JPH10101729A - Production of sulfonated polyvinyl alcohol resin - Google Patents
Production of sulfonated polyvinyl alcohol resinInfo
- Publication number
- JPH10101729A JPH10101729A JP27680896A JP27680896A JPH10101729A JP H10101729 A JPH10101729 A JP H10101729A JP 27680896 A JP27680896 A JP 27680896A JP 27680896 A JP27680896 A JP 27680896A JP H10101729 A JPH10101729 A JP H10101729A
- Authority
- JP
- Japan
- Prior art keywords
- water
- polyvinyl alcohol
- sulfonic acid
- reaction
- degree
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、スルホン酸基含有
ポリビニルアルコール系樹脂の製造方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a method for producing a sulfonic acid group-containing polyvinyl alcohol resin.
【０００２】[0002]
【従来の技術】スルホン酸基含有ポリビニルアルコール
系樹脂は、汎用のポリビニルアルコール（以下、ＰＶＡ
と略記する。）系樹脂に比べ水に対する溶解速度が大き
く、冷水易溶性フィルムとして有用であり、その製造方
法としては、スルホン酸基含有単量体と脂肪酸ビニルエ
ステルとの共重合体を鹸化する方法（特開昭５４−１３
８０３６号公報）、ＰＶＡ系樹脂をスルホン酸基含有ア
ルデヒド類でアセタ−ル化する方法（特開昭６３−２１
８７４１号公報）が知られている。前者の場合、スルホ
ン酸基含有単量体は通常ナトリウム塩になっており、工
業的に通常行われているアルコ−ルを溶媒とする溶液重
合系において、その溶解度が極端に小さいため、スルホ
ン酸基を１モル％未満しかＰＶＡ樹脂中へ導入できない
という問題がある。また、後者の場合、水溶液または水
分散系でＰＶＡとスルホン酸基含有アルデヒド類を反応
させた後、多量のアセトン中に滴下、再沈殿させてスル
ホン酸基含有ＰＶＡ系樹脂を得るため、溶剤回収設備や
回収エネルギ−が必要となり、工業的生産には問題があ
る。2. Description of the Related Art Sulfonic acid group-containing polyvinyl alcohol resins are commonly used polyvinyl alcohol (hereinafter referred to as PVA).
Abbreviated. ) The dissolution rate in water is higher than that of a resin, and it is useful as a cold water easily soluble film. As a method for producing the film, a method of saponifying a copolymer of a sulfonic acid group-containing monomer and a fatty acid vinyl ester (JP 54-13
No. 8036), a method of acetalizing a PVA-based resin with sulfonic acid group-containing aldehydes (JP-A-63-21).
No. 8741). In the former case, the sulfonic acid group-containing monomer is usually a sodium salt, and in a solution polymerization system using an alcohol as a solvent, which is industrially usually used, the solubility thereof is extremely small. There is a problem that less than 1 mol% of groups can be introduced into the PVA resin. In the latter case, after the PVA is reacted with the sulfonic acid group-containing aldehyde in an aqueous solution or an aqueous dispersion, the sulfonic acid group-containing PVA resin is obtained by dropping and reprecipitating in a large amount of acetone. Equipment and recovery energy are required, and there is a problem in industrial production.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記の問題
点のない、工業的に有利であって、かつ所望の量のスル
ホン酸基をＰＶＡ系樹脂へ導入することが可能な方法を
提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention provides a method which is free of the above-mentioned problems, is industrially advantageous, and can introduce a desired amount of sulfonic acid groups into a PVA-based resin. It is intended to do so.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記目的を達
成するものであって、水膨潤度が１．２倍以上のＰＶＡ
系樹脂粉末を反応混合物の総重量に対して２０〜６０重
量％の水の存在下で膨潤させ、スルホン酸基含有アルデ
ヒド類でアセタ−ル化することを特徴とするスルホン酸
基含有ＰＶＡ系樹脂の製造方法である。DISCLOSURE OF THE INVENTION The present invention achieves the above object and provides a PVA having a water swelling degree of at least 1.2 times.
