JPS6195053A - Production of polyvinyl alcohol polymer with high thermal stability - Google Patents
Production of polyvinyl alcohol polymer with high thermal stabilityInfo
- Publication number
- JPS6195053A JPS6195053A JP21408985A JP21408985A JPS6195053A JP S6195053 A JPS6195053 A JP S6195053A JP 21408985 A JP21408985 A JP 21408985A JP 21408985 A JP21408985 A JP 21408985A JP S6195053 A JPS6195053 A JP S6195053A
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- JP
- Japan
- Prior art keywords
- acid
- polyvinyl alcohol
- alkali metal
- polymer
- alcohol polymer
- 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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はポリビニルアルコール系ポリマーに対して、酢
酸と酢酸ナトリウム及び限定されｆｃｐｋａを有する有
機多塩基酸の部分アルカリ金属塩を含有させることによ
って、熱安定性良好なポリビニルアルコール系ポリマー
を製造する方法に関するものでおる。Detailed Description of the Invention The present invention provides polyvinyl alcohol with good thermal stability by incorporating acetic acid, sodium acetate, and a partial alkali metal salt of an organic polybasic acid having a limited fcpka into a polyvinyl alcohol-based polymer. This article relates to a method for producing a polymer.
但し１本発明でいうｐｋａとは、酸の解離定数をｋａと
する時、 ｐｋａ＝ −ｌｏｇ ｋａで定義される値で
ある０
本発明でいうポリビニルアルコール系ポリマーとは、ポ
リ酢酸ビニルケン化物（ポリビニルアルコール）または
、オレフィンのｌ′Ｎｉまたは２８以上と酢酸ビニルと
の二元おるいは多元共重合体ケン化物、あるいはこれら
のポリマーがら誘導される誘導体を言う。この場合、共
重合に使用されるオレフィンの例としては、エチレン、
プロピレンをいう。また誘導体の例としては、各種のエ
ステル化物、エーテル化物、アセタール化物、グラフト
化物１分子化合物、錯化合物あるいはキレート化合物等
が挙げられる。However, 1 pka as used in the present invention is a value defined by pka=-log ka, where ka is the dissociation constant of an acid.0 Polyvinyl alcohol-based polymer as used in the present invention refers to polyvinyl acetate It refers to a saponified binary or multi-component copolymer of l'Ni of olefin or 28 or more and vinyl acetate, or derivatives derived from these polymers. In this case, examples of olefins used for copolymerization include ethylene,
Refers to propylene. Further, examples of derivatives include various esterification products, etherification products, acetalization products, single-molecular grafted compounds, complex compounds, chelate compounds, and the like.
賞１本発明で言うケン化物とは５部分ケン化物及び完全
ケン化物の両者を含むものとする。Prize 1 The saponified product as used in the present invention includes both 5-partly saponified products and completely saponified products.
該ポリビニルアルコール系ポリマーは熱安定性に乏しく
、溶融成形不能であるか、あるいは可能であっても、溶
融成形時極めて着色、熱劣化しやすい特性がるる。また
溶融成形時のみならず熱処理、熱延伸、熱接着、乾燥等
、要するに加熱時。The polyvinyl alcohol polymer has poor thermal stability and cannot be melt-molded, or even if it can be melt-molded, it is extremely susceptible to coloring and thermal deterioration during melt-molding. Not only during melt molding, but also during heat treatment, hot stretching, thermal bonding, drying, etc., in short, during heating.
容易に着色し、また分解したり、あるいは逆に架橋現象
を呈しやすく、溶融粘度が変化したり、溶剤に対して不
溶化するなど、いわゆる熱安定性に劣る欠点がメリ、工
業上重大な問題点となっている０
本発明者等は、ポリビニルアルコール系ポリマーのかか
る欠点を克服し、アイシュ・アイが少なく、着色し難く
１分解や架橋を起こし難い、熱安定性良好なポリビニル
アルコール系ポリマーを製造する方法について、鋭意検
討し大結果１本発明に到達した。It easily colors, decomposes, or conversely exhibits crosslinking phenomena, changes melt viscosity, and becomes insolubilized in solvents, which is a major industrial problem due to its poor thermal stability. The present inventors have overcome these drawbacks of polyvinyl alcohol-based polymers, and have produced polyvinyl alcohol-based polymers with good thermal stability, which have less ice-eye, are less likely to be colored, are less likely to undergo mono-decomposition or cross-linking. We have conducted extensive research on methods to do this, and have arrived at one major result: the present invention.
すなわち、ポリビニルアルコール系ポリマーニ対して
■ 酢酸ナトリウムを０．００５〜０．１重量％と■
酢酸を１次式を満足するように含有させ、更に
■ ２５℃におけるｐｋａが式
％式％
を満足する有機多塩基酸であって、該有機多塩基酸のｐ
ｋｌに相当する酸基がアルカリ金属塩を形成し、 ｐ
ｋｚに相当する酸基が遊離状態にある様な有機多塩基酸
の部分アルカリ金属塩の１種または２種以上をｏ、ｏｏ
ｔ〜０．５重量％加えることによって。That is, (1) sodium acetate is added in an amount of 0.005 to 0.1% by weight (2) based on the polyvinyl alcohol-based polymer.
an organic polybasic acid containing acetic acid so as to satisfy the linear formula, and further having a pka at 25°C satisfying the formula % formula %;
The acid group corresponding to kl forms an alkali metal salt, p
One or more partial alkali metal salts of organic polybasic acids in which the acid group corresponding to kz is in a free state are o, oo
By adding t~0.5% by weight.
