JP2004074460A - Inkjet recording media - Google Patents
Inkjet recording media Download PDFInfo
- Publication number
- JP2004074460A JP2004074460A JP2002234663A JP2002234663A JP2004074460A JP 2004074460 A JP2004074460 A JP 2004074460A JP 2002234663 A JP2002234663 A JP 2002234663A JP 2002234663 A JP2002234663 A JP 2002234663A JP 2004074460 A JP2004074460 A JP 2004074460A
- Authority
- JP
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- Prior art keywords
- polyvinyl alcohol
- group
- oxyalkylene group
- containing polyvinyl
- recording medium
- 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.)
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Links
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 48
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 33
- 229920001567 vinyl ester resin Polymers 0.000 claims description 21
- 235000019422 polyvinyl alcohol Nutrition 0.000 abstract description 4
- -1 polyoxyethylene Polymers 0.000 description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 20
- 238000007127 saponification reaction Methods 0.000 description 20
- 239000000123 paper Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002689 polyvinyl acetate Polymers 0.000 description 5
- 239000011118 polyvinyl acetate Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000077 insect repellent Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、インクジェット方式により印字・印刷されるインクジェット記録用媒体に関し、さらに詳しくは、インク受理性、にじみ防止性、光沢性、耐候性等の印刷適性に優れたインクジェット記録用媒体に関する。
【０００２】
【従来の技術】
従来より、インクジェット方式により印字・印刷されるインクジェット記録用媒体の印刷性能を向上させるために、シート基材表面に特定のコーティング層（インク受容層）を設けることが検討されている。
【０００３】
たとえば、▲１▼特開昭６１−１０４８３号公報には、インク受容性及び記録画像の鮮明性等の改善を目的として、該層にポリビニルアルコールのカチオン変性物を用いることが、▲２▼特開平１０−３０９７８０号公報には、インク吸収性、耐水性、画像の解像度、耐ブロッキング性等の改善を目的として、該層にアルキレンオキサイド変性のポリビニルアルコール系樹脂を用いることが、▲３▼特開２００１−１２１８１４号公報には、画像均一性、鮮明性、耐水性等の改善を目的として、該層に架橋性基含有アクリル共重合体とポリビニルアルコール系樹脂の組成物を用いることが、それぞれ記載されている。
【０００４】
【発明が解決しようとする課題】
しかしながら、上記の各公報に記載の内容を詳細に検討したところ、▲１▼については、光沢性や耐候性に改善の余地があり、▲２▼については、塗工層がにじんで画像安定性が低下することがあり、さらに▲３▼についても光沢性や耐候性に改善の余地があることが判明し、それぞれ一長一短があることから、かかる問題点を解決することが望まれる。
すなわち、本発明の目的とするところは、インク受理性、にじみ防止性、光沢性、平滑性、耐候性の印刷適性に優れたインクジェット記録用媒体を提供することにある。
【０００５】
【問題を解決するための手段】
そこで、本発明者は、かかる目的を達成するために、オキシアルキレン基含有ポリビニルアルコール系樹脂の構造、特にオキシアルキレン基の含有量と樹脂の結晶化度との間に、インクジェット適性に大きな影響を及ぼす要因があるという事実に着目して鋭意研究を重ねた結果、下記（１）式の条件を満足するオキシアルキレン基含有ポリビニルアルコールが上記の問題を解決することを見出して本発明を完成するに至った。
ｙ≦−１．１２ｘ＋５８．１ ・・・（１）
〔但し、ｘはオキシアルキレン基含有ポリビニルアルコール系樹脂の完全ケン化状態におけるオキシアルキレン基含有量（重量％）、ｙはオキシアルキレン基含有ポリビニルアルコール系樹脂の結晶化度（％）をそれぞれ表す〕
【０００６】
なお、オキシアルキレン基の含有量（重量％）はオキシアルキレン鎖のみの値を示し、１Ｈ−ＮＭＲ測定により求めることができる。
また、上記の結晶化度を求めるにあたってはＤＳＣ測定を実施し、得られた結晶化過程における△Ｈ（ｊ／ｇ）を用いて、次式により結晶化度を算出すればよい。
結晶化度（％）＝（△Ｈ／１５６）×１００
［上式において、１５６は完全ケン化ポリビニルアルコール（未変性物）の１００％結晶化物の結晶化エネルギー（ｊ／ｇ）である］
【０００７】
結晶化度の測定にあたっては、厚さ１００μｍキャストフィルムを作製して、五酸化リンデシケータ中で１０日間乾燥したものを使用した。示差走査型熱量計（ＤＳＣ）によりファーストランで３０℃で１分間保持後、２３０℃まで昇温速度４０℃／ｍｉｎで昇温して、２３０℃で１分間保持後、２３０℃から−３０℃まで降温速度２０℃／ｍｉｎで降温して結晶化過程における△Ｈ（ｊ／ｇ）を求めた。
【０００８】
本発明においては、上記の条件を満たすオキシアルキレン基含有ポリビニルアルコールを製造するにあたって、オキシアルキレン基含有モノマーの全使用量とビニルエステル系モノマーの全使用量の１〜５０重量％とを重合系に仕込んで重合を開始し、その後残りのビニルエステル系モノマーを連続滴下仕込みあるいは多分割仕込しながら共重合して得られたオキシアルキレン基含有ビニルエステル系共重合体をケン化する条件で製造することが有用であることも見出したものである。