A sulfonic acid group-containing PVA resin, which is swollen in the presence of 20 to 60% by weight of water based on the total weight of the reaction mixture, and is acetalized with a sulfonic acid group-containing aldehyde. It is a manufacturing method of.
【０００５】[0005]
【発明の実施の形態】本発明で使用されるＰＶＡ系樹脂
粉末は、アセタ−ル化の反応温度における水膨潤度が
１．２倍以上、好ましくは１．５倍以上のものであれば
よく、重合度、鹸化度、立体規則性等は目的によって変
えることができる。またアセタ−ル化反応に影響を及ぼ
さない範囲であれば、他の単量体、例えばカルボキシル
基やスルホン酸基等のアニオン性やアンモニウム塩やア
ミン基等のカチオン性のイオン基、アルキル基、アルキ
レン基等の疎水性基、珪素含有基、フッ素含有基、チオ
−ル基、ジケテン基、エポキシ基、ハロゲン基等含有の
従来公知の単量体で共重合変性したり、後反応変性した
ものでもよい。ＰＶＡ系樹脂粉末の大きさは、細かい方
が有利であり、好ましくは５００μｍ以下、さらに好ま
しくは１５０μｍ以下である。BEST MODE FOR CARRYING OUT THE INVENTION The PVA-based resin powder used in the present invention has a degree of water swelling at an acetalization reaction temperature of 1.2 times or more, preferably 1.5 times or more. The degree of polymerization, degree of saponification, stereoregularity and the like can be changed depending on the purpose. In addition, as long as it does not affect the acetalization reaction, other monomers, for example, anionic groups such as a carboxyl group or a sulfonic acid group or cationic ionic groups such as an ammonium salt or an amine group, an alkyl group, Copolymerized or post-reaction modified with known monomers containing hydrophobic groups such as alkylene groups, silicon-containing groups, fluorine-containing groups, thiol groups, diketene groups, epoxy groups, halogen groups, etc. May be. The size of the PVA-based resin powder is advantageously small, preferably 500 μm or less, more preferably 150 μm or less.
【０００６】本発明で使用されるスルホン酸基含有アル
デヒド類は、各種のものを使用することができるが、工
業的に市販されているものが望ましい。例えば、２−ベ
ンズアルデヒドスルホン酸、２，４−ベンズアルデヒド
ジスルホン酸、４−クロロベンズアルデヒド−２−スル
ホン酸、４−メチルベンズアルデヒド−２−スルホン
酸、４−ヒドロキシルベンズアルデヒド−２−スルホン
酸、ブチルアルデヒド−３−スルホン酸、プロピオンア
ルデヒド−３−スルホン酸またはそれらの塩等を挙げる
ことができる。スルホン酸基含有アルデヒド類の添加量
は、所望とする導入量により決定されるが、通常、所望
の導入量に対して１〜２倍の量を添加する。As the sulfonic acid group-containing aldehyde used in the present invention, various aldehydes can be used, but those commercially available are preferred. For example, 2-benzaldehyde sulfonic acid, 2,4-benzaldehyde disulfonic acid, 4-chlorobenzaldehyde-2-sulfonic acid, 4-methylbenzaldehyde-2-sulfonic acid, 4-hydroxybenzaldehyde-2-sulfonic acid, butyraldehyde-3 -Sulfonic acid, propionaldehyde-3-sulfonic acid or salts thereof. The amount of the sulfonic acid group-containing aldehyde to be added is determined by the desired amount of introduction, but usually, the amount is 1-2 times the desired amount of introduction.