アイシュ・アイが少なく１着色し難く１分解や架橋を起
こし難い、熱安定性良好なポリビニルアル １コー
ル系ポリマーを得ることができることを認め本発明を完
成した。The inventors completed the present invention by recognizing that it is possible to obtain a polyvinyl alcohol-based polymer that has less ice-eye, is less likely to be colored, is less likely to cause decomposition or crosslinking, and has good thermal stability.
本発明で言うｐｋｘ 、 ｐｋｚとは有機多塩基酸の
大きい酸解離定数から順にに１． ｋ２． ｋｓ ・・
・・・・・・・・ｋｎとする時、 ｐｋｘ ＝ −ｌ
ｏｇ ｋｘ、 ｐｋｚ ＝ −ｌｏｇ ｋ２で定義され
る値でるる。In the present invention, pkx and pkz are 1. k2. ks...
......When kn, pkx = -l
The value is defined as og kx, pkz = -log k2.
０式を満足する有機多塩基酸の例としては、フタル酸、
イソフタル酸、テレフタル酸、アジピン酸、アゼライン
酸、クエン酸、グルタコン酸、ゲルタン酸、コハク酸、
スペリン酸、ピメリン酸。Examples of organic polybasic acids that satisfy formula 0 include phthalic acid,
Isophthalic acid, terephthalic acid, adipic acid, azelaic acid, citric acid, glutaconic acid, geltanic acid, succinic acid,
Speric acid, pimelic acid.
７マル酸、 ？Ｗｉ石酸、マレイン酸、マロン酸、リン
ゴ酸等の有機酸を挙げることができるが必ずしもこれら
に限定されるものではない。7 Malic acid, ? Organic acids such as acid, maleic acid, malonic acid, and malic acid can be mentioned, but are not necessarily limited to these.
本発明では、これらの有機多塩基酸のｐｋｌに相当する
酸基がアルカリ金属塩を形成しておシ。In the present invention, acid groups corresponding to pkl of these organic polybasic acids form an alkali metal salt.
ｐｋ＋に相当する酸基が遊離状態にあるものが使用され
る。Those in which the acid group corresponding to pk+ is in a free state are used.
但し、三塩基酸以上の有機多塩基酸の場合、該有機多塩
基酸の大きい方の酸解離定数から順にｋｒ、 ｋ２．
ｋｓ、 ・−・−・−・ｋｎ−１、ｋｎ、 ｋｎ＋１
・−・・−とする時、ｋｎｌ以下の酸基がすでに他の
置換基で置き換えられている場合１例えば塩を形成して
いたり。However, in the case of an organic polybasic acid of tribasic acid or higher, kr, k2.
ks, ・−・−・−・kn−1, kn, kn+1
・・・・When the acid group below knl has already been replaced with another substituent 1, for example, a salt is formed.
あるいはエステルを形成している様な場合には。Or if it forms an ester.
ｋｎ及びｋｎ ＋１について、弐Ｘ ＝ｊ（ｐｋｎ＋
ｐｋｎ＋１）が０式を満足し、しかもｐｋｎに相当する
酸基がアルカリ金属塩を形成しｈ Ｐｋｎ＋ｔに相当
する酸塩が遊離状態にるる様な有機多塩基酸の部分アル
カリ金属塩は本発明に含まれる。このような有機多塩基
酸の部分アルカリ金属塩の例としては、エチレンジアミ
ン四酢酸（ｐｋ１＝２．０ 、 ｐｋｚ ＝２．７、ｐ
ｋｓ＝６．２、ｐｋ４＝１０．３（２５℃））やクエン
酸（ｐｋｘ＝３．１３． ｐｋｚ＝４．７６． ｐｋｓ
＝６．４０ （２５℃））のジナトリウム塩やジカリウ
ム塩等が挙げられる。For kn and kn +1, 2X = j(pkn+
Partial alkali metal salts of organic polybasic acids in which pkn+1) satisfies the formula 0 and the acid group corresponding to pkn forms an alkali metal salt and the acid salt corresponding to hPkn+t is in a free state are included in the present invention. included. Examples of such partial alkali metal salts of organic polybasic acids include ethylenediaminetetraacetic acid (pk1 = 2.0, pkz = 2.7, p
ks = 6.2, pk4 = 10.3 (25°C)) and citric acid (pkx = 3.13. pkz = 4.76. pks
= 6.40 (25°C)), disodium salts and dipotassium salts, and the like.
但し、クエン酸についてはｐｋｌ、 ｐｋ２に着目し
た場合でも前記しｆｃＸ値が０式を満足するので。However, for citric acid, even when focusing on pkl and pk2, the fcX value satisfies the formula 0 as described above.
クエン酸のモノアルカリ金属塩もまた本発明で使用でき
るものの例でめる。Monoalkali metal salts of citric acid are also examples of those that can be used in the present invention.
ｔ＃１、本発明でいうアルカリ金属とは、周期律表の第
１族元素のうち、リチウム、ナトリウム、カリウム、セ
シウム等を言う０さて、本発明の効果を十分得るために
は１前記しｆｃａｔ々の本発明構成条件をすべて満足す
る必要があり、これらの条件の５ち１つでも満足しない
場合には１本発明の効果を十分に得ることができない。t#1. The alkali metals used in the present invention refer to lithium, sodium, potassium, cesium, etc. among the Group 1 elements of the periodic table. In order to fully obtain the effects of the present invention, the alkali metals mentioned above are It is necessary to satisfy all of the conditions constituting the present invention for fcat, and if even one of these conditions is not satisfied, the effects of the present invention cannot be fully obtained.