【０００９】
【発明の実施の形態】
本発明を以下に詳しく説明する。
本発明で言うオキシアルキレン基含有ポリビニルアルコール系樹脂とは、下記一般式（２）で示されるオキシアルキレン基を含有するポリビニルアルコール系樹脂で、より具体的には該一般式（２）で示されるオキシアルキレン基を含有するモノマーとビニルエステル系モノマーとの共重合体をケン化することによって得られる。
【００１０】
【００１１】
オキシアルキレン基を有するモノマーとしては次のようなものが例示されるが、本発明ではこれらのみに限定されるものではない。
［（メタ）アクリル酸エステル型］
【００１２】
上記一般式（３）で示される （但し、Ｒは水素又はメチル基、Ｒ１，Ｒ２はそれぞれ水素又はアルキル基、Ｒ３は水素又はアルキル基又はアルキルアミド基、Ａはアルキレン基、置換アルキレン基、フェニレン基、置換フェニレン基のいずれか、ｍは０又は１以上の整数、ｎは１〜１００の整数）もので、具体的にはポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等が挙げられる。
［（メタ）アクリル酸アミド型］
【００１４】
上記一般式（４）で示される（但し、Ｒ４は水素又はアルキル基又は下記一般式（５）で示されるもの、Ａ、Ｒ、Ｒ１、Ｒ２、Ｒ３、ｍ、ｎは前記と同様）もので、具体的にはポリオキシエチレン（メタ）アクリル酸アミド、ポリオキシプロピレン（メタ）アクリル酸アミド、ポリオキシエチレン（１−（メタ）アクリルアミド−１，１−ジメチルプロピル）エステル等が挙げられる。
【００１６】
〔但しＲ１、Ｒ２、Ｒ３は上記と同様、ｎは１〜３００の整数を示す〕
［（メタ）アリルアルコール型］
【００１８】
上記一般式（６）で示される（Ｒ、Ｒ１、Ｒ２、Ｒ３、ｎは前記と同様）もので、具体的にはポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテル等が挙げられる。
［ビニルエーテル型］
【００２０】
上記一般式（７）で示される（Ａ、Ｒ１、Ｒ２、ｍ、ｎは前記と同様）もので、具体的にはポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル等が挙げられる。
上記のオキシアルキレン基を有するモノマーの中で（メタ）アルコール型のものが好適に使用される。
【００２２】
また、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン等のポリオキシアルキレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン等のポリオキシアルキレンビニルアミン等を用いることも可能である。
【００２３】
本発明のインクジェット記録用媒体に用いられるオキシアルキレン基含有ポリビニルアルコールは、上記の如きオキシアルキレン基を含有させる以外に下記（１）式を満足するものでなければならない。
ｙ≦−１．１２ｘ＋５８．１ ・・・（１）
〔ｘ：オキシアルキレン基含有ポリビニルアルコール系樹脂の完全ケン化状態におけるオキシアルキレン基含有量（重量％）、ｙ：オキシアルキレン基含有ポリビニルアルコール系樹脂の結晶化度（％）〕
【００２４】
上記の（１）式を満足するオキシアルキレン基含有ポリビニルアルコールを得るには特に限定されないが、オキシアルキレン基含有モノマーの全使用量とビニルエステル系モノマーの全使用量の１〜５０重量％を重合系に仕込んで重合を開始し、その後残りのビニルエステル系モノマーを連続滴下仕込みあるいは多分割仕込しながら共重合して得られたオキシアルキレン基含有ビニルエステル系共重合体をケン化する方法で製造されることが、結晶化度のコントロールが容易にできるという点で好ましい。
【００２５】
以下、かかる製造方法について詳細に説明するが、これに限定されるものではない。
本発明のポリビニルアルコール系樹脂を製造するには、アルコール等の溶媒に初期一括仕込みしたオキシアルキレン基含有モノマーと初期仕込みした一部のビニルエステルモノマーを供給して触媒の存在下で重合を開始する。そして、ビニルエステルモノマーを連続滴下しながら、両者をさらに共重合してオキシアルキレン基含有ビニルエステル系共重合体をまず製造する。以下、この方法について説明する。
【００２６】
ビニルエステル系モノマーは、全使用量の５０重量％以上を重合開始後に滴下仕込みすることが必要で、樹脂中のオキシアルキレン基の変性度の分布を大きくすることができ、その結果得られるオキシアルキレン基ポリビニルアルコール系樹脂を用いたインクジェット記録用媒体のインク受理性、光沢性等の効果が一段と発揮できる。
また、上記以外のモノマー（カルボキシル基含有モノマー、スルホン酸基含有モノマー、カチオン基含有モノマーなど）の仕込み方法は特に限定なく、ビニルエステルモノマーと混合して、滴下したり、分割仕込みしたり、一括仕込することができる。
【００２７】
共重合反応は、アゾビスイソブチロニトリル、過酸化アセチル、過酸化ベンゾイル、過酸化ラウロイルなどの公知のラジカル重合触媒を用いて行われる。かかる触媒は通常アルコール等に溶解して仕込まれ、例えば初期重合時に一括して仕込まれたり、初期重合時に一部仕込まれ、ビニルエステルモノマーの滴下仕込み中に残りを分割仕込み、あるいは連続滴下仕込みされる。また反応温度は４０℃〜沸点程度の範囲から選択される。ビニルエステル系モノマーの滴下時間は特に限定されないが、４〜２４時間である。また、必要に応じて、低温活性触媒を用いて行われる。
【００２８】
かくして得られた共重合体は、次にメタノール等のアルコール溶媒中でケン化される。ケン化度は特に限定されないが、３０〜１００モル％（さらには５０〜１００モル％）が好ましく、かかるケン化度が３０モル％未満では、得られるインクジェット記録用媒体のインク受理性や耐候性が低下する傾向にあり好ましくない。
なお、本発明でいうケン化度はオキシアルキレン基含有ビニルエステル共重合体の酢酸ビニル成分が水酸基に変換される割合をモル％で示したものである。また、ケン化にあたり、３〜１０重量％程度の水を加えても良く、更には、ケン化時の溶媒の誘電率制御の目的で酢酸メチル等の各種エステル類やベンゼン、ヘキサン、ＤＭＳＯ等の各種溶剤類を添加しても良い。
【００２９】
ケン化触媒としては水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒を具体的に挙げることができ、かかる触媒の使用量はビニルエステル系モノマー単位に対して１〜１００ミリモルにすることが好ましい。
【００３０】
