JP2006213840A - Polyvinyl alcohol-modified graft polymer, method for producing the same and inkjet recording medium containing the same - Google Patents
Polyvinyl alcohol-modified graft polymer, method for producing the same and inkjet recording medium containing the same Download PDFInfo
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 24
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 47
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- 238000010559 graft polymerization reaction Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- ZIVBAAWXJUAKAR-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;pyrrolidin-2-one Chemical compound O=C1CCCN1.C=CN1CCCC1=O ZIVBAAWXJUAKAR-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Graft Or Block Polymers (AREA)
- Ink Jet (AREA)
Abstract
Description
本発明は、ポリビニルアルコール変性グラフト重合体、その製造方法及びそれを含有するインクジェット記録用媒体に関する。 The present invention relates to a polyvinyl alcohol-modified graft polymer, a production method thereof, and an inkjet recording medium containing the same.
ポリビニルアルコールは水溶性の高分子であり、繊維加工剤、紙加工剤、接着剤、無機物のバインダー等、広い範囲で利用されている。 Polyvinyl alcohol is a water-soluble polymer and is used in a wide range of fiber processing agents, paper processing agents, adhesives, inorganic binders, and the like.
しかし、ポリビニルアルコールは水に溶解させるときに、熱水にて溶解させる必要があり、しかも溶解に長時間を要するという問題があった。 However, when polyvinyl alcohol is dissolved in water, it needs to be dissolved in hot water, and it takes a long time to dissolve.
ポリビニルアルコールは、インクの吸収性が良好であるためインクジェット記録媒体にも使用され、その用途に関し、特開２００１−１１３８１８号公報には、ポリビニルアルコールと、ポリビニルピロリドンと、ポリビニルアルコールを選択的に架橋する架橋剤と、ポリビニルアルコール−ポリエステル共重合体と、カチオン樹脂とを含有するインク受容層を形成することが開示されている。 Polyvinyl alcohol is also used in ink jet recording media because of its good ink absorbability. JP-A-2001-113818 discloses a method for selectively cross-linking polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl alcohol. Forming an ink receiving layer containing a crosslinking agent, a polyvinyl alcohol-polyester copolymer, and a cationic resin.
しかし、この発明においても、その組成物を水に溶解させて使用する場合、溶解が困難で長時間を要するという問題は解決されていない。
本発明は上記に鑑みてなされたものであり、熱水を用いなくても速やかに水に溶解し、容易に水溶液が得られるポリビニルアルコール変性体を提供することを目的とする。また、そのポリビニルアルコール変性体の製造方法及びそのポリビニルアルコール変性体を用いたインクジェット記録用媒体を提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide a modified polyvinyl alcohol that can be quickly dissolved in water and an aqueous solution can be easily obtained without using hot water. Another object of the present invention is to provide a method for producing the modified polyvinyl alcohol and an inkjet recording medium using the modified polyvinyl alcohol.
本発明者は、ポリビニルアルコールにビニルピロリドンをグラフト重合することにより、常温で容易に水に溶解するポリビニルアルコール変性物を得られることを見出した。 The present inventor has found that a polyvinyl alcohol-modified product that easily dissolves in water at room temperature can be obtained by graft polymerization of polyvinyl pyrrolidone to polyvinyl alcohol.
すなわち、本発明のポリビニルアルコール変性グラフト重合体は、上記課題の解決のために、ポリビニルアルコールにビニルピロリドンがグラフト重合したものとする。 That is, the polyvinyl alcohol-modified graft polymer of the present invention is obtained by grafting vinyl pyrrolidone to polyvinyl alcohol in order to solve the above problems.
本発明のポリビニルアルコール変性グラフト重合体は、ポリビニルアルコール溶液にビニルピロリドンを配合し、開始剤として過酸化水素又は有機過酸化物を用いて重合する製造方法により得られる。 The polyvinyl alcohol-modified graft polymer of the present invention is obtained by a production method in which vinyl pyrrolidone is blended in a polyvinyl alcohol solution and polymerized using hydrogen peroxide or an organic peroxide as an initiator.
