JP2004285143A5 - - Google Patents

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JP2004285143A5
JP2004285143A5 JP2003077211A JP2003077211A JP2004285143A5 JP 2004285143 A5 JP2004285143 A5 JP 2004285143A5 JP 2003077211 A JP2003077211 A JP 2003077211A JP 2003077211 A JP2003077211 A JP 2003077211A JP 2004285143 A5 JP2004285143 A5 JP 2004285143A5
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polyvinyl alcohol
side chain
glycol bond
based resin
mol
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JP2003077211A
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JP2004285143A (en )
JP4079806B2 (en )
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上記のビニルエステル系モノマーと3,4−ジアセトキシ−1−ブテン(さらには他のモノマー)を共重合するに当たっては、特に制限はなく、塊状重合、溶液重合、懸濁重合、分散重合、またはエマルジョン重合等の公知の方法を採用することができるが、通常は溶液重合が行われる。 The above vinyl ester-based monomer 3,4-diacetoxy-1-butene (and other monomers) is when copolymerizing is not particularly limited, bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, or emulsion can be employed a known method such as polymerization, usually solution polymerization is conducted.
共重合時のモノマー成分の仕込み方法としては特に制限されず、一括仕込み、分割仕込み、連続仕込み等任意の方法が採用されるが、3,4−ジアセトキシ−1−ブテンがポリビニルエステル系ポリマーの分子鎖中に均一に分布させられる、架橋剤との反応性が向上する、ポリビニルアルコールの融点が降下する等の物性面から滴下重合が好ましく、特にはHANNA法に基づく重合方法が好ましい。 There are no particular limitations on the charging method of the monomer components during the copolymerization, batch charging, divided charging, Although any methods such as continuous charging is employed, 3,4-diacetoxy-1-butene of the polyvinyl ester-based polymer molecule brought uniformly distributed in the chain, thereby improving the reactivity with the crosslinking agent, physical properties or et dropping polymerization, such as the melting point of the polyvinyl alcohol falls are preferred, the polymerization method based on HANNA method is preferred.

また、ポリビニルアルコール系樹脂中に導入される1,2−グリコール結合量としては特に制限はされないが、0.1〜40モル%(さらには0.1〜20モル%、特には1〜15モル%)で、かかる導入量が0.1モル%未満では架橋剤等を併用して用いたときに架橋剤との反応性が低く、また水溶液としたときの粘度安定性が低下する傾向にあり、さらには水溶液を高速塗工用途に供したときにはその塗工性も低下して好ましくなく、逆に40モル%を越えるとポリビニルアルコール系樹脂の重合度が低くなりすぎる傾向にあり好ましくない。 In particular limitation is imposed on the 1,2-glycol bond amount is introduced into the polyvinyl alcohol resin are not limited to, 0.1 to 40 mol% (further 0.1 to 20 mol%, particularly 1 to 15 moles in%), such introduction amount is less than 0.1 mole% tends to have low reactivity with the crosslinking agent and the viscosity stability when the aqueous solution decreased when used in combination with crosslinking agent , more unfavorably decreases also its coating property when subjected to an aqueous solution at a high speed coating applications, when it exceeds 40 mol% on the contrary tend to polymerization degree of the polyvinyl alcohol resin is too low is not preferable.
特に、本発明においては、前述のように1,2−グリコール結合量を7モル%以上の如く多量導入する場合でも、工業的な実施には何の支障もなく、その製造が容易にでき、しかも導入量の高いポリビニルアルコール系樹脂は、さらに結晶性が低下して、水溶解性が容易となったり、また著しくポリビニルアルコール系樹脂の水溶液安定性にも優れ、かつ該ポリビニルアルコール系樹脂から得られるフィルムは、アルカリ下に長期期間放置されても水溶解性は低下することがないという特徴を有するため、アルカリ洗剤包装等の水溶性包装材用途に有用である。 Particularly, in the present invention, even when a large amount introduced as 1,2-glycol bond content of more than 7 mol%, as described above, the industrial practice without any trouble, the production can be easily, Moreover high polyvinyl alcohol resin having introduction amount is further reduced crystallinity, or become water soluble and easily, also excellent in significantly aqueous stability of the polyvinyl alcohol-based resin, and obtained from the polyvinyl alcohol resin is the film, since it has a characteristic that does not decrease the water solubility is left long period under alkaline, useful in water-soluble packaging applications, such as alkaline detergent packaging. また一方では、1,2−グリコール結合は1級水酸基を持ち、その導入量も大幅に向上することができるため、水性ビニルウレタン接着剤用途等に供した場合には、接着強度を大幅に向上させることができ、木工接着、特に針葉樹合板等の接着剤用途に有用である。 On the one hand also 1,2-glycol bond has a primary hydroxyl group, it is possible to also greatly improve the quantity incorporated, when subjected to an aqueous vinyl urethane adhesive applications, etc., greatly improve the adhesive strength it is to be able, woodworking adhesive, which is particularly useful for adhesive applications, such as softwood plywood.
また、本発明のポリビニルアルコール系樹脂は、ケン化度が99モル%前後の高鹸化度であっても融点が低いため、エチレン−酢酸ビニル共重合体(酢酸ビニル含有量1〜40重量%程度)等のオレフィン系樹脂に相溶化剤(マレイン酸変性の各種オレフィン系樹脂等)と共にブレンドする場合、容易に溶融ブレンドすることができ、例えばエチレン−酢酸ビニル共重合体に対して、本発明のポリビニルアルコール系樹脂を20重量%程度ブレンドすることで、塩ビフィルムと同等の保温性をもった農業用フィルムを得ることができる等の有用性も有している。 The polyvinyl alcohol resin of the present invention, since the degree of saponification is low melting point even at high saponification degree of about 99 mol%, ethylene - vinyl acetate copolymer (vinyl acetate content 40 wt% or so when blending olefinic resin to compatibilizer with (such as maleic acid-modified various olefin resins)) of such, it can be easily melt blending, for example, ethylene - the vinyl acetate copolymer, of the present invention a polyvinyl alcohol-based resin by blending about 20% by weight, also has utility such as can be obtained the agricultural film having the same warmth and PVC film.