平均重合度についても特に限定されないが、１００〜４０００（さらには２０００〜３０００）が好ましく、かかる平均重合度が１００未満では、得られるインクジェット記録用媒体表面にべたつき等が残ってブロッキングを起こしたり、逆に４０００を越えると、塗工時の塗工液の粘度が上がりすぎて作業性が低下したり、塗工表面が平滑にならない場合があり好ましくない。
【００３１】
かくして、本発明のインクジェット記録用媒体に用いられるオキシアルキレン基含有ポリビニルアルコール系樹脂が得られるわけであるが、かかる樹脂をインクジェット記録用媒体に適用（塗工）するにあたっては、必要に応じて、無機充填剤（合成シリカ、コロイダルシリカ、アルミナ等）、消泡剤、離型剤、界面活性剤（シリコン系、フッ素系、ポリエチレングリコール系等）、防腐剤、防虫剤、防錆剤、増粘剤等の公知の添加剤を添加することもでき、また本発明の特徴を損なわない範囲であれば他の紙加工剤、例えば、従来公知の他のポリビニルアルコール、澱粉、カルボキシメチルセルロース、アクリル系ラテックス、ＳＢＲラテックス等の樹脂も混合することができる。
【００３２】
本発明のインクジェット記録用媒体の基材としては、たとえば、上質紙、中質紙、（セミ）グラシン紙、光沢紙、（樹脂）コート紙、合成紙、ＰＥＴシート、ＰＶＣシート、ＰＥＮ（ポリエチレンナフタレート）シート、ＰＥＴフイルム、ＰＶＣフイルム、ＰＥＮフイルムなどを挙げることができるが、これらに限定されるものではない。
【００３３】
上記のオキシアルキレン基含有ポリビニルアルコール系樹脂をインクジェット記録用媒体に適用するにあたっては、該媒体の基材に、該樹脂（あるいは樹脂組成物）を塗工すればよく、かかる塗工にあたっては、サイズプレスコート、ロールコーター法、エヤードクター法、ブレードコーター法、ゲートロールコーター法等の公知の任意の方法が採用されるが、該樹脂（あるいは樹脂組成物）を塗工するときは、固形分が１〜７０重量％（更には２〜６０重量％、特に５〜５０重量％）の水溶液とすることが好ましく、かかる固形分が、１重量％未満では、付着量が少なく、印字濃度や表面紙力強度も低く実用性に乏しいものとなり、逆に７０重量％を越えると塗工液の粘度が高くなるため、塗工が困難になり、また塗工斑も生じるために好ましくない。基材に塗工される該樹脂（あるいは樹脂組成物）の塗布量は、固形分換算で０．１〜４０ｇ／ｍ２、特に好ましくは０．５〜２０ｇ／ｍ２程度になるようにするのが適当である。得られたインクジェット記録用媒体は、必要に応じて、ポリビニルアルコール系樹脂等からなるトップコート層を設けることも可能である。
【００３４】
かくして得られた本発明のインクジェット記録用媒体は、表面に良好なインク受理層が形成され、印刷適性（インク受理性、にじみ防止性、光沢性、耐候性）に優れる。
【００３５】
【実施例】
以下、実施例を挙げて本発明を具体的に説明する。
尚、実施例中、「部」、「％」とあるのは、特にことわりのない限り重量基準を示す。
【００３６】
実施例１
重合缶にオキシエチレン基含有モノマー（平均鎖長ｎ＝１０のポリオキシエチレンアリルエーテル）１４．５部と酢酸ビニル１５部、メタノール１０部を仕込み、還流状態になるまで昇温した後、２０分間還流させてから、アゾビスイソブチロニトリルを０．３モル％（対全酢酸ビニル）仕込んだ。次いで、３０分重合させた後、酢酸ビニル８５部（全使用量の８５％）を重合缶中へ５時間３０分かけて、ポンプにより一定速度で滴下仕込みしながら、重合反応を行い、滴下仕込み終了後、３０分間反応を追込みオキシアルキレン基含有ポリ酢酸ビニルのメタノール溶液を得た。また、反応途中にアゾビスイソブチロニトリル０．１モル％（対全酢ビ）を１回追加した。重合率は９５％であった。
【００３７】
次いで、該液を連続脱モノマー塔で液中の残存モノマー量が、０．０６％になるまでモノマーを追い出し、メタノールを添加してポリ酢酸ビニル濃度を５０％に調整してから、５ミリモル（対酢酸ビニルモノマー単位）の水酸化ナトリウムをメタノール溶液で加えて、バッチ式ケン化（３５℃で約７０分）を行い、その後酢酸を加えて中和して、目的とするポリオキシエチレン基含有ポリビニルアルコール系樹脂を得た。
得られたポリオキシエチレン基含有ポリビニルアルコールは、ケン化度９０モル％、平均重合度９００、完全ケン化物のポリオキシエチレン基含有量１８．８％、ＤＳＣにより測定される結晶化度は２７％で上述の（１）式を満足する（２７≦−１．１２×１８．８＋５８．１＝３７．０４）ものであった。
【００３８】
上記で得られたポリオキシエチレン基含有ポリビニルアルコールを用いて、以下の要領で、インクジェット記録用紙（ａ）及びインクジェット記録用フィルム（ｂ）を作製した。
（インクジェット記録用媒体の作製）
上記得られたポリオキシエチレン基含有ポリビニルアルコールの１５％水溶液にコロイダルシリカ（日産化学社製『スノーテックス』）を該ポリビニルアルコール１００部に対して２００部になるように添加してから、坪量６５ｇ／ｍ２の上質紙にアプリケーターにて塗布量１０ｇ／ｍ２（固形分換算）になるように塗工した後、１１０℃で２分間乾燥させてインクジェット記録用紙（ａ）を得た。また、透明度９６％のＰＥＴフィルム（厚さ１００μｍ）にも同様にして、該ポリビニルアルコールを塗工して同様に乾燥させてインクジェット記録用フィルム（ｂ）を得た。
【００３９】
次いで、得られたインクジェット記録用紙（ａ）及びフィルム（ｂ）について、以下の評価を行った。
（インク受理性）
得られたインクジェット記録用紙（ａ）及びフィルム（ｂ）に、インクジェットプリンター（セイコーエプソン社製『ＰＭ−７７０Ｃ』）でイエロー、シアン、マゼンダの各色を記録（印字）して、２０℃，６５％ＲＨで２０秒間放置後、その記録面に別の未記録のインクジェット記録用紙あるいはフィルムを重ねて、５ｇ／１０ｃｍ２の荷重を３０秒間かけて、未記録のインクジェット記録用紙あるいはフィルムへのインクの付着具合を目視観察して以下の通り評価した。
○・・・全くインクの付着が認められない
△・・・わずかにインクの痕跡が認められる
×・・・明らかにインクの付着が認められる
【００４０】
（にじみ性）
得られたインクジェット記録用紙（ａ）、（ｂ）に、上記と同様のインクジェットプリンターを用いてマゼンダ単色で印字後、その上から、シアンインクで約１ｍｍ幅の線を印刷して、該線の境界域でのにじみ具合を顕微鏡で観察して以下の通り評価した。
○・・・インク幅に対してにじみ幅の発生割合が１０％未満
△・・・ 〃 が１０〜３０％未満
×・・・ 〃 が３０％以上
【００４１】
（光沢度）
得られたインクジェット記録用紙（ａ）、（ｂ）に、上記と同様にマゼンダ単色でベタ印字後、２０℃，６５％ＲＨで７２時間放置後、印字部分の光沢度を変角光度計（日本電色工業社製『ＶＧ−Σ８０』）で測定した。
【００４２】
（耐候性）
得られたインクジェット記録用紙（ａ）、（ｂ）に、上記と同様にマゼンダ単色でベタ印字後、４０℃，９０％ＲＨで１０日間放置後、印字部分の印字濃度をマクベス濃度計（マクベス社製『ＲＤ９１４型』）で測定して、１０日間放置前（印字後、２０℃，６５％ＲＨで１時間後）の印字濃度との差を求めた。