さらに、本発明のインクジェット記録用媒体は、上記本発明のポリビニルアルコール変性グラフト重合体を含有してなるものとする。 Furthermore, the ink jet recording medium of the present invention contains the polyvinyl alcohol-modified graft polymer of the present invention.
本発明のポリビニルアルコール変性グラフト重合体は常温の水に速やかに溶解するので、容易に水溶液を調製することができる。 Since the polyvinyl alcohol-modified graft polymer of the present invention dissolves quickly in water at room temperature, an aqueous solution can be easily prepared.
また、本発明のポリビニルアルコール変性グラフト重合体を使用したインクジェット記録用媒体によれば、ポリビニルアルコールを単独で使用したときと比較して色鮮やかな印刷が可能となる。 In addition, according to the ink jet recording medium using the polyvinyl alcohol-modified graft polymer of the present invention, it is possible to print more vividly than when polyvinyl alcohol is used alone.
本発明のポリビニルアルコール変性グラフト重合体とは、ポリビニルアルコールにビニルピロリドン（Ｎ−ビニル−２−ピロリドン）をグラフト重合したものである。 The polyvinyl alcohol-modified graft polymer of the present invention is obtained by graft polymerization of polyvinyl pyrrolidone (N-vinyl-2-pyrrolidone) to polyvinyl alcohol.
本発明のポリビニルアルコール変性グラフト重合体の製造方法は、ポリビニルアルコール溶液にビニルピロリドンを配合し、適当な開始剤を用いて重合する製造方法により得ることができる。 The production method of the polyvinyl alcohol-modified graft polymer of the present invention can be obtained by a production method in which vinyl pyrrolidone is blended in a polyvinyl alcohol solution and polymerized using an appropriate initiator.
用いるポリビニルアルコールは重合度が１００〜４０００であり、かつケン化度が７０〜１００モル％であることが好ましい。重合度が１００未満であるとバインダー性能が発現せず、４０００を超えると水への溶解に要する時間が長くなる傾向がある。また、ケン化度が７０モル％未満であると水に均一に溶解しにくい。 The polyvinyl alcohol to be used preferably has a polymerization degree of 100 to 4000 and a saponification degree of 70 to 100 mol%. When the degree of polymerization is less than 100, the binder performance does not appear, and when it exceeds 4000, the time required for dissolution in water tends to increase. Further, when the degree of saponification is less than 70 mol%, it is difficult to uniformly dissolve in water.
ビニルピロリドンの量は、ポリビニルアルコールに対して５〜９００重量％であることが好ましい。５重量％未満であると本発明の目的とする効果が十分に得られず、９００重量％を超えると得られたグラフト重合体をインクジェット記録用媒体に使用した場合に、耐水性が低下する傾向がある。 The amount of vinylpyrrolidone is preferably 5 to 900% by weight with respect to polyvinyl alcohol. When the amount is less than 5% by weight, the intended effect of the present invention cannot be sufficiently obtained, and when the amount exceeds 900% by weight, the water resistance tends to decrease when the obtained graft polymer is used in an ink jet recording medium. There is.
開始剤としてはラジカル重合に通常用いられる過酸化水素又は有機過酸化物を用いることができる。有機過酸化物の例としては、ｔｅｒｔ−ブチルハイドロパーオキシド、ジ−ｔｅｒｔ−ブチルパーオキシド、ベンゾイルパーオキシド等が挙げられる。 As the initiator, hydrogen peroxide or organic peroxide usually used for radical polymerization can be used. Examples of the organic peroxide include tert-butyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide and the like.
反応方法及び反応条件は一般的なラジカル重合の例に従って選択すればよい。 What is necessary is just to select the reaction method and reaction conditions according to the example of general radical polymerization.
上記により得られる本発明のポリビニルアルコール変性グラフト重合体はＫ値が１２〜１５０であることが好ましい。Ｋ値とは、ドイツの化学者フィケンチャーにより提案された重合度を表わす定数であり、Ｋ値がこれより小さいと、インクジェット記録用媒体に使用した場合に耐水性が低下し、Ｋ値がこれより大きいと水への溶解性が悪化する。 The polyvinyl alcohol-modified graft polymer of the present invention obtained as described above preferably has a K value of 12 to 150. The K value is a constant representing the degree of polymerization proposed by German chemist Fikencher. If the K value is smaller than this, the water resistance decreases when used in an ink jet recording medium, and the K value is lower than this. If it is large, the solubility in water deteriorates.