【０００７】本発明において使用される水の量は、ＰＶ
Ａ系樹脂粉末が膨潤状態となるように、反応混合物の総
重量に対して２０〜６０重量％であることが必要であ
る。ここで、反応混合物とはＰＶＡ系樹脂粉末、スルホ
ン酸基含有アルデヒド類、水を主とするもので、このほ
かに少量の酸触媒などの添加剤が含まれる。水の量が２
０重量％未満では、アセタール化の反応効率が極度に低
下し、本発明の効果を発揮できない。また、水の量が６
０重量％を超えると、アセタール化の反応系においてＰ
ＶＡ系樹脂粉末の溶解が起こることとなる。好ましく
は、反応混合物の総重量に対して水の量は３０〜５０重
量％である。[0007] The amount of water used in the present invention is PV
It is necessary that the content is 20 to 60% by weight based on the total weight of the reaction mixture so that the A-based resin powder is in a swollen state. Here, the reaction mixture mainly contains PVA-based resin powder, sulfonic acid group-containing aldehydes, and water, and further includes a small amount of an additive such as an acid catalyst. The amount of water is 2
If the amount is less than 0% by weight, the reaction efficiency of acetalization is extremely reduced, and the effect of the present invention cannot be exhibited. If the amount of water is 6
If it exceeds 0% by weight, P in the reaction system for acetalization
Dissolution of the VA-based resin powder will occur. Preferably, the amount of water is from 30 to 50% by weight, based on the total weight of the reaction mixture.
【０００８】前記ＰＶＡ系樹脂をスルホン酸基含有アル
デヒド類でアセタ−ル化する方法において、ＰＶＡ系樹
脂粉末、スルホン酸基含有アルデヒド類および水の混合
方法としては、各種の方法を採用することができる。Ｐ
ＶＡ系樹脂粉末にスルホン酸基含有アルデヒド類の水溶
液を添加、混合する方法がより好ましい。この際、反応
を有利に行うために通常、酸触媒が用いられる。酸触媒
としては、通常硫酸、塩酸、燐酸等の無機酸またはそれ
らのアンモニウム塩が使用され、反応系のｐＨが５以下
になるように添加される。反応終了後は、必要に応じて
アルカリ性物質で中和する。反応温度は、反応時間が極
端に長時間とならず、またＰＶＡ系樹脂が熱溶融しない
程度の温度であれば、各種の温度を採用することができ
る。通常、５〜７０℃、望ましくは１０〜６０℃で反応
が行われる。In the method of acetalizing a PVA-based resin with a sulfonic acid group-containing aldehyde, various methods may be employed as a method of mixing the PVA-based resin powder, the sulfonic acid group-containing aldehyde, and water. it can. P
A more preferred method is to add and mix an aqueous solution of a sulfonic acid group-containing aldehyde to the VA resin powder. At this time, an acid catalyst is usually used to perform the reaction advantageously. As the acid catalyst, an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like or an ammonium salt thereof is usually used, and is added so that the pH of the reaction system becomes 5 or less. After the completion of the reaction, the mixture is neutralized with an alkaline substance, if necessary. Various reaction temperatures can be employed as long as the reaction time does not become extremely long and the PVA-based resin does not melt by heat. Usually, the reaction is carried out at 5 to 70 ° C, preferably 10 to 60 ° C.
【０００９】本発明の製造方法においては、上記のＰＶ
Ａ系樹脂粉末、スルホン酸基含有アルデヒド類および水
の混合物を反応機内においてアセタール化反応を進行さ
せてもよく、または、上記の混合物を混合した後、一旦
包装し、それを室温下に放置してアセタール化反応を進
行させてもよい。In the production method of the present invention, the above PV
The acetalization reaction of the mixture of the A-based resin powder, the sulfonic acid group-containing aldehyde, and water may be allowed to proceed in a reactor, or after the mixture is mixed, the mixture is once packaged and left at room temperature. The acetalization reaction may be allowed to proceed.
【００１０】本発明で得られるスルホン酸基含有ＰＶＡ
系樹脂は、汎用のＰＶＡと同様に、接着剤、紙加工剤、
繊維加工剤、乳化・分散剤、各種バインダ−、フィルム
・成形物、各種表面処理剤等に有用である。中でも、水
溶解速度が非常に大きいことから、冷水易溶性フィルム
やシ−トとして特に有用である。The sulfonic acid group-containing PVA obtained by the present invention
The system resin, like general-purpose PVA, adhesives, paper processing agents,
It is useful for fiber processing agents, emulsifying and dispersing agents, various binders, films and molded products, various surface treatment agents, and the like. Among them, it is particularly useful as a cold water easily soluble film or sheet because of its extremely high water dissolution rate.