例えは、０式を満足する有機多塩基酸を用いた場合であ
っても、該有機多塩基酸の酸基がすべて遊離状態でめつ
７？、９．あるいは、酸基のすべてが金属塩を形成して
いるような場合、または、０式を満足しない有機多塩基
酸の部分アルカリ金属塩を用いた場合には、核ポリビニ
ルアルコール系ポリマーに対する熱安定化作用は、はと
んど認められず、むしろ加熱時、該ポリビニルアルコー
ル系ポリマーの着色や分解あるいは、不溶化を積極的に
促進する傾向さえ認められる。For example, even when using an organic polybasic acid that satisfies formula 0, all the acid groups of the organic polybasic acid are in a free state. ,9. Alternatively, if all of the acid groups form metal salts, or if a partial alkali metal salt of an organic polybasic acid that does not satisfy formula 0 is used, thermal stabilization of the core polyvinyl alcohol polymer This effect is hardly observed; on the contrary, there is a tendency to actively promote coloration, decomposition, or insolubilization of the polyvinyl alcohol polymer upon heating.
また、本発明にかかる該有機多塩基酸の部分アルカリ金
属塩の含有率が０．５重量−を越える程度に多い場合に
は該ポリビニルアルコール系ポＩＪ 。In addition, when the content of the partial alkali metal salt of the organic polybasic acid according to the present invention is so large as to exceed 0.5 weight, the polyvinyl alcohol-based poly-IJ.
−はむしろ着色、不溶化しｆすくなるし、逆に。- is more likely to become colored and insolubilized, and vice versa.
該有機多塩基酸の部分アルカリ金属塩の含有率が０．０
０１ｇ量チを下まわる１！度に少なくなると、該有機多
塩基酸の部分アルカリ金属塩の効果は、小さくなるので
、該ポリビニルアルコール系ポＩＪ −ｒ−の熱劣化を
十分に防止することができない。The content of the partial alkali metal salt of the organic polybasic acid is 0.0.
01g quantity is less than 1! If the amount decreases, the effect of the partial alkali metal salt of the organic polybasic acid becomes small, and therefore it is not possible to sufficiently prevent thermal deterioration of the polyvinyl alcohol-based POIJ-r-.
一方、該ポリビニルアルコール系ポリマー中の酢酸ナト
リウムの含有率が０．１東ｍｓを越える程度に多い場合
には、該ポリビニルアルコール系ポリマーの着色１分解
を促進する傾向があるし、また酢酸ナトリウム含有率が
ｏ、ｏｏｓ重量％を下まゎる程度に少なくなると１本発
明の効果は極めて小さいものとなるのでどの°場合もま
た。該ポリビニルアルコール系ポリマーの熱劣化を防止
することができない。爽にまｆｃ、酢酸ナトリウム含有
率がｏ、ｏｏｓ重量％を下まわると、該ポリビニルアル
コール系ポリマー中の酢酸の含有率に著しい制約を−生
じ、ポリビニルアルコール系ポリマーの熱劣化防止に対
する酢酸の含有率の・有効範囲は０式に比較して極めて
狭いものとなるので好ましくない。On the other hand, if the content of sodium acetate in the polyvinyl alcohol polymer exceeds 0.1 mS, it tends to promote coloring and decomposition of the polyvinyl alcohol polymer. In any case, the effect of the present invention becomes extremely small when the ratio is less than o, oos weight percent. Thermal deterioration of the polyvinyl alcohol polymer cannot be prevented. When the sodium acetate content is less than o, oos weight%, there is a significant restriction on the acetic acid content in the polyvinyl alcohol polymer, and the inclusion of acetic acid for preventing thermal deterioration of the polyvinyl alcohol polymer. This is not preferable because the effective range of the ratio is extremely narrow compared to the 0 formula.
また該ポリビニルアルコール系ポリマー中ノ酢酸含有率
が０式をはずれて多い場合には、該ポリ′１ビニルアル
コール系ポリマーは黄褐色を呈して。Further, when the content of noacetic acid in the polyvinyl alcohol polymer is higher than 0, the poly'1 vinyl alcohol polymer exhibits a yellowish brown color.
不溶化しｆすくなるし、酢酸含有率が０式をはずれて少
ない場合には、該ポリビニルアルコール系ポリマーは黄
色に着色し、分解しやすい傾向を呈する。If the acetic acid content is less than 0, the polyvinyl alcohol polymer becomes yellow and tends to be easily decomposed.
すなわち、ポリビニルアルコール系ボリマーニ対して、
酢酸ナトリウムをｏ、ｏｏｓ〜０．１重量％と酢酸を、
前記した０式を満足するように含有させ。That is, for polyvinyl alcohol-based Bolimani,
Sodium acetate o, oos ~ 0.1% by weight and acetic acid,
It is contained so as to satisfy the above-mentioned formula 0.
更に、前記した０式を満足する有機多塩基酸の部分アル
カリ金属塩を０．０ Ｏ１〜０．５重量％加えることに
よって極めて艮好な結果が得られるのである。Furthermore, very good results can be obtained by adding 0.01 to 0.5% by weight of a partial alkali metal salt of an organic polybasic acid that satisfies the above-mentioned formula 0.
とくに特記すべき点は、酢酸及び酢酸ナトリウムと該有
機多塩基酸の部分アルカリ金属塩を併用した時には、相
乗効果が認められ、加熱時の黄色度が極めて少なく、白
土が一段と優れ、しかも厳しい加熱条件下でも熱安定性
を持続しうるポリビニルアルコール系ポリマーを得るこ
とができることである。Particularly noteworthy is that when acetic acid and sodium acetate are used in combination with the partial alkali metal salt of the organic polybasic acid, a synergistic effect is observed, the yellowness during heating is extremely low, and white clay is even better, and moreover, it can withstand severe heating. It is possible to obtain a polyvinyl alcohol-based polymer that can maintain thermal stability under various conditions.