本発明のインクジェット記録用媒体は、上記本発明のポリビニルアルコール変性グラフト重合体を含有してなるものであり、より具体的には紙又は樹脂フィルム等の基材に、ポリビニルアルコール変性グラフト重合体を含む塗工液を塗布し、乾燥させて得られるものである。塗布及び乾燥方法としては公知の種々の方法が利用できる。 The inkjet recording medium of the present invention comprises the polyvinyl alcohol-modified graft polymer of the present invention. More specifically, the polyvinyl alcohol-modified graft polymer is applied to a substrate such as paper or a resin film. It is obtained by applying a coating liquid containing it and drying it. Various known methods can be used as the coating and drying method.
塗工液にはポリビニルアルコール変性グラフト重合体の他に、シリカ、アルミナ、タルク、カオリンクレー、炭酸カルシウム、雲母等の無機フィラー、ポリアクリル酸メチル、ポリスチレン系、ポリアクリロニトリル系等の有機フィラー、チタン系やクロム系の無機顔料や有機顔料、ブロッキング防止剤、帯電防止剤、紫外線吸収剤、抗酸化剤、インク定着剤等の公知の添加剤を必要に応じて含有させることができる。 In addition to polyvinyl alcohol-modified graft polymer, the coating solution includes inorganic fillers such as silica, alumina, talc, kaolin clay, calcium carbonate, mica, organic fillers such as polymethyl acrylate, polystyrene, polyacrylonitrile, titanium, etc. Known additives such as organic and chromium inorganic pigments and organic pigments, antiblocking agents, antistatic agents, ultraviolet absorbers, antioxidants, and ink fixing agents can be contained as necessary.
塗工液中のポリビニルアルコール変性グラフト重合体の含有量は特に限定されるものではないが、通常は１．０〜１０重量％（固形分換算）程度である。また、塗工液の塗布量も特に限定されるものではないが、通常は１．００〜１００ｇ／ｍ２（固形分換算）程度である。 The content of the polyvinyl alcohol-modified graft polymer in the coating liquid is not particularly limited, but is usually about 1.0 to 10% by weight (solid content conversion). Moreover, although the application quantity of a coating liquid is not specifically limited, Usually, it is about 1.00-100 g / m < 2 > (solid content conversion) grade.
以下に、本発明の実施例を示すが、本発明は以下の実施例によって限定されるものではない。 Examples of the present invention are shown below, but the present invention is not limited to the following examples.
［実施例１］
純水７００ｇにポリビニルアルコール（ＰＶＡ）（（株）クラレ製、ＰＶＡ−１０２、重合度２００、ケン化度９８〜９９モル％）２８５ｇを溶解させた。次いでビニルピロリドン（ＶＰ）１５．０ｇ（対ＰＶＡ ５．２６重量％）を添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を２５℃に温度調節した。これに１重量％硫酸銅０．７５０ｍｇ（対ＶＰ ０．５ｐｐｍ）、２８重量％アンモニア水７５．０ｍｇ（対ＶＰ ０．１４重量％）及び３０重量％過酸化水素水３５０ｍｇ（対ＶＰ ０．７重量％）を添加し、重合を開始させた。反応熱により系の温度が上昇するが、冷却又は加温により温度を８０±２℃に調節し、その後８０±２℃を維持した。残存モノマー濃度が５０００ｐｐｍ以下になったことを確認した後（重合開始約９０分後）、３０重量％過酸化水素水１７５ｍｇ（対ＶＰ ０．３５重量％）を添加し、残存モノマー処理工程を開始した。この時、アンモニア水によりｐＨ４．５〜６．５に保持した。合計２１０分間重合させた後、スプレー乾燥を行い、粉末状重合物１を得た。粉末状重合物１は、１３Ｃ−ＮＭＲ測定により、ポリビニルアルコール主鎖の水酸基及びエステル基に結合する炭素にグラフトすることによって生成した４級炭素のピークを化学シフト５３ｐｐｍ及び５８ｐｐｍ付近に確認することにより、ポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認された。また、粉末状重合物１は、固形分９７．１％、Ｋ値２３であった。
[Example 1]
In 700 g of pure water, 285 g of polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd., PVA-102, polymerization degree 200, saponification degree 98 to 99 mol%) was dissolved. Next, 15.0 g of vinylpyrrolidone (VP) (5.26% by weight of PVA) was added, mixed, and deoxygenated by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 25 ° C. 1 wt% copper sulfate 0.750 mg (vs 0.5 ppm), 28 wt% ammonia water 75.0 mg (vs VP 0.14 wt%) and 30 wt% hydrogen peroxide water 350 mg (vs VP 0.7 Wt%) was added to initiate the polymerization. Although the temperature of the system increased due to the