【００１１】[0011]
【実施例】以下に本発明を実施例により具体的に説明す
る。ここで、用いられた測定法を以下に示す。The present invention will be specifically described below with reference to examples. Here, the measuring method used is shown below.
【００１２】．水膨潤度 ＰＶＡ粉末５ｇを１００ｃｃのビ−カ−に取り、所定の
温度の水５０ｃｃを入れ、ガラス棒で数回かき混ぜ、ビ
−カ−を所定の温度の水槽に１０分間漬けた後、ガラス
フィルタ−で吸引濾過し、水膨潤ＰＶＡ粉末の重量を測
定して下式にて算出した。 水膨潤度（倍）＝水膨潤ＰＶＡ粉末の重量（ｇ）／５
（ｇ） ．アセタ−ル化度 ＪＩＳ Ｋ６７２８ ポリビニルブチラ−ル試験方法の
５．５．２項に準じて測定した。[0012] Degree of water swelling Take 5 g of PVA powder in a 100 cc beaker, add 50 cc of water at a predetermined temperature, stir several times with a glass rod, immerse the beaker in a water bath of a predetermined temperature for 10 minutes, The solution was suction-filtered with a filter, and the weight of the water-swelled PVA powder was measured and calculated by the following equation. Water swelling degree (times) = weight of water-swelled PVA powder (g) / 5
(G). Degree of acetalization Measured in accordance with JIS K6728, Test Method, Section 5.5.2 of Polyvinyl Butyral.
【００１３】実施例１ 卓上ニ−ダ混合機に１５０メッシュ篩をパスしたもので
４０℃における水膨潤度が２．９倍のＰＶＡ粉末（鹸化
度９９．３モル％、平均重合度１７００）１００ｇを仕
込み、反応系を４０℃に設定して攪拌下でベンズアルデ
ヒド−２−スルホン酸ナトリウム１９ｇを溶解した水溶
液８０ｇを添加、混合した。水がＰＶＡ粉末に充分に吸
収された後、０．１規定の硫酸５mlを添加し混合して反
応混合物のｐＨを２．５に調整した。この状態で４０℃
で７時間維持して反応させた後、水酸化ナトリウム水溶
液で中和した。得られた反応生成物のスルホン酸基含有
ＰＶＡを精製してアセタ−ル化度を測定したところ、
３．３モル％であった。Example 1 100 g of PVA powder having a water swelling degree of 2.9 times at 40 ° C. (a saponification degree of 99.3 mol% and an average degree of polymerization of 1700) obtained by passing a 150-mesh sieve through a table kneader mixer. The reaction system was set to 40 ° C., and 80 g of an aqueous solution in which 19 g of sodium benzaldehyde-2-sulfonate was dissolved was added and mixed with stirring. After the water was sufficiently absorbed by the PVA powder, 5 ml of 0.1N sulfuric acid was added and mixed to adjust the pH of the reaction mixture to 2.5. 40 ° C in this state
For 7 hours, and then neutralized with an aqueous sodium hydroxide solution. The sulfonic acid group-containing PVA of the obtained reaction product was purified and the degree of acetalization was measured.
3.3 mol%.
【００１４】実施例２ ３０メッシュ篩をパスしたもので４０℃における水膨潤
度が３．８倍のＰＶＡ粉末（鹸化度９８．０モル％、平
均重合度１１００）１００ｇを用いた以外は、実施例１
と同様に反応させた。得られた反応生成物を精製してア
セタ−ル化度を測定したところ、２．８モル％であっ
た。Example 2 The procedure was carried out except that 100 g of PVA powder (a saponification degree of 98.0 mol% and an average degree of polymerization of 1100) which passed through a 30-mesh sieve and had a water swelling degree at 40 ° C. of 3.8 times was used. Example 1
The reaction was carried out in the same manner as described above. The obtained reaction product was purified and the degree of acetalization was measured. As a result, it was 2.8 mol%.