かかる相乗効果は５本発明者等の予期しないところであ
って、誠に意外な現・象であった。Such a synergistic effect was not anticipated by the present inventors and was a truly unexpected phenomenon.
すなわちポリビニルアルコール系ポリマーに対して、酢
酸のみを含有せしめた場合、あるいは酢酸ナトリウムの
みを含有せしめた場合には、該ポリビニルアルコール系
ポリマーの熱安定性は劣悪なものとなるし、また酢酸と
酢酸ナトリウムを併用した場合には弱い加熱条件下、例
えは、比較的低温での加熱あるいは比較的短時間での加
熱の場合、または１回のみの溶融成型の場合にはがなり
の熱安定化作用が認められるものの、厳しい加熱条件下
１例えば、比較的高温での加熱るるいは比較的長時間で
の加熱の場合、または溶融成型を繰夛返した場合には、
はとんど効果が認められず。In other words, if a polyvinyl alcohol-based polymer contains only acetic acid or only sodium acetate, the thermal stability of the polyvinyl alcohol-based polymer will be poor; When sodium is used in combination, it has a thermal stabilizing effect under weak heating conditions, for example, when heating at a relatively low temperature or for a relatively short time, or when melting and molding is performed only once. However, under severe heating conditions (for example, heating at relatively high temperatures or heating for a relatively long time, or repeated melt molding),
Almost no effect was observed.
むしろ該ポリビニルアルコール系ポリマーの熱劣化を促
進する傾向さえ認められる。In fact, there is even a tendency to accelerate thermal deterioration of the polyvinyl alcohol polymer.
他方、ポリビニルアルコール系ポリマーに対して１本発
明にかかる該有機多塩基酸の部分アルカリ金属塩のみを
含有せしめた場合には厳しい加熱条件下においてでさえ
、該ポリビニルアルコール系ポリマーの分解や不溶化を
比較的良く防止し°うるが、加熱時の自腹については、
必ずしも十分ではない。On the other hand, when a polyvinyl alcohol polymer contains only the partial alkali metal salt of the organic polybasic acid according to the present invention, the polyvinyl alcohol polymer does not decompose or become insolubilized even under severe heating conditions. Although it can be prevented relatively well, it costs out of pocket when heating.
Not necessarily enough.
すなわち、酢酸及び酢酸ナトリウムと該有機多塩基酸の
部分アルカリ金へ塩を併用した時、相乗効果が認められ
、厳しい加熱条件下においても、黄色度が極めて少なく
、白匿に優れ、アイシュ・アイが少なく、熱劣化し難い
ポリビニルアルコール系ポリマーを得ることができるの
である。In other words, when acetic acid, sodium acetate, and the partially alkali gold salt of the organic polybasic acid are used in combination, a synergistic effect is observed, and even under severe heating conditions, the yellowness is extremely low, the whitening property is excellent, and the eyelid This makes it possible to obtain polyvinyl alcohol-based polymers that have less heat deterioration and are less susceptible to thermal deterioration.
該ポリビニルアルコール系ポリマー中援本発明にかかる
酢酸及び酢酸ナトリウムを含有させ、かつ該有機多塩基
酸の部分アルカリ金属塩を加える方法としては、該ポリ
ビニルアルコール系ポリ゛マーの粉末ｆベレットに直接
付着させる方法、あるいは酢酸及び酢酸ナトリウムと該
有機多塩基酸の部分アルカリ金属塩の混合水溶液あるい
はアルコール溶液または水−アルコール溶液等で該ポリ
ビニルアルコール系ポリマーを処理する方法、まなは該
ポリビニルアルコール系ポリマーの溶液に。The method of incorporating acetic acid and sodium acetate according to the present invention into the polyvinyl alcohol polymer and adding the partial alkali metal salt of the organic polybasic acid includes direct attachment to the powder pellet of the polyvinyl alcohol polymer. Alternatively, a method of treating the polyvinyl alcohol polymer with a mixed aqueous solution, alcohol solution, or water-alcohol solution of acetic acid, sodium acetate, and a partial alkali metal salt of the organic polybasic acid, or a method of treating the polyvinyl alcohol polymer with into solution.
酢酸と、酢酸す） ＩＪウム及び該有機多塩基酸の部分
アルカリ金属塩を添力りする方法１等いずれも使用でき
るが、必ずしも、これらに限定されるものではなく、種
々の状況を勘案して、適轟な方法を選択すれば良い。Any method such as method 1 of adding acetic acid, IJium, and a partial alkali metal salt of the organic polybasic acid can be used, but it is not necessarily limited to these methods, and various methods may be used in consideration of various situations. You just have to choose an appropriate method.
本発明は、該ポリビニルアルコール系ポリマーを加熱成
型する場合に、特に、顕著に、その効果を発揮するが、
その他、熱処理、熱延伸、熱接着。The present invention particularly exhibits its effects particularly when heat molding the polyvinyl alcohol-based polymer.
Others include heat treatment, heat stretching, and heat bonding.
乾燥等、要するに加熱時、その効果を発揮するものであ
る。更に本発明は、該ポリビニルアルコール系ポリマー
が溶液状態で加熱される場合、わるいはエマルジョン状
態で加熱される場合であっても、その効果を発揮するも
のである。This effect is exhibited during drying, in other words, during heating. Furthermore, the present invention exhibits its effects even when the polyvinyl alcohol polymer is heated in a solution state, or even when it is heated in an emulsion state.