【００４３】
（平滑性）
得られたインクジェット記録用紙（ａ）をＳＥＭによる電子顕微鏡写真をとり、平滑性を観察。
○・・・コロイダルシリカ分散状態良好で、凹凸がなく、平滑である。
△・・・コロイダルシリカ分散性やや不良でわずかに凹凸が見られる。
×・・・コロイダルシリカ分散性不良で凹凸が多く見られる。
【００４４】
得られたインクジェット記録用紙（ａ）に、上記と同様にマゼンダ単色でベタ印字後、４０℃，９０％ＲＨで１０日間放置後、印字部分の印字濃度をマクベス濃度計（マクベス社製『ＲＤ９１４型』）で測定して、１０日間放置前（印字後、２０℃，６５％ＲＨで１時間後）の印字濃度との差を求めた。
【００４５】
実施例２
実施例１において、ケン化反応を約６５分行った時点で中和した以外は同様に行って、ケン化度８５モル％、平均重合度９００、完全ケン化物のポリオキシエチレン基含有量１８．８％、結晶化度２４％のポリオキシエチレン基含有ポリビニルアルコールを得て同様に評価を行った。なお、得られたポリオキシエチレン基含有ポリビニルアルコールは上述の（１）式を満足する（２４≦−１．１２×１８．８＋５８．１＝３７．０）ものであった。
【００４６】
実施例３
実施例１において、ケン化反応を約７５分行った時点で中和した以外は同様に行って、ケン化度９５モル％、平均重合度９００、完全ケン化物のポリオキシエチレン基含有量１８．８％、結晶化度３０％のポリオキシエチレン基含有ポリビニルアルコールを得て同様に評価を行った。なお、得られたポリオキシエチレン基含有ポリビニルアルコールは上述の（１）式を満足する（３０≦−１．１２×１８．８＋５８．１＝３７．０）ものであった。
【００４７】
実施例４
重合缶にオキシプロピレン基含有モノマー（平均鎖長ｎ＝１０のポリオキシプロピレンアリルエーテル）１１．１部と酢酸ビニル３５部、メタノール１０部を仕込み還流状態になるまで昇温した後、２０分間還流させてから、アゾビスイソブチルニトリル０．２モル％（対全酢酸ビニル）を仕込んだ。次いで３０分間重合させた後、酢酸ビニル６５部（全仕込量の６５％）を重合缶中へ６時間かけてポンプにより一定速度で滴下仕込みしながら、重合反応を行い、滴下仕込み終了後、３０分間反応を追い込み、オキシプロピレン基含有ポリ酢酸ビニルのメタノール溶液を得た。また、反応途中にアゾビスイソブチロニトリル０．１モル％（対全酢酸ビニル）を２回追加した。重合率は９４％であった。
次いで、実施例１と同様にケン化を行って、ケン化度９０モル％、平均重合度１０００、完全ケン化物のポリオキシプロピレン基含有量１５．７％、結晶化度２０％のポリオキシプロピレン基含有ポリビニルアルコールを得て同様に評価を行った。なお、得られたポリオキシプロピレン基含有ポリビニルアコールは、上記（１）式を満足する（３５≦−１．１２×１５．７＋５８．１＝４０．５）ものであった。
【００４８】
実施例５
重合缶にオキシエチレン基含有モノマー（平均鎖長ｎ＝２１のポリオキシエチレンアリルエーテル）２２．９部と酢酸ビニル３５部、メタノール１０部を仕込み還流状態になるまで昇温した後、２０分間還流させてから、アゾビスイソブチルニトリル０．３モル％（対全酢酸ビニル）を仕込んだ。次いで３０分間重合させた後、酢酸ビニル６５部（全仕込量の６５％）を重合缶中へ６時間かけてポンプにより一定速度で滴下仕込みしながら、重合反応を行い、滴下仕込み終了後、３０分間反応を追い込み、オキシアルキレン基含有ポリ酢酸ビニルのメタノール溶液を得た。また、反応途中にアゾビスイソブチロニトリル０．１モル％（対全酢酸ビニル）を１回追加した。重合率は９４％であった。
次いで、実施例１と同様にケン化を行って、ケン化度９０モル％、平均重合度７００、完全ケン化物のポリオキシエチレン基含有量２７．４％、結晶化度２１％のポリオキシエチレン基含有ポリビニルアルコールを得て、同様に評価を行った。なお、得られたポリオキシエチレン基含有ポリビニルアルコールは、上記の（１）式を満足する（２１≦−１．１２×２７．４＋５８．１＝２２．７）ものであった。
【００４９】
実施例６
重合缶にオキシエチレン基含有モノマー（平均鎖長ｎ＝１５のポリオキシエチレンアリルエーテル）２５．０部と酢酸ビニル３５部、メタノール１５部を仕込み還流状態になるまで昇温した後、２０分間還流させてから、アゾビスイソブチルニトリル０．３モル％（対全酢酸ビニル）を仕込んだ。次いで３０分間重合させた後、酢酸ビニル６５部（全仕込量の６５％）を重合缶中へ６時間かけてポンプにより一定速度で滴下仕込みしながら、重合反応を行い、滴下仕込み終了後、３０分間反応を追い込み、オキシアルキレン基含有ポリ酢酸ビニルのメタノール溶液を得た。また、反応途中にアゾビスイソブチロニトリル０．１モル％（対全酢酸ビニル）を２回追加した。重合率は９４％であった。
次いで、実施例１と同様にケン化を行って、ケン化度９０モル％、平均重合度５５０、完全ケン化物のポリオキシエチレン基含有量２９．０％、結晶化度２０％のポリオキシエチレン基含有ポリビニルアルコール系樹脂を得て、同様に評価を行った。なお、得られたポリオキシエチレン基含有ポリビニルアルコールは、上記の（１）式を満足する（２０≦−１．１２×２９．０＋５８．１＝２５．６）ものであった。
【００５０】
比較例１
実施例１で酢酸ビニルとポリオキシエチレンモノアリルエーテルを初期一括仕込（初期の酢酸ビニルの仕込量１５部を１００部に、メタノール１０部を１５部に変更し、その後、１０時間反応させ、同様にケン化して、ケン化度９０モル％、平均重合度９００、完全ケン化物のポリオキシエチレン基含有量１８．８％、結晶化度４０％のポリオキシエチレン基含有ポリビニルアルコール系樹脂を得て、同様に評価を行った。なお、得られたポリオキシエチレン基含有ポリビニルアルコールは、上記の（１）式を逸脱する（４０＞−１．１２×１８．８−５８．１＝３７．０）ものであった。
【００５１】
実施例及び比較例の評価結果を表１に示す。
【００５２】
【発明の効果】
本発明のインクジェット記録用媒体は、インク受理性、にじみ防止性、光沢性、耐候性、平滑性等の印刷適性に優れ、基材も紙基材のみならず、ＰＥＴ、ＰＶＣ、ＰＰ等の樹脂基材にも最適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an ink jet recording medium which is printed / printed by an ink jet system, and more particularly to an ink jet recording medium having excellent printability such as ink receptivity, bleeding prevention, gloss, and weather resistance.
