JPH0699499B2 - Purification method of water-soluble polyvinyl acetal - Google Patents
Purification method of water-soluble polyvinyl acetalInfo
- Publication number
- JPH0699499B2 JPH0699499B2 JP34054889A JP34054889A JPH0699499B2 JP H0699499 B2 JPH0699499 B2 JP H0699499B2 JP 34054889 A JP34054889 A JP 34054889A JP 34054889 A JP34054889 A JP 34054889A JP H0699499 B2 JPH0699499 B2 JP H0699499B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- polyvinyl acetal
- weight
- solution
- soluble polyvinyl
- 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.)
- Expired - Lifetime
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
- C08F8/28—Condensation with aldehydes or ketones
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)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、水溶性ポリビニルアセタールの精製方法に関
する。TECHNICAL FIELD The present invention relates to a method for purifying a water-soluble polyvinyl acetal.
（従来の技術） 従来、セラミツク・バインダーとしては、ポリビニルア
ルコールやアクリル系樹脂が用いられているが、前者は
硬く、脆く、後者は柔らかすぎて、共にハンドリング性
に劣る。これらに対して、ポリビニルブチラール樹脂
は、適度の硬さを有するが、従来、知られているポリビ
ニルブチラール樹脂は、多くは、ブチラール化度が50〜
80モル％であつて、これは、水溶性でなく、有機溶剤に
のみ溶解する。(Prior Art) Conventionally, polyvinyl alcohol or an acrylic resin has been used as a ceramic binder, but the former is hard and brittle, and the latter is too soft, and both are inferior in handleability. On the other hand, polyvinyl butyral resins have an appropriate hardness, but conventionally known polyvinyl butyral resins often have a butyralization degree of 50 to 50.
At 80 mol%, it is not water soluble and only soluble in organic solvents.
そこで、例えば、特開昭62−156112号公報には、アセタ
ール環におけるアルキル基の平均鎖長が炭素数0.34〜1.
70であるポリビニルアセタール樹脂が提案されている。
しかし、このように、アセタール環におけるアルキル基
の鎖長が短いポリビニルアセタール樹脂は、柔軟性に欠
ける。Therefore, for example, in JP-A-62-156112, the average chain length of the alkyl group in the acetal ring is 0.34 to 1.
A polyvinyl acetal resin of 70 has been proposed.
However, as described above, the polyvinyl acetal resin having a short chain length of the alkyl group in the acetal ring lacks flexibility.
（発明が解決しようとする課題） 本発明者らは、適度の柔軟性を有し、しかも、水溶性で
あるポリビニルブチラール樹脂を得るべく鋭意検討した
結果、ポリビニルアルコールの水溶液に所定量のブチル
アルデヒドを反応させて、ブチラール化度を所定の小さ
い範囲とすることによつて、上記のような水溶性ポリビ
ニルブチラール樹脂を得ることができることを見出し
た。(Problems to be Solved by the Invention) As a result of intensive investigations by the present inventors to obtain a polyvinyl butyral resin which has appropriate flexibility and is water-soluble, a predetermined amount of butyraldehyde was added to an aqueous solution of polyvinyl alcohol. It was found that the water-soluble polyvinyl butyral resin as described above can be obtained by reacting the above with the butyralization degree within a predetermined small range.
一般に、水溶性樹脂の精製には、再沈法がよく用いられ
る。即ち、樹脂の水溶液に樹脂の貧溶剤としての有機溶
剤を加えて、イオン等の不純物を水中に溶解させ、樹脂
を沈澱させて、このようにして、樹脂から不純物を分離
するのである。In general, the reprecipitation method is often used to purify the water-soluble resin. That is, an organic solvent as a poor solvent for the resin is added to the aqueous solution of the resin, impurities such as ions are dissolved in water to precipitate the resin, and thus the impurities are separated from the resin.
しかし、このような方法は、有機溶剤を用いる危険性の
みならず、水／有機溶剤混合物の後処理にも問題があ
る。However, such a method has problems not only in the danger of using an organic solvent but also in the post-treatment of the water / organic solvent mixture.
そこで、本発明者らは、上記した問題を解決するために
鋭意研究した結果、水溶性ポリビニルアセタールの水溶
液から水系のままでの処理によつて、特にイオン類等の
不純物を有効に除去し得る精製方法を見出して、本発明
を完成したものである。Therefore, as a result of intensive research to solve the above problems, the present inventors can effectively remove impurities such as ions by treatment of an aqueous solution of a water-soluble polyvinyl acetal as an aqueous system. The present invention has been completed by finding a purification method.
即ち、本発明は、水溶性ポリビニルアセタールの精製方
法を提供することを目的とする。That is, the object of the present invention is to provide a method for purifying a water-soluble polyvinyl acetal.
（課題を解決するための手段） 本発明による水溶性ポリビニルアセタールの精製方法
は、水溶性ポリビニルアセタールを含む水溶液を加熱し
て、水溶性ポリビニルアセタールの濃厚水溶液層と水層
とを形成し、この水層を前記ポリビニルアセタールの濃
厚水溶液から分離することを特徴とする。(Means for Solving the Problems) The method for purifying a water-soluble polyvinyl acetal according to the present invention is to heat an aqueous solution containing a water-soluble polyvinyl acetal to form a concentrated aqueous solution layer and a water layer of the water-soluble polyvinyl acetal, The aqueous layer is separated from the concentrated aqueous solution of polyvinyl acetal.