本発明によって作成されたポリビニルアルコール系ポリ
マーは溶融成型法、湿式成型法、乾式成型法１等によっ
て成型物、フィルム、繊維、等に成型されるほか、エマ
ルジョンや溶液にして、塗料、接着剤、繊維加工剤ある
いは紙加工剤などの各槙処理剤等に使用することができ
る。The polyvinyl alcohol-based polymer created according to the present invention can be molded into molded products, films, fibers, etc. by melt molding, wet molding, dry molding, etc., or can be made into emulsions or solutions to be used as paints, adhesives, etc. It can be used in various pine processing agents such as fiber processing agents and paper processing agents.
また１本発明は、可塑剤−？着色剤あるいは安定剤や滑
剤等、通常、プラスチックス製品に添加される添加剤を
加えた場合でも、十分、その効果を発揮するものでるる
。 町・。In addition, one aspect of the present invention is a plasticizer-? Even when additives that are normally added to plastic products, such as colorants, stabilizers, and lubricants, are added, the effect can be fully demonstrated. town·.
次に実施例によって本発明の詳細な説明する。Next, the present invention will be explained in detail by way of examples.
！Ｊ！施例施
工１レン−酢酸ビニル共重合体（エチレン成分含有率３
３モルチ、酢酸ビニル成分含有率６７モルチ、重合度２
１５０）４０部（重量）をメタノール６０部に溶解し、
これに苛性ソーダの１０重量％メタノール溶溶液０都を
加え６０℃で３時間ケン化した。! J! Example construction 1 Ren-vinyl acetate copolymer (ethylene component content 3
3 molti, vinyl acetate component content 67 molti, degree of polymerization 2
150) Dissolve 40 parts (by weight) in 60 parts of methanol,
A 10% by weight methanol solution of caustic soda was added to this and saponified at 60°C for 3 hours.
該ケン化原液を５００部の水中に投入して、ポリマーを
析出させ次いで、析出したポリマーを脱赦後、大型ソッ
クスレ一式抽出機で５０℃にて水で１週間、連続抽出し
て洗浄した。The saponified stock solution was poured into 500 parts of water to precipitate a polymer, and then the precipitated polymer was released and washed by continuous extraction with water at 50° C. for one week using a large Soxhlet extractor.
この抽出、洗浄したエチレン−酢酸ビニル共重合体ケン
化物（ケン化［９９，５モル％）１００部をメタノール
−水混合物（メタノール７０車量チ＋水３０重量％）４
００部に６０℃で溶解させた。100 parts of the extracted and washed saponified ethylene-vinyl acetate copolymer (saponified [99.5 mol%)] was mixed with a methanol-water mixture (70 volumes of methanol + 30% by weight of water) 4
00 parts at 60°C.
該溶液に酢酸ナトリウム０．０４部、酢酸０．１５部及
び２５℃におけるｐｋａが、前記した０式を満足するコ
ハク酸（ｐｋｒ ＝４．２１、ｐｋ２＝ ５．’６４
。The solution contains 0.04 part of sodium acetate, 0.15 part of acetic acid, and succinic acid whose pka at 25°C satisfies the above formula 0 (pkr = 4.21, pk2 = 5.'64).
.
Ｘ値４．９３）のモノナトリウム塩（コハク酸水素ナト
リウム）０．０５部を添加し６０℃で十分攪拌して溶解
した。0.05 part of the monosodium salt (sodium hydrogen succinate) having an X value of 4.93) was added and dissolved by stirring thoroughly at 60°C.
該組成物を室温まで冷却してゲル化はせこれをミキサー
で粉砕後、２０時間風乾し、更に熱風循環式乾燥器にて
１００℃、１６時間加熱して乾燥させた。The composition was cooled to room temperature, and the gelled sesame was pulverized with a mixer, air-dried for 20 hours, and further dried by heating at 100° C. for 16 hours in a hot air circulation dryer.
かくして得らｆ′Ｌｆｃ該共重合体ケン化物中の酢酸ナ
トリウム含有率は０．０３６４東量チ、酢酸含有率は０
．１２３１重量％（α値３．３Ｂ）、 コハク酸水素
ナトリウム含有率は０．０４８６重量％であった。The sodium acetate content in the saponified copolymer thus obtained was 0.0364 H, and the acetic acid content was 0.
．． 1231% by weight (α value 3.3B), and the sodium hydrogen succinate content was 0.0486% by weight.
該共重合体ケン化物３ｆを２３０°Ｃに加熱した熱板（
シンド一式卓上型テストプレスｙｓ −５）の間にはさ
み、熱板間の間隙を５％に保って、１０分間及び３０分
間加熱（加熱着色試験）シ、この加熱着色試験後の試料
の黄色戚（ＹＩ、日本電色工業製ＮＤ−に５型）を測定
した。The saponified copolymer 3f was heated on a hot plate (
The sample was sandwiched between two Shindo set tabletop test presses (SYS-5) and heated for 10 minutes and 30 minutes (thermal coloring test) while keeping the gap between the heating plates at 5%.The yellow color of the sample after this heat coloring test was (YI, ND-5 type manufactured by Nippon Denshoku Industries) was measured.
一方、溶融積置の熱劣化特性を見るために、該共重合体
ケン化物の溶融指数（メルト・インデックス）をＡＳＴ
Ｍ Ｄ１２３８（Ｅ）に準じて、１９０℃。On the other hand, in order to examine the thermal deterioration characteristics of the melt-deposited copolymer, the melt index of the saponified copolymer was measured using AST.