[0002]
[Prior art]
Conventionally, in order to improve the printing performance of an ink jet recording medium printed / printed by an ink jet method, it has been studied to provide a specific coating layer (ink receiving layer) on the surface of a sheet substrate.
[0003]
For example, (1) Japanese Patent Application Laid-Open No. 61-10483 discloses that a cation-modified product of polyvinyl alcohol is used in the layer for the purpose of improving ink receptivity and clearness of a recorded image. Japanese Unexamined Patent Publication No. Hei 10-309780 discloses that an alkylene oxide-modified polyvinyl alcohol resin is used in the layer for the purpose of improving ink absorption, water resistance, image resolution, blocking resistance, and the like. Japanese Patent Application Laid-Open No. 2001-121814 discloses that for the purpose of improving image uniformity, sharpness, water resistance, and the like, a composition of a crosslinkable group-containing acrylic copolymer and a polyvinyl alcohol-based resin is used for the layer. Has been described.
[0004]
[Problems to be solved by the invention]
However, when the contents described in each of the above publications were examined in detail, there was room for improvement in glossiness and weather resistance in (1), and in (2), the coating layer was blurred and the image stability was poor. It has been found that there is still room for improvement in glossiness and weather resistance of (3), and each has its advantages and disadvantages. Therefore, it is desired to solve such problems.
That is, an object of the present invention is to provide an ink jet recording medium having excellent ink acceptability, anti-bleeding properties, glossiness, smoothness, and weatherability and excellent printability.
[0005]
[Means to solve the problem]
Therefore, the present inventor has found that in order to achieve such an object, the structure of the oxyalkylene group-containing polyvinyl alcohol-based resin, particularly between the content of the oxyalkylene group and the crystallinity of the resin, has a great influence on inkjet suitability. As a result of intensive studies focusing on the fact that there is a factor that exerts an effect, it was found that an oxyalkylene group-containing polyvinyl alcohol satisfying the condition of the following formula (1) solves the above-mentioned problems and completed the present invention. Reached.
y ≦ −1.12x + 58.1 (1)
[Where x represents the oxyalkylene group content (% by weight) in the completely saponified state of the oxyalkylene group-containing polyvinyl alcohol resin, and y represents the crystallinity (%) of the oxyalkylene group-containing polyvinyl alcohol resin].
[0006]
The content (% by weight) of the oxyalkylene group indicates the value of only the oxyalkylene chain, and can be determined by 1 H-NMR measurement.
In order to determine the above crystallinity, DSC measurement is performed, and the crystallinity may be calculated by the following equation using ΔH (j / g) in the obtained crystallization process.
Crystallinity (%) = (ΔH / 156) × 100
[In the above formula, 156 is the crystallization energy (j / g) of a 100% crystallized product of completely saponified polyvinyl alcohol (unmodified product)]
[0007]
In the measurement of the crystallinity, a cast film having a thickness of 100 μm and dried in a phosphorus pentoxide desiccator for 10 days was used. After a first run at 30 ° C. for 1 minute by a differential scanning calorimeter (DSC), the temperature was raised to 230 ° C. at a heating rate of 40 ° C./min. The temperature was lowered at a rate of 20 ° C./min until ΔH (j / g) in the crystallization process was determined.
[0008]
In the present invention, in producing an oxyalkylene group-containing polyvinyl alcohol satisfying the above conditions, the total amount of the oxyalkylene group-containing monomer and 1 to 50% by weight of the total amount of the vinyl ester monomer are used as the polymerization system. The polymerization is started, and then the remaining vinyl ester-based monomer is continuously dripped or multi-divided while being copolymerized while the oxyalkylene group-containing vinyl ester-based copolymer is obtained. Is also found to be useful.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in detail below.
The oxyalkylene group-containing polyvinyl alcohol-based resin referred to in the present invention is a polyvinyl alcohol-based resin having an oxyalkylene group represented by the following general formula (2), and more specifically represented by the general formula (2). It is obtained by saponifying a copolymer of a monomer containing an oxyalkylene group and a vinyl ester monomer.
[0010]
[0011]
Examples of the monomer having an oxyalkylene group include the following, but the present invention is not limited thereto.
[(Meth) acrylate type]
[0012]
Wherein R is hydrogen or a methyl group, R 1 and R 2 are each a hydrogen or alkyl group, R 3 is a hydrogen or alkyl group or an alkylamide group, A is an alkylene group, a substituted alkylene Group, a phenylene group, or a substituted phenylene group, m is an integer of 0 or 1 or more, and n is an integer of 1 to 100), and specifically, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) Acrylate and the like.
[(Meth) acrylamide type]
[0014]
Represented by the above formula (4) (where R4 is hydrogen or an alkyl group or a compound represented by the following formula (5); A, R, R 1 , R 2 , R 3 , m and n are the same as those described above) And specific examples thereof include polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, and polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester. Can be
[0016]
[However, n represents an integer of 1 to 300 as in the above, for R 1 , R 2 , and R 3 ]
[(Meth) allyl alcohol type]
[0018]
(R, R 1 , R 2 , R 3 , and n are the same as those described above) represented by the general formula (6), specifically, polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl Ether and the like.
[Vinyl ether type]
[0020]
(A, R 1 , R 2 , m, and n are the same as those described above) represented by the general formula (7), and specific examples thereof include polyoxyethylene vinyl ether and polyoxypropylene vinyl ether.
Among the above-mentioned monomers having an oxyalkylene group, (meth) alcohol type monomers are preferably used.