heat of reaction, the temperature was adjusted to 80 ± 2 ° C. by cooling or heating, and then maintained at 80 ± 2 ° C. After confirming that the residual monomer concentration was 5000 ppm or less (about 90 minutes after the start of polymerization), 175 mg of 30% by weight hydrogen peroxide water (0.35% by weight with respect to VP) was added to start the residual monomer treatment process. did. At this time, the pH was maintained at 4.5 to 6.5 with aqueous ammonia. After polymerization for a total of 210 minutes, spray drying was performed to obtain a powdery polymer 1. The powdered polymer 1 is confirmed by 13 C-NMR measurement to confirm the peak of the quaternary carbon produced by grafting to the carbon bonded to the hydroxyl group and ester group of the polyvinyl alcohol main chain at around 53 ppm and 58 ppm of chemical shift. Thus, it was confirmed that vinyl pyrrolidone was graft polymerized with polyvinyl alcohol. In addition, the powdered polymer 1 had a solid content of 97.1% and a K value of 23.
［実施例２］
純水７００ｇにポリビニルアルコール（ＰＶＡ）（（株）クラレ製、ＰＶＡ−１２４、重合度２４００、ケン化度９８〜９９モル％）２１０ｇを溶解させた。次いでビニルピロリドン（ＶＰ）９０．０ｇ（対ＰＶＡ４２．９重量％）を添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を２５℃に温度調節した。これに１重量％硫酸銅を４．５０ｍｇ（対ＶＰ ０．５０ｐｐｍ）、２８重量％アンモニア水４５０ｍｇ（対ＶＰ ０．１４重量％）及び３０重量％過酸化水素水２１００ｍｇ（対ＶＰ ０．７０重量％）を添加し、重合を開始させた。反応熱により系の温度が上昇するが、冷却又は加温により温度を８０±２℃に調節し、その後８０±２℃を維持した。残存モノマー濃度が５０００ｐｐｍ以下になったことを確認した後（重合開始約９０分後）、３０重量％過酸化水素水１０５０ｍｇ（対ＶＰ ０．３５重量％）を添加し、残存モノマー処理工程を開始した。この時、アンモニア水によりｐＨ４．５〜６．５に保持した。合計２１０分間重合させた後、ホットプレートで乾燥を行い、粉末状重合物２を得た。粉末状重合物２は、実施例１と同じ１３Ｃ−ＮＭＲ測定を用いた方法によりポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認された。また、粉末状重合物は、固形分９８．５％、Ｋ値３１であった。
[Example 2]
210 g of polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd., PVA-124, polymerization degree 2400, saponification degree 98 to 99 mol%) was dissolved in 700 g of pure water. Subsequently, 90.0 g of vinyl pyrrolidone (VP) (42.9% by weight of PVA with respect to PVA) was added, mixed, and deoxygenated by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 25 ° C. To this, 4.50 mg (vs. 0.50 ppm) of 1 wt% copper sulfate, 450 mg of 28 wt% aqueous ammonia (vs. 0.14 wt%), and 2100 mg of 30 wt% aqueous hydrogen peroxide (vs. 0.70 wt. Vs. VP). %) Was added to initiate the polymerization. Although the temperature of the system increased due to the heat of reaction, the temperature was adjusted to 80 ± 2 ° C. by cooling or warming, and then maintained at 80 ± 2 ° C. After confirming that the residual monomer concentration was 5000 ppm or less (about 90 minutes after the start of polymerization), 1050 mg of 30 wt% hydrogen peroxide solution (0.35 wt% with respect to VP) was added to start the residual monomer treatment process. did. At this time, the pH was maintained at 4.5 to 6.5 with aqueous ammonia. After polymerization for a total of 210 minutes, drying was performed on a hot plate to obtain a powdery polymer 2. It was confirmed that the powdery polymer 2 was obtained by graft polymerization of vinyl pyrrolidone to polyvinyl alcohol by the same method using 13 C-NMR measurement as in Example 1. The powdery polymer had a solid content of 98.5% and a K value of 31.