190°C according to MD1238(E).
荷ｍ２ｔｓｏｒにて測定（全工業製メルト・インデクサ
−ＭＸ−ＩＱｌ−Ａ型オリフィス外径９．５％。Measured with load m2tsor (Zen Kogyo melt indexer MX-IQl-A type orifice outer diameter 9.5%.
オリフィス内径２．０９５％、長さ８．０％）した。Orifice inner diameter 2.095%, length 8.0%).
但し、該共重合体ケン化物をメルト・インデクサーに仕
込み、荷重をかけないで３０分間、１９０℃で予熱した
後、荷重をかけて測定しｆｃ。However, the saponified copolymer was charged into a melt indexer, preheated at 190°C for 30 minutes without applying a load, and then measured with a load applied.
測定結果を表−１に示す。The measurement results are shown in Table-1.
一万、対照例として、該共重合体ケン化物に対して酢酸
と酢酸ナトリウムのみを添加した場合（対照例１）、及
びコＩ’ｓり酸水素ナトリウムのみを添加した場合（対
照例２）、更に、酢酸、酢酸ナトリウム及びコノ・り酸
水素ナトリウムのいずれも添加しない場合（対照例３）
について実施例１の場合と同様な方法で試料を作成し、
同方法にて評価した。評価結果を表−１に示す０
以下余白
酢酸、酢酸ナトリウム及びコハク酸水素ナトリウムを含
有させた実施例１の場合には、加熱時の着色が極めて小
さく、 −１７を溶融特性の目安でめるメルト・インデ
ックスも正常であって、溶融成形加工に施した値を示し
た。As a control example, a case where only acetic acid and sodium acetate were added to the saponified copolymer (Control Example 1), and a case where only sodium hydrogen phosphate was added (Control Example 2) , Furthermore, when neither acetic acid, sodium acetate nor sodium hydrogen phosphate is added (Control Example 3)
A sample was prepared in the same manner as in Example 1,
It was evaluated using the same method. The evaluation results are shown in Table 1. In the case of Example 1 containing acetic acid, sodium acetate, and sodium hydrogen succinate, the coloration during heating was extremely small, and -17 was used as a rough guide for melting properties. The melt index was also normal and showed the value given to the melt molding process.
一方、酢酸、酢酸ナトリウムのみを添加し、コハク酸水
素ナトリウムを添加しない対照例１の場合は、厳しい加
熱条件下（２３０℃、３０分間加熱）での着色が著しく
、また、メルト・インデックスの値も大きく、やや分解
傾向を示した。On the other hand, in the case of Control Example 1, in which only acetic acid and sodium acetate were added, and sodium hydrogen succinate was not added, the coloration was significant under severe heating conditions (heating at 230°C for 30 minutes), and the melt index value was also large and showed a slight tendency to decompose.
また、酢酸、酢酸ナトリウムを添加せず、コハク酸水素
ナトリウムのみを添加した対照例２の場合には、メルト
・インデックスの値は、はぼ正常であるが、加熱時の着
色の点で不満足である。In addition, in the case of Control Example 2 in which only sodium hydrogen succinate was added without adding acetic acid or sodium acetate, the melt index value was almost normal, but the coloration during heating was unsatisfactory. be.
更に、酢酸、酢酸ナトリウム及びコノ・り酸水素ナトリ
ウムのいずれも添加しない対照例３の場合は、加熱時の
着色、溶融特性共に劣悪でめった。Furthermore, in the case of Control Example 3 in which neither acetic acid, sodium acetate nor sodium hydrogen phosphate was added, both the coloration upon heating and the melting properties were poor, resulting in failure.
次に実施例１で作成した試料を溶融押出成膜（日本製鋼
新製Ｐ−１１５型押出機使用、シリンダ一温度２３０℃
、ダイ温度２１０℃）して、１７μフイルムを作成した
ところ、フィルム・アイの数は極めて少なく、着色のな
い、美しいフィルムを得た。更に該フィルムを圧縮切断
してチップ状に成型（三菱重工製ＮＣＰ−３型クリンペ
ルユニット使用）シ、該チップを再び同押出機にて、同
条件で１７μフイルムを成膜し、繰り返し溶融押出成膜
を行なった。かくして１０回溶融押出成膜したところ、
フィルム・アイの数は、はとんど増加せず着色のない粂
しいフィルムを得た。対照例１〜３で作成した試料を同
様な方法で溶融押出成膜した場合の結果を併せて１表−
２に示す。Next, the sample prepared in Example 1 was formed into a film by melt extrusion (using a P-115 type extruder manufactured by Nippon Steel Corporation, the cylinder temperature was 230°C).
, die temperature: 210° C.) to produce a 17μ film, the number of film eyes was extremely small and a beautiful film without coloring was obtained. Furthermore, the film was compressed and cut into chips (using the NCP-3 type crimpel unit manufactured by Mitsubishi Heavy Industries), and the chips were again used in the same extruder to form a 17μ film under the same conditions and melt-extruded repeatedly. Film formation was performed. When the film was formed by melt extrusion 10 times in this way,
The number of film eyes hardly increased and a clear film with no coloration was obtained. Table 1 shows the results when the samples prepared in Control Examples 1 to 3 were melt-extruded into films using the same method.
Shown in 2.
゛ 以下余白
対照例１及び２の場合、１回のみの溶融押出成膜でＦｉ
看色及び成膜性共に、大きな問題点は認められないが、
溶融押出成膜を繰シ返した場合に５フイシユ・アイの増
加１着色、溶融結反の変化、成膜性の不良等の現象が認
められた。゛ In the case of margin control examples 1 and 2, Fi
No major problems were observed in terms of color appearance or film formation, but
When the melt extrusion film formation was repeated, phenomena such as an increase in the number of fiber eyes by 5, coloration by 1, change in melt curl, and poor film formability were observed.