[0022]
It is also possible to use polyoxyalkylene allylamine such as polyoxyethylene allylamine and polyoxypropylene allylamine, and polyoxyalkylene vinylamine such as polyoxyethylene vinylamine and polyoxypropylene vinylamine.
[0023]
The oxyalkylene group-containing polyvinyl alcohol used in the ink jet recording medium of the present invention must satisfy the following formula (1) in addition to containing the oxyalkylene group as described above.
y ≦ −1.12x + 58.1 (1)
[X: oxyalkylene group-containing polyvinyl alcohol-based resin in a completely saponified state (% by weight), y: crystallinity of oxyalkylene-group-containing polyvinyl alcohol-based resin (%)]
[0024]
Although there is no particular limitation on obtaining an oxyalkylene group-containing polyvinyl alcohol satisfying the above formula (1), 1 to 50% by weight of the total amount of the oxyalkylene group-containing monomer and the total amount of the vinyl ester-based monomer is polymerized. Polymerization is started by charging into the system and then saponifying the oxyalkylene group-containing vinyl ester-based copolymer obtained by continuously dropping the remaining vinyl ester-based monomer or copolymerizing while charging in multiple divisions. It is preferable that the crystallinity can be easily controlled.
[0025]
Hereinafter, such a manufacturing method will be described in detail, but is not limited thereto.
In order to produce the polyvinyl alcohol-based resin of the present invention, polymerization is started in the presence of a catalyst by supplying an oxyalkylene group-containing monomer initially charged in a solvent such as alcohol and a part of the initially charged vinyl ester monomer. . Then, while the vinyl ester monomer is continuously dropped, the two are further copolymerized to first produce an oxyalkylene group-containing vinyl ester copolymer. Hereinafter, this method will be described.
[0026]
It is necessary to charge 50% by weight or more of the total amount of the vinyl ester-based monomer after the initiation of the polymerization, and it is possible to increase the distribution of the modification degree of the oxyalkylene group in the resin. The effects such as ink receptivity and glossiness of an inkjet recording medium using a base polyvinyl alcohol-based resin can be further exhibited.
The method of charging the monomers other than those described above (such as a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, and a cation group-containing monomer) is not particularly limited, and may be mixed with a vinyl ester monomer and dropped, dividedly charged, or batched. Can be stocked.
[0027]
The copolymerization reaction is performed using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide. Such a catalyst is usually charged by dissolving in alcohol or the like, for example, it is charged all at once during the initial polymerization, or is partially charged during the initial polymerization, and the remaining portion is charged during the dropwise addition of the vinyl ester monomer, or is charged continuously. You. The reaction temperature is selected from the range of 40 ° C. to about the boiling point. Although the dropping time of the vinyl ester monomer is not particularly limited, it is 4 to 24 hours. In addition, if necessary, the reaction is performed using a low-temperature active catalyst.
[0028]
The copolymer thus obtained is then saponified in an alcoholic solvent such as methanol. Although the saponification degree is not particularly limited, it is preferably 30 to 100 mol% (more preferably 50 to 100 mol%), and when the saponification degree is less than 30 mol%, the ink receptivity and weather resistance of the obtained ink jet recording medium are obtained. Tends to decrease, which is not preferred.
The degree of saponification as used in the present invention indicates the ratio of the conversion of the vinyl acetate component of the oxyalkylene group-containing vinyl ester copolymer into a hydroxyl group by mol%. In the saponification, about 3 to 10% by weight of water may be added. Further, for the purpose of controlling the dielectric constant of the solvent during the saponification, various esters such as methyl acetate, benzene, hexane, DMSO, etc. Various solvents may be added.
[0029]
Specific examples of the saponification catalyst include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate. The amount used is preferably from 1 to 100 mmol per vinyl ester monomer unit.
[0030]
The average degree of polymerization is not particularly limited, but is preferably from 100 to 4000 (more preferably from 2,000 to 3,000). If the average degree of polymerization is less than 100, stickiness or the like remains on the surface of the obtained inkjet recording medium, causing blocking, On the other hand, if it exceeds 4,000, the viscosity of the coating liquid at the time of coating becomes too high, and the workability may be lowered, or the coated surface may not be smooth, which is not preferable.
[0031]
Thus, the oxyalkylene group-containing polyvinyl alcohol-based resin used in the inkjet recording medium of the present invention is obtained. When applying such a resin to the inkjet recording medium (coating), if necessary, Inorganic fillers (synthetic silica, colloidal silica, alumina, etc.), defoamers, release agents, surfactants (silicone, fluorine, polyethylene glycol, etc.), preservatives, insect repellents, rust inhibitors, thickeners It is also possible to add a known additive such as an agent, and other paper processing agents within a range that does not impair the characteristics of the present invention, for example, other conventionally known polyvinyl alcohol, starch, carboxymethyl cellulose, acrylic latex , SBR latex and other resins can also be mixed.
[0032]
Examples of the base material of the ink jet recording medium of the present invention include fine paper, medium paper, (semi) glassine paper, glossy paper, (resin) coated paper, synthetic paper, PET sheet, PVC sheet, and PEN (polyethylene resin). (Phthalate) sheet, PET film, PVC film, PEN film, and the like, but are not limited thereto.
[0033]
When the above oxyalkylene group-containing polyvinyl alcohol-based resin is applied to an inkjet recording medium, the resin (or resin composition) may be applied to a base material of the medium. A known arbitrary method such as a press coat, a roll coater method, an air yard method, a blade coater method, and a gate roll coater method is employed. When the resin (or the resin composition) is applied, a solid content is reduced. An aqueous solution of 1 to 70% by weight (more preferably 2 to 60% by weight, particularly 5 to 50% by weight) is preferable. When the strength exceeds 70% by weight, the viscosity of the coating liquid becomes high, so that the coating becomes difficult and the coating becomes uneven. Not properly. The coating amount of the resin to be coated on the base material (or resin composition), 0.1 to 40 g / m 2 in terms of solid content, particularly preferably set to be about 0.5 to 20 g / m 2 Is appropriate. The obtained ink jet recording medium can be provided with a top coat layer made of a polyvinyl alcohol-based resin or the like, if necessary.
[0034]
The ink-jet recording medium of the present invention thus obtained has a good ink-receiving layer formed on the surface, and is excellent in printability (ink-reception, bleeding prevention, gloss, weather resistance).
[0035]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples.
In the examples, “parts” and “%” are based on weight unless otherwise specified.