［実施例３］
純水７００ｇにポリビニルアルコール（ＰＶＡ）（（株）クラレ製、ＰＶＡ−５０５、重合度５００、ケン化度７２．５〜７４．５モル％）１２０ｇを溶解させた。次いでビニルピロリドン（ＶＰ）１８０ｇ（対ＰＶＡ １５０重量％）を添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を３０℃に温度調節した。これに２０重量％亜硫酸アンモニウム水溶液９．００ｇ（対ＶＰ １．００重量％）及び２０重量％ｔｅｒｔ−ブチルハイドロパーオキシド水溶液２．７０ｇ（対ＶＰ ０．３０重量％）を添加し、重合を開始させた。３時間後、重合液温度を８０±２℃に調節した。２０重量％亜硫酸アンモニウム水溶液４．５０ｇ（対ＶＰ ０．５０重量％）及び２０重量％ｔｅｒｔ−ブチルハイドロパーオキシド水溶液４．５０ｇ（対ＶＰ ０．５０重量％）を添加し、さらに３時間重合を行った。その後スプレー乾燥を行い、粉末状重合物３を得た。粉末状重合物３は、実施例１と同じ１３Ｃ−ＮＭＲ測定を用いた方法によりポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認された。また、粉末状重合物は、固形分９６．３％、Ｋ値４０であった。
[Example 3]
120 g of polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd., PVA-505, polymerization degree 500, saponification degree 72.5 to 74.5 mol%) was dissolved in 700 g of pure water. Next, 180 g of vinyl pyrrolidone (VP) (150% by weight of PVA with respect to PVA) was added, mixed, and deoxygenated by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 30 ° C. To this was added 9.00 g of a 20% by weight ammonium sulfite aqueous solution (based on 1.00% by weight of VP) and 2.70 g of a 20% by weight aqueous solution of tert-butyl hydroperoxide (based on 0.30% by weight of VP) to initiate polymerization. I let you. After 3 hours, the temperature of the polymerization solution was adjusted to 80 ± 2 ° C. 4.50 g of 20% by weight ammonium sulfite aqueous solution (with respect to VP 0.50% by weight) and 4.50 g of 20% by weight aqueous solution of tert-butyl hydroperoxide (with respect to VP 0.50% by weight) were added, and polymerization was conducted for another 3 hours. went. Thereafter, spray drying was performed to obtain a powdery polymer 3. It was confirmed that the powdery polymer 3 was obtained by graft polymerization of vinyl pyrrolidone to polyvinyl alcohol by the same method as in Example 1 using 13 C-NMR measurement. The powdery polymer had a solid content of 96.3% and a K value of 40.