また対照例３の場合は、１回目の溶融押出成膜で著しく
黄色に着色し、しかもフィルム全面にアイシュ・アイが
多発し、また溶融粘度の低下のため押出機の背圧は低く
、またフィルムに穴あきが多り、シばしばグイリップで
フィルムが切断し。In addition, in the case of Control Example 3, the first melt-extrusion film formation was markedly yellow, and there were many ice-eyes all over the film.Also, the back pressure of the extruder was low due to the decrease in melt viscosity, and the film There are many holes in the film, and the film is often cut by the grip.
捲き取りが困難であった。It was difficult to unroll.
実施例２〜３及び対照例４
エチレン−プロピレン−酢酸ビニル共重合体（エチレン
成分含有率３１モルラ、プロピレン成分含有率２モル−
１酢酸ビニル成分含有率ロアモルー１重合度１７００）
４０部（重量）をメタノール６０部に溶解し、これに苛
性ソーダの５重量％メタノール溶液４０部を加えて、６
０℃、３時間ケン化した。Examples 2 to 3 and Control Example 4 Ethylene-propylene-vinyl acetate copolymer (ethylene component content 31 mol, propylene component content 2 mol)
1 Vinyl acetate component content Roamoru 1 Degree of polymerization 1700)
40 parts (by weight) was dissolved in 60 parts of methanol, and 40 parts of a 5% by weight methanol solution of caustic soda was added thereto.
Saponification was performed at 0°C for 3 hours.
ケン化原液を５００部の水中に投入して該共重合体ケン
化物を析出させ、更に該共重合体ケン化物を流水にて５
°時間洗浄した。The saponified solution was poured into 500 parts of water to precipitate the saponified copolymer, and the saponified copolymer was further diluted with 500 parts of water under running water.
Washed for an hour.
洗浄シフ？：該エチレン−プロピレン−酢酸ビニル共重
合体ケン化物（ケン化［９８，５モル％）４０部を、酢
酸、酢酸ナトリウム及び２５℃におけるｐｋａが前記し
た０式を満足するクエン酸（ｐｋ１＝３．１３． ｐｋ
ｚ＝４．７６、 ｐｋｓ＝６．４０． Ｘ値３．９５）
のモノナトリウム塩（クエン酸二水素ナトリウム）を溶
解した水溶液（溶液ｌｌ中に酢酸２．Ｏｆ）。Cleaning sif? : 40 parts of the saponified ethylene-propylene-vinyl acetate copolymer (saponified [98.5 mol%)] was mixed with acetic acid, sodium acetate, and citric acid whose pka at 25°C satisfies the above formula 0 (pk1=3 .13.pk
z=4.76, pks=6.40. X value 3.95)
An aqueous solution of the monosodium salt (sodium dihydrogen citrate) of (2.Of acetic acid in 1 liter of solution).
酢酸ナトリウム０．１２５Ｆ、 クエン酸二水素ナト
リウム１，５？を溶解しているもの）３００部中に２時
間、浸漬して処理した。脱液後、熱風循環式乾燥器にて
、８０℃、１６時間、乾燥した。Sodium acetate 0.125F, sodium dihydrogen citrate 1.5? (dissolved)) for 2 hours. After removing the liquid, it was dried in a hot air circulation dryer at 80°C for 16 hours.
かくして得られた該共重合体ケン化物中の酢酸含有率は
０．１２５７重量％、酢酸ナトリウム含有率０、０２９
８重量％（α値４．２２）、 クエン酸二水素ナトリウ
ム含有率０．０ ？ ２１重ｔＳであった。The acetic acid content in the saponified copolymer thus obtained was 0.1257% by weight, and the sodium acetate content was 0.029% by weight.
8% by weight (α value 4.22), sodium dihydrogen citrate content 0.0? It was 21 times tS.
また実施例２におけるクエン酸二水素ナトリウムをクエ
ン酸水素二ナトリウム（Ｘ値５．５８ ）に置き換え１
表−３（実施例３）に示す試料を作成した。In addition, sodium dihydrogen citrate in Example 2 was replaced with disodium hydrogen citrate (X value 5.58).
Samples shown in Table 3 (Example 3) were prepared.
一方、対照例として、実施例２におけるクエン酸二水素
ナトリウムを２５℃におけるｐｋａが前記した０式を満
足しないサルチル酸（ｐｋ１＝ ２．８、Ｐｋ２＝１２
．４．Ｘ値７．６）のモノナトリウム塩（サルチル酸ナ
トリウム）に置き換えた場合について表−３（対照例４
）に示す試料を作成し、同様に評価した。結果を併せて
表−３に示す。On the other hand, as a control example, sodium dihydrogen citrate in Example 2 was treated with salicylic acid (pk1 = 2.8, Pk2 = 12
．． 4. Table 3 (Control Example 4) when replacing with monosodium salt (sodium salicylate) of
) was prepared and evaluated in the same manner. The results are also shown in Table 3.
実施例２及び３の場合、加熱時の着色及びメルト・イン
デックス共にほぼ良好でるるか、対照例４の場合には、
−加熱時の着色が著しく、しかもメルト・インデックス
の値は大きく、やや分解傾向を示した。In the case of Examples 2 and 3, both the coloring and melt index during heating were almost good, and in the case of Control Example 4,
-Coloration during heating was significant, the melt index value was large, and there was a slight tendency to decompose.