Claims (8)

  1. ビニルエステル系モノマーと3,4−ジアセトキシ−1−ブテンとの共重合体をケン化して得られたことを特徴とする側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂。 Vinyl ester-based monomer and 3,4-diacetoxy-1-butene, a copolymer of polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain, characterized in that obtained by saponifying.
  2. ケン化度が99.0モル%以上であることを特徴とする請求項1記載の側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂。 Saponification degree polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain of claim 1, wherein a is 99.0 mol% or more.
  3. ケン化度が99.0モル%未満であることを特徴とする請求項1記載の側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂。 Saponification degree polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain of claim 1, wherein less than 99.0 mol%.
  4. 3,4−ジアセトキシ−1−ブテンの共重合割合が0.1〜20モル%であることを特徴とする請求項1〜3いずれか記載の側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂。 Polyvinyl alcohol having a 1,2-glycol bond to claims 1 to 3 the side chain of any one of copolymerization ratio of 3,4-diacetoxy-1-butene, characterized in that 0.1 to 20 mol% system resin.
  5. ビニルエステル系モノマーと3,4−ジアセトキシ−1−ブテンとの共重合体をケン化することを特徴とする側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂の製造方法。 Method for producing a polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain, which comprises saponifying a copolymer of vinyl ester monomer and 3,4-diacetoxy-1-butene.
  6. ケン化度が99.0モル%以上であることを特徴とする請求項記載の側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂の製造方法。 Method for producing a polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain according to claim 5, wherein the saponification degree is 99.0 mol% or more.
  7. ケン化度が99.0モル%未満であることを特徴とする請求項記載の側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂の製造方法。 Method for producing a polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain according to claim 5, wherein the saponification degree is less than 99.0 mol%.
  8. 3,4−ジアセトキシ−1−ブテンの共重合割合が0.1〜20モル%であることを特徴とする請求項5〜7いずれか記載の側鎖に1,2−グリコール結合を有するポリビニルアルコール系樹脂の製造方法。 Polyvinyl alcohol having a claim 5-7 1,2-glycol bond in a side chain according to any one of copolymerization ratio of 3,4-diacetoxy-1-butene, characterized in that 0.1 to 20 mol% method for producing a system resin.
JP2003077211A 2003-03-20 2003-03-20 Polyvinyl alcohol resin and a manufacturing method thereof having a 1,2-glycol bond in a side chain Active JP4079806B2 (en)

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JP2003077211A JP4079806B2 (en) 2003-03-20 2003-03-20 Polyvinyl alcohol resin and a manufacturing method thereof having a 1,2-glycol bond in a side chain

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JP2003077211A JP4079806B2 (en) 2003-03-20 2003-03-20 Polyvinyl alcohol resin and a manufacturing method thereof having a 1,2-glycol bond in a side chain

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JP2004285143A true JP2004285143A (en) 2004-10-14
JP2004285143A5 true true JP2004285143A5 (en) 2006-04-06
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Families Citing this family (31)