［実施例４］
純水７００ｇにポリビニルアルコール（ＰＶＡ）（（株）クラレ製、ＰＶＡ−２３５、重合度３５００、ケン化度８７〜８９モル％）３０．０ｇを溶解させた。次いでビニルピロリドン（ＶＰ）２７０ｇ（対ＰＶＡ ９００重量％）を添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を６０℃に温度調節した。これに２０重量％亜硫酸アンモニウム水溶液０．６７５ｇ（対ＶＰ ０．０５重量％）及び２０重量％ｔｅｒｔ−ブチルハイドロパーオキシド水溶液０．６７５ｇ（対ＶＰ ０．０５重量％）を添加し、重合を開始させた。３時間後、２０重量％亜硫酸アンモニウム水溶液４．０５ｇ（対ＶＰ ０．３０重量％）及び２０重量％ｔｅｒｔ−ブチルハイドロパーオキシド水溶液２．７０ｇ（対ＶＰ ０．２０重量％）を添加し、さらに３時間重合を行った。その後ホットプレートにて乾燥を行い、粉末状重合物４を得た。粉末状重合物４は、実施例１と同じ１３Ｃ−ＮＭＲ測定を用いた方法によりポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認された。また、粉末状重合物４は、固形分９９．０％、Ｋ値９４であった。
[Example 4]
30.0 g of polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd., PVA-235, polymerization degree 3500, saponification degree 87 to 89 mol%) was dissolved in 700 g of pure water. Next, 270 g of vinylpyrrolidone (VP) (900% by weight of PVA with respect to PVA) was added, mixed, and deoxygenated by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 60 ° C. To this was added 0.675 g of 20 wt% ammonium sulfite aqueous solution (0.05 wt% of VP) and 0.675 g of 20 wt% aqueous solution of tert-butyl hydroperoxide (0.05 wt% of VP) to initiate polymerization. I let you. After 3 hours, 4.05 g of a 20 wt% aqueous ammonium sulfite solution (0.30 wt% of VP) and 2.70 g of a 20 wt% aqueous solution of tert-butyl hydroperoxide (0.20 wt% of VP) were added. Polymerization was performed for 3 hours. Thereafter, drying was performed on a hot plate to obtain a powdery polymer 4. It was confirmed that the powdery polymer 4 was obtained by graft polymerization of vinyl pyrrolidone to polyvinyl alcohol by the same method using 13 C-NMR measurement as in Example 1. In addition, the powdered polymer 4 had a solid content of 99.0% and a K value of 94.
［比較例１］
ポリビニルアルコール（（株）クラレ製、ＰＶＡ−２３５、重合度３５００、ケン化度８７〜８９モル％）を粉末状重合物５とした。
[Comparative Example 1]
Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235, polymerization degree 3500, saponification degree 87 to 89 mol%) was designated as powdered polymer 5.
［比較例２］
ビニルピロリドン（ＶＰ）３００ｋｇ（対水溶液３０．０重量％）及び水７００ｋｇを混合し、窒素パージにより脱酸素を行った。続いて、反応系を２５℃に温度調節した。これに１重量％硫酸銅を１５．０ｍｇ（対ＶＰ ０．５００ｐｐｍ）、２８重量％アンモニア水１．５０ｇ（対ＶＰ ０．１４０重量％）及び３０重量％過酸化水素水７．００ｇ（対ＶＰ ０．７００重量％）を添加し、重合を開始させた。反応熱により系の温度が上昇するが、冷却又は加温により温度を８０±２℃に調節し、その後８０±２℃を維持した。残存モノマー濃度が５０００ｐｐｍ以下になったことを確認した後（重合開始約９０分後）、３０重量％過酸化水素水３．５０ｇ（対ＶＰ ０．３５０重量％）を添加し、残存モノマー処理工程を開始した。この時、アンモニア水によりｐＨ４．５〜６．５に保持した。合計２１０分間重合させた後、スプレー乾燥を行い、粉末状重合物６を得た。粉末状重合物６は、固形分９６．８％、Ｋ値３０であった。
[Comparative Example 2]
300 kg of vinyl pyrrolidone (VP) (30.0% by weight with respect to the aqueous solution) and 700 kg of water were mixed and deoxygenated by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 25 ° C. 15.0 mg of 1 wt% copper sulfate (vs. 0.500 ppm), 1.50 g of 28 wt% aqueous ammonia (vs. 0.140 wt% of VP) and 7.00 g of 30 wt% hydrogen peroxide (vs. VP) 0.700% by weight) was added to initiate the polymerization. Although the temperature of the system increased due to the heat of reaction, the temperature was adjusted to 80 ± 2 ° C. by cooling or heating, and then maintained at 80 ± 2 ° C. After confirming that the residual monomer concentration was 5000 ppm or less (about 90 minutes after the start of polymerization), 3.50 g of 30% by weight hydrogen peroxide (vs. 0.350% by weight of VP) was added, and the residual monomer treatment step Started. At this time, the pH was maintained at 4.5 to 6.5 with aqueous ammonia. After polymerization for a total of 210 minutes, spray drying was performed to obtain a powdery polymer 6. The powdery polymer 6 had a solid content of 96.8% and a K value of 30.