【００１５】実施例３ ベンズアルデヒド−２−スルホン酸ナトリウム１９ｇを
溶解した水溶液８０ｇに変えて、ベンズアルデヒド−
２，４ージスルホン酸ナトリウム２８ｇを溶解した水溶
液１４０ｇを用いた以外は、実施例１と同様に反応させ
た。得られた反応生成物を同様にしてアセタ−ル化度を
測定したところ、３．２モル％であった。Example 3 A solution of benzaldehyde-2-sodium sulfonate in an amount of 80 g was prepared by dissolving 19 g of sodium benzaldehyde-2-sulfonate.
The reaction was carried out in the same manner as in Example 1 except that 140 g of an aqueous solution in which 28 g of sodium 2,4-disulfonate was dissolved was used. When the degree of acetalization of the obtained reaction product was measured in the same manner, it was 3.2 mol%.
【００１６】実施例４ ２０℃で反応混合物を作製した以外は、実施例１と同様
にして反応混合物を作製した。なお、ＰＶＡ粉末の２０
℃における水膨潤度は１．９倍であった。得られた反応
混合物をビニ−ル袋に取り、袋を良くシ−ルした後、室
温下で２日間放置して反応させた。得られた反応生成物
を同様にしてアセタ−ル化度を測定したところ、１日放
置で３．３モル％、２日放置で３．５モル％であった。Example 4 A reaction mixture was prepared in the same manner as in Example 1 except that a reaction mixture was prepared at 20 ° C. In addition, 20 of PVA powder
The degree of water swelling at ℃ was 1.9 times. The resulting reaction mixture was placed in a vinyl bag, the bag was well sealed, and allowed to react at room temperature for 2 days. When the degree of acetalization of the obtained reaction product was measured in the same manner, it was 3.3 mol% after standing for 1 day and 3.5 mol% after leaving for 2 days.
【００１７】実施例５ 実施例４において、ＰＶＡ粉末（２０℃における水膨潤
度が２．８倍、鹸化度８８．５モル％、重合度１８０
０）を用いた以外は、実施例４と同様に反応させた。３
日放置で得られた反応生成物のアセタ−ル化度は、２．
７モル％であった。Example 5 In Example 4, a PVA powder (having a water swelling degree at 20 ° C. of 2.8 times, a saponification degree of 88.5 mol%, and a polymerization degree of 180) was used.
The reaction was carried out in the same manner as in Example 4 except that 0) was used. 3
The degree of acetalization of the reaction product obtained after standing for one day is:
It was 7 mol%.
【００１８】比較例１ ベンズアルデヒド−２−スルホン酸ナトリウム１９ｇを
溶解した水溶液の量を４０ｇに変えて用いた以外は、実
施例１と同様に反応させた。得られた反応生成物物を精
製してアセタ−ル化度を測定したところ、１．１モル％
で非常に低かった。Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the amount of the aqueous solution in which 19 g of sodium benzaldehyde-2-sulfonate was dissolved was changed to 40 g. The obtained reaction product was purified and the degree of acetalization was measured.
Was very low.
【００１９】比較例２ ベンズアルデヒド−２−スルホン酸ナトリウム１９ｇを
溶解した水溶液の量を２１０ｇに変えて用いた以外は、
実施例５と同様に反応させた。放置途中よりＰＶＡが餅
状の塊となってしまった。得られた反応生成物のアセタ
−ル化度は、２．５モル％であった。COMPARATIVE EXAMPLE 2 Except that the amount of the aqueous solution in which 19 g of sodium benzaldehyde-2-sulfonate was dissolved was changed to 210 g, and used.
The reaction was carried out in the same manner as in Example 5. PVA became a cake-like mass from the middle of standing. The degree of acetalization of the obtained reaction product was 2.5 mol%.