以下余白Margin below
Claims (1)
ウムを０．００５〜０．１重量％と酢酸を式ポリビニル
アルコール系ポリマー中の α＝酢酸の含有量（重量％）／ポリビニルアルコール系
ポリマー中の＜α＜１０酢酸ナトリウムの含有率（重量
％） を満足するように含有させ、更に２５℃におけるｐｋａ
が式 Ｘ＝１／２（ｐｋ＿１＋ｐｋ＿２）３．５＜Ｘ＜６．０
（但し、ｐｋ＿１＜ｐｋ＿２） を満足する有機多塩基酸であって、該有機多塩基酸のｐ
ｋ＿１に相当する酸基がアルカリ金属塩を形成し、ｐｋ
＿２に相当する酸基が遊離状態にある様な有機多塩基酸
の部分アルカリ金属塩の１種または２種以上を０．００
１〜０．５重量％加えることを特徴とする熱安定性に優
れたポリビニルアルコール系ポリマーの製造方法。[Claims] 0.005 to 0.1% by weight of sodium acetate and acetic acid based on the polyvinyl alcohol polymer. α in the polyvinyl alcohol polymer = content of acetic acid (weight %)/polyvinyl alcohol system The content of sodium acetate (wt%) <α<10 in the polymer is satisfied, and the pka at 25°C is
is the formula X=1/2(pk_1+pk_2)3.5<X<6.0
(However, pk_1<pk_2) An organic polybasic acid that satisfies pk_1<pk_2, and p of the organic polybasic acid
The acid group corresponding to k_1 forms an alkali metal salt, pk
0.00 of one or more partial alkali metal salts of organic polybasic acids in which the acid group corresponding to _2 is in a free state.
A method for producing a polyvinyl alcohol polymer with excellent thermal stability, characterized by adding 1 to 0.5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21408985A JPS6195053A (en) | 1985-09-26 | 1985-09-26 | Production of polyvinyl alcohol polymer with high thermal stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21408985A JPS6195053A (en) | 1985-09-26 | 1985-09-26 | Production of polyvinyl alcohol polymer with high thermal stability |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7811575A Division JPS52955A (en) | 1975-06-24 | 1975-06-24 | Process for preparing a polyvinyl alcohol polymer having excellent hea t stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6195053A true JPS6195053A (en) | 1986-05-13 |
| JPS6236065B2 JPS6236065B2 (en) | 1987-08-05 |
Family
ID=16650043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21408985A Granted JPS6195053A (en) | 1985-09-26 | 1985-09-26 | Production of polyvinyl alcohol polymer with high thermal stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6195053A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6469652A (en) * | 1987-09-09 | 1989-03-15 | Kuraray Co | Ethylene/vinyl alcohol copolymer composition |
| US5051222A (en) * | 1989-09-01 | 1991-09-24 | Air Products And Chemicals, Inc. | Method for making extrudable polyvinyl alcohol compositions |
| EP0488886A1 (en) * | 1990-11-30 | 1992-06-03 | Taoka Chemical Co., Ltd | Composition of ethylene-vinyl acetate copolymers |
| JPH10325907A (en) * | 1997-05-23 | 1998-12-08 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-base phase difference film |
| JP2000026690A (en) * | 1998-07-07 | 2000-01-25 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and its manufacture and its application |
| JP2002097209A (en) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP2002097208A (en) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP2002097210A (en) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP2006265369A (en) * | 2005-03-24 | 2006-10-05 | Ako Kasei Co Ltd | Polyvinyl alcohol composition |
| CN102834439A (en) * | 2010-04-20 | 2012-12-19 | 可乐丽股份有限公司 | Polyvinyl alcohol film |
| JP2016537480A (en) * | 2013-09-12 | 2016-12-01 | ソルティア・インコーポレーテッド | Polymer interlayer containing stabilized fluorescent particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5064349A (en) * | 1973-10-08 | 1975-05-31 |
-
1985
- 1985-09-26 JP JP21408985A patent/JPS6195053A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5064349A (en) * | 1973-10-08 | 1975-05-31 |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6469652A (en) * | 1987-09-09 | 1989-03-15 | Kuraray Co | Ethylene/vinyl alcohol copolymer composition |
| US5051222A (en) * | 1989-09-01 | 1991-09-24 | Air Products And Chemicals, Inc. | Method for making extrudable polyvinyl alcohol compositions |
| EP0488886A1 (en) * | 1990-11-30 | 1992-06-03 | Taoka Chemical Co., Ltd | Composition of ethylene-vinyl acetate copolymers |
| JPH10325907A (en) * | 1997-05-23 | 1998-12-08 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-base phase difference film |
| JP2000026690A (en) * | 1998-07-07 | 2000-01-25 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and its manufacture and its application |
| JP2002097208A (en) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP2002097209A (en) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP2002097210A (en) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP4615152B2 (en) * | 2000-07-19 | 2011-01-19 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization of vinyl compounds |
| JP4615153B2 (en) * | 2000-07-19 | 2011-01-19 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization of vinyl compounds |
| JP2006265369A (en) * | 2005-03-24 | 2006-10-05 | Ako Kasei Co Ltd | Polyvinyl alcohol composition |
| CN102834439A (en) * | 2010-04-20 | 2012-12-19 | 可乐丽股份有限公司 | Polyvinyl alcohol film |
| JP2016537480A (en) * | 2013-09-12 | 2016-12-01 | ソルティア・インコーポレーテッド | Polymer interlayer containing stabilized fluorescent particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6236065B2 (en) | 1987-08-05 |
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