［比較例３］
純水７００ｇにポリビニルアルコール（ＰＶＡ）（（株）クラレ製、ＰＶＡ−１２４、重合度２４００、ケン化度９８〜９９モル％）２１０ｇを溶解させた。次いで比較例２で得られた粉末重合物５９０．０ｇ（対ＰＶＡ ４２．９重量％）を添加、溶解させ、その後スプレー乾燥を行い、粉末状重合物７を得た。粉末状重合物７は、固形分９７．２％、Ｋ値３０であった。
[Comparative Example 3]
210 g of polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd., PVA-124, polymerization degree 2400, saponification degree 98 to 99 mol%) was dissolved in 700 g of pure water. Next, 590.0 g (42.9% by weight of PVA) of the powder polymer obtained in Comparative Example 2 was added and dissolved, followed by spray drying to obtain a powdery polymer 7. The powdery polymer 7 had a solid content of 97.2% and a K value of 30.
なお、上記実施例・比較例で得られた粉末状重合物の固形分及びＫ値は、次の方法で測定した；
固形分：重合により得られたポリマー水溶液約５ｇを精秤し、１０５℃で１２時間乾燥し、蒸発残分を固形分として算出した。
Ｋ値：Ｆｉｋｅｎｔｓｃｈｅｒ法により測定した。
In addition, solid content and K value of the powdery polymer obtained in the above Examples and Comparative Examples were measured by the following methods;
Solid content: About 5 g of an aqueous polymer solution obtained by polymerization was precisely weighed and dried at 105 ° C. for 12 hours, and the evaporation residue was calculated as a solid content.
K value: Measured by the Fikentscher method.
また、これら粉末状重合物１〜７の水に対する溶解性を評価し、結果を表１に示した。すなわち、水１００ｇをスターラーにて撹拌しながら、得られた粉末状重合物を１ｇ添加し、外観上完全に溶解したと認められるまでの時間を測定し、次の基準で評価した；
１分未満 … ○、
１分以上１０分未満 … ×、
１０分以上 …××。
Moreover, the solubility with respect to the water of these powdery polymers 1-7 was evaluated, and the result was shown in Table 1. That is, while stirring 100 g of water with a stirrer, 1 g of the obtained powdered polymer was added, and the time until it was recognized that it was completely dissolved in appearance was measured and evaluated according to the following criteria:
Less than 1 minute… ○,
1 minute to less than 10 minutes… ×,
10 minutes or more… XX.
さらに、実施例・比較例で得られた粉末状重合物１〜７を用いて以下の方法で塗工液を調製して、塗工し、色の鮮やかさ及び塗膜強度を評価し、結果を表１に示した。 Furthermore, using the powdered polymers 1 to 7 obtained in Examples and Comparative Examples, a coating solution was prepared by the following method, applied, evaluated for color vividness and coating strength, and results Is shown in Table 1.
１．塗工液調製方法
得られた粉末状重合物１〜７、シリカ（（株）トクヤマ製、ファインシールＸ−３７Ｂ）、インク定着剤としてのポリジアリルジメチルアンモニウムクロリド（第一工業製薬（株）製、シャロールＤＣ９０２Ｐ）を重量比３０：１００：１０で混合し、最終固形分１５％となるように水を加え、ホモミキサーにて４０００〜５０００ｒｐｍで２分間撹拌した。
1. Coating liquid preparation method The obtained powdery polymers 1 to 7, silica (manufactured by Tokuyama Co., Ltd., Fine Seal X-37B), polydiallyldimethylammonium chloride as an ink fixing agent (Daiichi Kogyo Seiyaku Co., Ltd.) , Charol DC902P) was mixed at a weight ratio of 30: 100: 10, water was added so that the final solid content was 15%, and the mixture was stirred for 2 minutes at 4000 to 5000 rpm with a homomixer.
