剤処理に先だつて、含水酸化アルミニウム
で二酸化チタンに対して0.2〜1.2重量％（Al2O3
換算）表面処理された二酸化チタンである特許請
求の範囲第１項、第２項記載の写真用支持体。 ４ 樹脂がポリオレフイン樹脂である特許請求の
範囲第１項、第２項、第３項記載の写真用支持
体。 ５ ポリオレフイン樹脂がポリエチレン樹脂であ
る特許請求の範囲第４項記載の写真用支持体。[Scope of Claims] 1. In a photographic support in which at least one side of a paper or synthetic paper substrate is coated with a resin composition consisting of a titanium dioxide pigment and a resin, the titanium dioxide pigment is removed during the manufacturing process. 1. A photographic support, which is coated with a zircoaluminate coupling agent. 2. The photographic support according to claim 1, wherein the treatment amount of the zircoaluminate coupling agent is 0.01 to 5% by weight (calculated as solid content) based on titanium dioxide. 3 Titanium dioxide is mixed with hydrated aluminum oxide at a concentration of 0.2 to 1.2% by weight (Al 2 O 3
The photographic support according to claims 1 and 2, which is surface-treated titanium dioxide. 4. A photographic support according to claims 1, 2, and 3, wherein the resin is a polyolefin resin. 5. The photographic support according to claim 4, wherein the polyolefin resin is a polyethylene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29104985A JPS62148946A (en) | 1985-12-23 | 1985-12-23 | Base for photography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29104985A JPS62148946A (en) | 1985-12-23 | 1985-12-23 | Base for photography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62148946A JPS62148946A (en) | 1987-07-02 |
| JPH0476463B2 true JPH0476463B2 (en) | 1992-12-03 |
Family
ID=17763772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29104985A Granted JPS62148946A (en) | 1985-12-23 | 1985-12-23 | Base for photography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62148946A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2750974B1 (en) * | 1996-07-11 | 1998-11-20 | Kodak Pathe | POLYMERIC MATERIAL BASED ON ALUMINUM AND USE OF SUCH MATERIAL IN A PHOTOGRAPHIC PRODUCT |
| DE19710358C2 (en) * | 1997-03-13 | 2000-11-30 | Bosch Gmbh Robert | Microstructured sensor |
-
1985
- 1985-12-23 JP JP29104985A patent/JPS62148946A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62148946A (en) | 1987-07-02 |
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