[0036]
Example 1
A polymerization vessel was charged with 14.5 parts of an oxyethylene group-containing monomer (polyoxyethylene allyl ether having an average chain length of n = 10), 15 parts of vinyl acetate, and 10 parts of methanol, and heated to a reflux state, followed by 20 minutes. After refluxing, azobisisobutyronitrile was charged at 0.3 mol% (vs. total vinyl acetate). Then, after polymerization for 30 minutes, a polymerization reaction was carried out while 85 parts of vinyl acetate (85% of the total amount used) was dropped into the polymerization vessel at a constant speed over 5 hours and 30 minutes by a pump. After completion, the reaction was continued for 30 minutes to obtain a methanol solution of oxyalkylene group-containing polyvinyl acetate. During the reaction, 0.1 mol% of azobisisobutyronitrile (based on total vinyl acetate) was added once. The conversion was 95%.
[0037]
Next, the liquid was removed from the liquid in a continuous demonomerization column until the amount of residual monomers in the liquid became 0.06%, and methanol was added to adjust the polyvinyl acetate concentration to 50%. Sodium hydroxide of vinyl acetate monomer unit) is added in a methanol solution to perform batch saponification (at 35 ° C. for about 70 minutes), and then neutralized by adding acetic acid to obtain the desired polyoxyethylene group-containing A polyvinyl alcohol-based resin was obtained.
The obtained polyoxyethylene group-containing polyvinyl alcohol had a degree of saponification of 90 mol%, an average degree of polymerization of 900, a polyoxyethylene group content of a completely saponified product of 18.8%, and a degree of crystallization as measured by DSC of 27%. Satisfying the above-mentioned expression (1) (27 ≦ −1.12 × 18.8 + 58.1 = 37.04).
[0038]
Using the polyoxyethylene group-containing polyvinyl alcohol obtained above, an inkjet recording paper (a) and an inkjet recording film (b) were produced in the following manner.
(Preparation of inkjet recording medium)
Colloidal silica ("Snowtex" manufactured by Nissan Chemical Industries, Ltd.) was added to a 15% aqueous solution of the above-obtained polyoxyethylene group-containing polyvinyl alcohol so as to be 200 parts with respect to 100 parts of the polyvinyl alcohol. After applying to a high quality paper of 65 g / m 2 with an applicator so as to have an application amount of 10 g / m 2 (in terms of solid content), it was dried at 110 ° C. for 2 minutes to obtain an inkjet recording paper (a). Similarly, the polyvinyl alcohol was coated on a PET film having a transparency of 96% (thickness: 100 μm) and dried in the same manner to obtain an inkjet recording film (b).
[0039]
Next, the following evaluation was performed on the obtained inkjet recording paper (a) and film (b).
(Ink acceptability)
On the obtained ink jet recording paper (a) and film (b), each color of yellow, cyan and magenta was recorded (printed) by an ink jet printer (“PM-770C” manufactured by Seiko Epson Corporation), and the temperature was 20 ° C., 65% After leaving at RH for 20 seconds, another unrecorded inkjet recording paper or film is superimposed on the recording surface, and a load of 5 g / 10 cm 2 is applied for 30 seconds to adhere the ink to the unrecorded inkjet recording paper or film. The condition was visually observed and evaluated as follows.
・ ・ ・: No ink adhesion was observed at all わ ず か: slight ink traces were observed ×: ink adhesion was clearly observed
(Bleedability)
After printing on the obtained ink jet recording papers (a) and (b) with a single color of magenta using the same ink jet printer as above, a line having a width of about 1 mm was printed thereon with cyan ink, and the line was printed. The degree of bleeding at the boundary area was observed with a microscope and evaluated as follows.
・ ・ ・: Occurrence ratio of bleed width to ink width is less than 10 %％: 未 満 is less than 10 to 30% X: 〃 is 30% or more
(Glossiness)
On the obtained ink jet recording papers (a) and (b), after solid printing with magenta single color in the same manner as described above, and after leaving at 20 ° C. and 65% RH for 72 hours, the glossiness of the printed portion was measured with a goniophotometer (Japan). It was measured by Denki Kogyo Co., Ltd. “VG- $ 80”).
[0042]
(Weatherability)
On the obtained ink jet recording papers (a) and (b), after solid printing with magenta single color in the same manner as described above, after leaving at 40 ° C. and 90% RH for 10 days, the print density of the printed portion was measured with a Macbeth densitometer (Macbeth Co., Ltd.). (RD914) manufactured by the company), and the difference from the print density before standing for 10 days (after printing, at 1 hour at 20 ° C. and 65% RH) was determined.
[0043]
(Smoothness)
The obtained inkjet recording paper (a) was photographed with an electron microscope using an SEM, and the smoothness was observed.
・ ・ ・: Good colloidal silica dispersion state, no irregularities, and smooth.
Δ: Colloidal silica dispersibility is slightly poor, and slight irregularities are observed.
C: Many irregularities are observed due to poor dispersibility of colloidal silica.
[0044]
On the obtained ink jet recording paper (a), after solid printing with magenta single color in the same manner as described above, after leaving it at 40 ° C. and 90% RH for 10 days, the printing density of the printing portion was measured with a Macbeth densitometer (“RD914 type” manufactured by Macbeth). )) To determine the difference from the print density before standing for 10 days (after printing, after 1 hour at 20 ° C. and 65% RH).
[0045]
Example 2
In the same manner as in Example 1, except that the saponification reaction was carried out for about 65 minutes and then neutralized, the degree of saponification was 85 mol%, the average degree of polymerization was 900, and the polyoxyethylene group content of the completely saponified product was 18. A polyoxyethylene group-containing polyvinyl alcohol having a crystallinity of 8% and a crystallinity of 24% was obtained and similarly evaluated. The obtained polyoxyethylene group-containing polyvinyl alcohol satisfied the above-mentioned formula (1) (24 ≦ −1.12 × 18.8 + 58.1 = 37.0).
[0046]
Example 3
Example 1 was repeated in the same manner as in Example 1 except that the saponification reaction was carried out for about 75 minutes, except that the saponification was neutralized. The degree of saponification was 95 mol%, the average degree of polymerization was 900, and the polyoxyethylene group content of the completely saponified product was 18. Polyoxyethylene group-containing polyvinyl alcohol having a crystallinity of 8% and a crystallinity of 30% was obtained and similarly evaluated. The obtained polyoxyethylene group-containing polyvinyl alcohol satisfies the above formula (1) (30 ≦ −1.12 × 18.8 + 58.1 = 37.0).