２．塗工方法
バーコーターにてケント紙に１０ｇ／ｍ２（固形分換算）塗工後、オーブンにて１０５℃で５分間乾燥を行った。
2. Coating method After coating at 10 g / m 2 (in terms of solid content) on Kent paper with a bar coater, drying was performed at 105 ° C. for 5 minutes in an oven.
３．評価方法
色の鮮やかさ及び塗膜強度を、次の方法で評価した。
3. Evaluation method The color vividness and the coating film strength were evaluated by the following methods.
色の鮮やかさ：プリンターとしてＥＰＳＯＮ製ＰＭ−７７０Ｃを使用し、シアン（Ｃ）、マゼンダ（Ｍ）、イエロー（Ｙ）及びブラック（Ｂ）をべた塗り印刷し、反射濃度計ＲＤ−１９Ｔ（サカタインクスエンジニアリング（株）製）で色濃度を測定し、次の基準で評価した；
色濃度がいずれも２．００以上であった … ○、
いずれかの色濃度において２．００未満があった … ×。
Color vividness: Using PM-770C manufactured by EPSON as the printer, cyan (C), magenta (M), yellow (Y), and black (B) were solidly printed, and reflection densitometer RD-19T (Sakata Inx Engineering) Measured by the following standards:
The color density was 2.00 or higher.
There was less than 2.00 at any color density.
塗膜強度：印字部に粘着テープを貼った後、剥がし、その部分の剥がれ具合から、次の基準で評価した；
剥がれなかった … ○、
一部剥がれた … ×。
Coating film strength: After sticking an adhesive tape on the printed part, it was peeled off and evaluated according to the following criteria from the degree of peeling of the part;
It did not come off… ○,
Some peeled off.
表１に示された結果から分かるように、本発明のポリビニルアルコール変性グラフト重合体は、ポリビニルアルコール単独又はポリビニルアルコールとビニルピロリドンとの混合物と比較して、水への溶解性に優れ、またこれを含有するインクジェット記録用媒体は、特に印刷の色の鮮明性において優れたものとなる。 As can be seen from the results shown in Table 1, the polyvinyl alcohol-modified graft polymer of the present invention is superior in solubility in water as compared with polyvinyl alcohol alone or a mixture of polyvinyl alcohol and vinyl pyrrolidone. The ink jet recording medium containing the ink is particularly excellent in the color clarity of printing.
本発明のポリビニルアルコール変性グラフト重合体は、繊維加工剤、紙加工剤、接着剤、無機物のバインダー等、従来ポリビニルアルコールが利用されてきた広い範囲で利用可能であり、特にインクジェット記録用媒体に好適に用いられる。
The polyvinyl alcohol-modified graft polymer of the present invention can be used in a wide range where polyvinyl alcohol has been conventionally used, such as fiber processing agents, paper processing agents, adhesives, inorganic binders, etc., and is particularly suitable for inkjet recording media. Used for.
Claims (3)
An inkjet recording medium comprising the polyvinyl alcohol-modified graft polymer according to claim 1.
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| JP2009108111A (en) * | 2007-10-26 | 2009-05-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Metal surface-treating agent |
| WO2010084896A1 (en) * | 2009-01-21 | 2010-07-29 | 日本パーカライジング株式会社 | Hydrophilizing agent for aluminum-containing metal material, hydrophilizing method, and hydrophilized aluminum-containing metal material |
| JP5503556B2 (en) * | 2009-01-21 | 2014-05-28 | 日本パーカライジング株式会社 | Hydrophilic treatment agent for aluminum-containing metal material, hydrophilic treatment method, and hydrophilized aluminum-containing metal material |
| KR101441176B1 (en) * | 2009-01-21 | 2014-09-17 | 니혼 파커라이징 가부시키가이샤 | Hydrophilizing agent for aluminum-containing metal material, hydrophilizing method, and hydrophilized aluminum-containing metal material |
| WO2017138581A1 (en) * | 2016-02-10 | 2017-08-17 | 株式会社クラレ | Powder comprising graft copolymer, and method for producing said powder |
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