【００２０】比較例３ ３０メッシュ篩をパスしたもので４０℃における水膨潤
度が１．１倍のＰＶＡ粉末（鹸化度９９．９モル％、平
均重合度１８００）１００ｇを用いた以外は、実施例３
と同様に反応させた。得られた反応生成物のアセタ−ル
化度は、０．８モル％で非常に低く、また反応生成物は
染み出しの水分が多く、固形物としての取り扱いが困難
であった。Comparative Example 3 The procedure was carried out except that 100 g of PVA powder (99.9 mol% of saponification degree, average degree of polymerization of 1800) which passed through a 30-mesh sieve and had a water swelling degree at 40 ° C. of 1.1 times was used. Example 3
The reaction was carried out in the same manner as described above. The degree of acetalization of the obtained reaction product was very low at 0.8 mol%, and the reaction product had a large amount of seeping water and was difficult to handle as a solid.
【００２１】[0021]
【発明の効果】以上の説明から明らかなように、本発明
によれば、工業的に有利であって、かつ取り扱いの容易
な固形状のスルホン酸基含有ＰＶＡ系樹脂を提供するこ
とが可能となった。As is apparent from the above description, according to the present invention, it is possible to provide a solid sulfonic acid group-containing PVA-based resin which is industrially advantageous and easy to handle. became.
Claims (1)
ルコール系樹脂粉末を反応混合物の総重量に対して２０
〜６０重量％の水の存在下で膨潤させ、スルホン酸基含
有アルデヒド類でアセタ−ル化することを特徴とするス
ルホン酸基含有ポリビニルアルコール系樹脂の製造方
法。1. A polyvinyl alcohol-based resin powder having a water swelling ratio of 1.2 times or more is added in an amount of 20 to the total weight of the reaction mixture.
A method for producing a sulfonic acid group-containing polyvinyl alcohol-based resin, comprising swelling in the presence of 〜60% by weight of water and acetalizing with a sulfonic acid group-containing aldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27680896A JPH10101729A (en) | 1996-09-30 | 1996-09-30 | Production of sulfonated polyvinyl alcohol resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27680896A JPH10101729A (en) | 1996-09-30 | 1996-09-30 | Production of sulfonated polyvinyl alcohol resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10101729A true JPH10101729A (en) | 1998-04-21 |
Family
ID=17574681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27680896A Pending JPH10101729A (en) | 1996-09-30 | 1996-09-30 | Production of sulfonated polyvinyl alcohol resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10101729A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019004352A1 (en) * | 2017-06-30 | 2019-01-03 | 株式会社クラレ | Method for producing modified polyvinyl alcohol resin |
| WO2019159756A1 (en) * | 2018-02-14 | 2019-08-22 | 株式会社クラレ | Resin material, production method therefor, and water-soluble film |
| WO2019159757A1 (en) | 2018-02-14 | 2019-08-22 | 株式会社クラレ | Modified vinyl alcohol polymer and production method therefor |
-
1996
- 1996-09-30 JP JP27680896A patent/JPH10101729A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019004352A1 (en) * | 2017-06-30 | 2019-01-03 | 株式会社クラレ | Method for producing modified polyvinyl alcohol resin |
| JPWO2019004352A1 (en) * | 2017-06-30 | 2020-04-30 | 株式会社クラレ | Method for producing modified polyvinyl alcohol resin |
| US11174327B2 (en) | 2017-06-30 | 2021-11-16 | Kuraray Co., Ltd. | Method for producing modified polyvinyl alcohol resin |
| WO2019159756A1 (en) * | 2018-02-14 | 2019-08-22 | 株式会社クラレ | Resin material, production method therefor, and water-soluble film |
| WO2019159757A1 (en) | 2018-02-14 | 2019-08-22 | 株式会社クラレ | Modified vinyl alcohol polymer and production method therefor |
| US11155651B2 (en) | 2018-02-14 | 2021-10-26 | Kuraray Co., Ltd. | Modified vinyl alcohol polymer and method for producing same |
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