* Cited by examiner, † Cited by third party
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US7915341B2 (en) 2004-06-10 2011-03-29 The Nippon Synthetic Chemical Industry Co., Ltd. Ethylene-vinyl alcohol copolymer and molded article thereof
ES2381886T3 (en) * 2004-06-10 2012-06-01 The Nippon Synthetic Chemical Industry Co., Ltd. Ethylene / vinyl alcohol and molded article therefrom
DE602004029617D1 (en) 2004-08-18 2010-11-25 Nippon Synthetic Chem Ind Polyvinyl alcohol having 1,2-glycol bond in the side chain, and production method thereof
WO2006035516A1 (en) * 2004-09-28 2006-04-06 The Nippon Synthetic Chemical Industry Co., Ltd. Ethylene/vinyl alcohol copolymer composition and multilayer structure comprising the same
JP4498872B2 (en) * 2004-09-28 2010-07-07 日本合成化学工業株式会社 Solution and laminates
JP4761945B2 (en) * 2005-01-31 2011-08-31 日本合成化学工業株式会社 Polarizing film for polyvinyl alcohol-based film and a polarizing film, a polarizing plate
JP5000127B2 (en) * 2005-01-31 2012-08-15 日本合成化学工業株式会社 Optical polyvinyl alcohol-based film and a polarizing film, a polarizing plate
JP5288683B2 (en) * 2005-02-02 2013-09-11 日本合成化学工業株式会社 A dispersion stabilizer for suspension polymerization of a vinyl compound
JP2006257225A (en) * 2005-03-16 2006-09-28 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based film and its application
JP4520887B2 (en) * 2005-03-22 2010-08-11 日本合成化学工業株式会社 Heat-sensitive recording medium
JP5078268B2 (en) * 2005-03-22 2012-11-21 日本合成化学工業株式会社 RESIN COMPOSITION AND USE THEREOF
JP4883281B2 (en) * 2005-04-05 2012-02-22 日本合成化学工業株式会社 Laminated structure
JP4968657B2 (en) * 2005-07-28 2012-07-04 日本合成化学工業株式会社 Hydrogel
JP4634893B2 (en) * 2005-09-02 2011-02-23 日本合成化学工業株式会社 Electrolyte for an electric double layer capacitor
JP5006061B2 (en) 2006-02-07 2012-08-22 日本合成化学工業株式会社 Water-soluble polyvinyl alcohol resin long fiber nonwoven fabric
EP2006308B1 (en) 2006-04-05 2010-09-01 The Nippon Synthetic Chemical Industry Co., Ltd. Polyvinyl acetal-based resin
WO2007129368A1 (en) * 2006-04-25 2007-11-15 The Nippon Synthetic Chemical Industry Co., Ltd. Resin composition and multilayer structure making use of the same
JP2008050574A (en) * 2006-07-24 2008-03-06 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based film for optical use, polarizing film and polarizing plate
CN101528817B (en) 2006-07-27 2012-11-28 日本合成化学工业株式会社 Polyvinyl alcohol-based film for optical uses and polarizing membrane and polarizing plate
EP2058342B1 (en) * 2006-08-01 2011-05-11 The Nippon Synthetic Chemical Industry Co., Ltd. Dispersion stabilizer for suspension polymerization of vinyl-based compound
JP5089106B2 (en) * 2006-08-21 2012-12-05 日本合成化学工業株式会社 Glass laminate
RU2009148679A (en) * 2007-07-10 2011-08-20 Де Ниппон Синтетик Кемикал Индастри Ко., Лтд. (JP) The aqueous synthetic resin emulsion for a cement additive in the solution, re-emulsifiable powder additive into the slurry of the aqueous synthetic resin emulsion and an additive in a cement slurry comprising said emulsion or said powder
JP5235364B2 (en) * 2007-09-05 2013-07-10 日本合成化学工業株式会社 The method of producing a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain
JP5091011B2 (en) * 2008-05-29 2012-12-05 日本合成化学工業株式会社 Hair styling agents
JP5241619B2 (en) * 2009-06-08 2013-07-17 日本合成化学工業株式会社 Alkaline aqueous composition, and surface treatment coating solution containing the same
CN102443319B (en) * 2011-10-24 2014-04-02 北京高盟新材料股份有限公司 Alcohol water-soluble amino modified vinyl acetate-acrylic system ink connecting material and preparation method thereof
JP6110678B2 (en) * 2012-02-10 2017-04-05 株式会社クラレ Hydroxymethyl-group-containing vinyl alcohol polymer
WO2014021422A1 (en) 2012-08-02 2014-02-06 日本合成化学工業株式会社 High-pressure gas hose or storage vessel
JP6338451B2 (en) 2013-05-28 2018-06-06 日本合成化学工業株式会社 Coating composition and the coating film obtained from it, a method for manufacturing a multilayer structure and the multilayer structure
JP6193723B2 (en) * 2013-10-25 2017-09-06 日本酢ビ・ポバール株式会社 Polyvinyl alcohol resin and a manufacturing method thereof in the main chain 1,2,3-triol group
JPWO2016027720A1 (en) * 2014-08-20 2017-06-01 日本合成化学工業株式会社 Pesticide dispersant and agrochemical dispersions using the same

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