[0047]
Example 4
In a polymerization vessel, 11.1 parts of an oxypropylene group-containing monomer (polyoxypropylene allyl ether having an average chain length of n = 10), 35 parts of vinyl acetate, and 10 parts of methanol were charged and heated to a reflux state, and then refluxed for 20 minutes. After that, 0.2 mol% of azobisisobutylnitrile (based on total vinyl acetate) was charged. Then, after polymerization for 30 minutes, a polymerization reaction was carried out while 65 parts of vinyl acetate (65% of the total charged amount) was dropped into the polymerization vessel at a constant speed by a pump over 6 hours. The reaction was driven for a minute to obtain a methanol solution of oxypropylene group-containing polyvinyl acetate. During the reaction, 0.1 mol% of azobisisobutyronitrile (based on total vinyl acetate) was added twice. The conversion was 94%.
Next, saponification was carried out in the same manner as in Example 1 to obtain a polyoxypropylene having a degree of saponification of 90 mol%, an average degree of polymerization of 1,000, a polyoxypropylene group content of completely saponified product of 15.7%, and a crystallinity of 20%. A group-containing polyvinyl alcohol was obtained and similarly evaluated. In addition, the obtained polyoxypropylene group-containing polyvinyl alcohol satisfied the above formula (1) (35 ≦ −1.12 × 15.7 + 58.1 = 40.5).
[0048]
Example 5
A polymerization vessel was charged with 22.9 parts of an oxyethylene group-containing monomer (polyoxyethylene allyl ether having an average chain length of n = 21), 35 parts of vinyl acetate, and 10 parts of methanol, heated to a reflux state, and then refluxed for 20 minutes. After that, 0.3 mol% of azobisisobutylnitrile (based on total vinyl acetate) was charged. Then, after polymerization for 30 minutes, a polymerization reaction was carried out while 65 parts of vinyl acetate (65% of the total charged amount) was dropped into the polymerization vessel at a constant speed by a pump over 6 hours. The reaction was driven for a minute to obtain a methanol solution of oxyalkylene group-containing polyvinyl acetate. During the reaction, azobisisobutyronitrile 0.1 mol% (based on total vinyl acetate) was added once. The conversion was 94%.
Subsequently, saponification was carried out in the same manner as in Example 1, to obtain a polyoxyethylene having a degree of saponification of 90 mol%, an average degree of polymerization of 700, a polyoxyethylene group content of a completely saponified substance of 27.4% and a degree of crystallinity of 21% A group-containing polyvinyl alcohol was obtained and similarly evaluated. In addition, the obtained polyoxyethylene group-containing polyvinyl alcohol satisfied the above formula (1) (21 ≦ −1.12 × 27.4 + 58.1 = 22.7).
[0049]
Example 6
A polymerization vessel was charged with 25.0 parts of an oxyethylene group-containing monomer (polyoxyethylene allyl ether having an average chain length of n = 15), 35 parts of vinyl acetate, and 15 parts of methanol, and heated to a reflux state, and then refluxed for 20 minutes. After that, 0.3 mol% of azobisisobutylnitrile (based on total vinyl acetate) was charged. Then, after polymerization for 30 minutes, a polymerization reaction was carried out while 65 parts of vinyl acetate (65% of the total charged amount) was dropped into the polymerization vessel at a constant speed by a pump over 6 hours. The reaction was driven for a minute to obtain a methanol solution of oxyalkylene group-containing polyvinyl acetate. During the reaction, azobisisobutyronitrile 0.1 mol% (based on total vinyl acetate) was added twice. The conversion was 94%.
Then, saponification was carried out in the same manner as in Example 1, and polyoxyethylene having a degree of saponification of 90 mol%, an average degree of polymerization of 550, a polyoxyethylene group content of completely saponified product of 29.0%, and a crystallinity of 20% was obtained. A group-containing polyvinyl alcohol-based resin was obtained and similarly evaluated. In addition, the obtained polyoxyethylene group-containing polyvinyl alcohol satisfied the above formula (1) (20 ≦ −1.12 × 29.0 + 58.1 = 25.6).
[0050]
Comparative Example 1
In Example 1, vinyl acetate and polyoxyethylene monoallyl ether were initially charged at once (the initial charge of vinyl acetate was changed from 15 parts to 100 parts, methanol was changed to 15 parts, and then reacted for 10 hours. To obtain a polyoxyethylene group-containing polyvinyl alcohol resin having a saponification degree of 90 mol%, an average degree of polymerization of 900, a polyoxyethylene group content of completely saponified product of 18.8%, and a crystallinity of 40%. The obtained polyoxyethylene group-containing polyvinyl alcohol deviated from the above formula (1) (40> −1.12 × 18.8-58.1 = 37.0). ).
[0051]
Table 1 shows the evaluation results of the examples and the comparative examples.
[0052]
【The invention's effect】
The ink jet recording medium of the present invention is excellent in printing suitability such as ink receptivity, bleeding prevention, gloss, weather resistance, and smoothness. The base material is not only a paper base material but also a resin such as PET, PVC, or PP. Ideal for substrates.
Claims (4)
ｙ≦−１．１２ｘ＋５８．１ ・・・（１）
〔ｘ：オキシアルキレン基含有ポリビニルアルコール系樹脂の完全ケン化状態におけるオキシアルキレン基含有量（重量％）、ｙ：オキシアルキレン基含有ポリビニルアルコール系樹脂の結晶化度（％）〕An ink jet recording medium comprising a layer containing an oxyalkylene group-containing polyvinyl alcohol resin satisfying the following condition (1).
y ≦ −1.12x + 58.1 (1)
[X: oxyalkylene group-containing polyvinyl alcohol-based resin in a completely saponified state (% by weight), y: crystallinity of oxyalkylene-group-containing polyvinyl alcohol-based resin (%)]
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002234663A JP3868868B2 (en) | 2002-08-12 | 2002-08-12 | Inkjet recording medium |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002234663A JP3868868B2 (en) | 2002-08-12 | 2002-08-12 | Inkjet recording medium |
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| JP2004074460A true JP2004074460A (en) | 2004-03-11 |
| JP3868868B2 JP3868868B2 (en) | 2007-01-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008163179A (en) * | 2006-12-28 | 2008-07-17 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and inkjet recording medium using the same |
| CN114426621A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Nonionic modified polyvinyl alcohol and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008163179A (en) * | 2006-12-28 | 2008-07-17 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and inkjet recording medium using the same |
| CN114426621A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Nonionic modified polyvinyl alcohol and preparation method thereof |
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