水溶性ポリビニルブチラールは、ポリビニルアルコール
を水に溶解させ、例えば、塩酸のような酸触媒の存在下
に、所定量のブチルアルデヒドを反応させた後、例え
ば、水酸化ナトリウムのようなアルカリで中和すること
によつて得ることができる。Water-soluble polyvinyl butyral is obtained by dissolving polyvinyl alcohol in water, reacting a predetermined amount of butyraldehyde in the presence of an acid catalyst such as hydrochloric acid, and then neutralizing it with an alkali such as sodium hydroxide. It can be obtained by doing.
従つて、このようにして得られた水溶性ポリビニルアセ
タールの水溶液には、塩素イオンやナトリウムイオンが
不純物として含まれる。Therefore, the aqueous solution of the water-soluble polyvinyl acetal thus obtained contains chlorine ions and sodium ions as impurities.
本発明によれば、このような水溶性ポリビニルアセター
ルを含む水溶液を、好ましくは撹拌しながら加熱し、水
溶性ポリビニルアセタールの濃厚水溶液層（上層）と水
層（下層）とに分離させ、下層となる水層を前記水溶性
ポリビニルアセタールの濃厚水溶液層から抜き出して分
離し、必要に応じて、このような分離操作を繰り返して
行なうことによつて、不純物としての塩素イオンやナト
リウムイオンが除去された高純度のポリビニルアセター
ルの水溶液を得ることができる。According to the present invention, an aqueous solution containing such a water-soluble polyvinyl acetal is preferably heated with stirring to separate a concentrated aqueous solution layer of the water-soluble polyvinyl acetal (upper layer) and an aqueous layer (lower layer) into a lower layer. The resulting aqueous layer is extracted from the concentrated aqueous solution layer of the water-soluble polyvinyl acetal and separated, and if necessary, such separation operation is repeated to remove chlorine ions and sodium ions as impurities. A highly pure aqueous solution of polyvinyl acetal can be obtained.
本発明の方法は、樹脂濃度が20重量％以下のポリビニル
アセタールの水溶液の精製に好適である。また、水溶液
の加熱温度は、通常、50〜100℃の範囲であるが、好ま
しくは80〜100℃の範囲である。The method of the present invention is suitable for purifying an aqueous solution of polyvinyl acetal having a resin concentration of 20% by weight or less. The heating temperature of the aqueous solution is usually in the range of 50 to 100 ° C, preferably 80 to 100 ° C.
（発明の効果） 以上のように、本発明によれば、特に、無機イオンを不
純物として含む水溶性ポリビニルアセタールの水溶液か
らそれら不純物を効果的に除去することができる。特
に、本発明によれば、水系で水溶性ポリビニルアセター
ルを製造し、水系のままでの処理によつて不純物を除去
して、精製されたポリビニルアセタールの水溶液を得る
ことができる。(Effect of the Invention) As described above, according to the present invention, particularly, the impurities can be effectively removed from the aqueous solution of the water-soluble polyvinyl acetal containing the inorganic ion as the impurity. In particular, according to the present invention, a water-soluble polyvinyl acetal can be produced in an aqueous system, impurities can be removed by treatment in an aqueous system as it is, and a purified aqueous solution of polyvinyl acetal can be obtained.
このようにして得られた不純物イオンを含まない精製ポ
リビニルアセタール水溶液は、例えば、電子工業におい
て、セラミツク・コンデンサー製造用のセラミツク・グ
リーン・シートのための水性バインダーとして好適に用
いることができる。また、水性インクジエツト記録紙用
コーテイング剤や親水性付与添加剤等に用いることがで
きる。The purified polyvinyl acetal aqueous solution containing no impurity ions thus obtained can be suitably used, for example, in the electronics industry as an aqueous binder for a ceramic green sheet for producing a ceramic capacitor. Further, it can be used as a coating agent for water-based ink jet recording paper, an additive for imparting hydrophilicity, and the like.
（実施例） 以下に実施例を挙げて本発明の方法を具体的に説明す
る。(Examples) The method of the present invention will be specifically described below with reference to Examples.
実施例１ 重合度500、ケン化度88モル％のポリビニルアルコール7
90重量部を純水2120重量部に加え、90℃で約２時間撹拌
して、溶解させた。この後、45℃に冷却し、35重量％塩
酸27重量部を加えて、35℃まで冷却した。次いで、これ
に純度99重量％のブチルアルデヒド62重量部を２時間か
けて滴下した後、35℃で３時間反応させたところ、白濁
した溶液を得た。Example 1 Polyvinyl alcohol 7 having a polymerization degree of 500 and a saponification degree of 88 mol% 7
90 parts by weight was added to 2120 parts by weight of pure water, and stirred at 90 ° C. for about 2 hours to dissolve. Then, the mixture was cooled to 45 ° C, 27 parts by weight of 35% by weight hydrochloric acid was added, and the mixture was cooled to 35 ° C. Next, 62 parts by weight of butyraldehyde having a purity of 99% by weight was added dropwise thereto over 2 hours, and the mixture was reacted at 35 ° C. for 3 hours to obtain a cloudy solution.
撹拌下にこれに10重量％水酸化ナトリウム水溶液66重量
部を加え、中和した後、20℃まで冷却して、透明な溶液
を得た。While stirring, 66 parts by weight of a 10% by weight aqueous sodium hydroxide solution was added to neutralize the mixture and then cooled to 20 ° C. to obtain a transparent solution.
この溶液５重量部をアルミニウム皿に分取し、70℃で３
時間真空乾燥したところ、上記溶液は約25重量％の固形
物を含んでおり、この固形物は、その赤外線吸収スペク
トルからポリビニルブチラール樹脂であることを確認し
た。JIS K 6728の方法によつて測定した樹脂のブチラー
ル化度は、約10モル％であつた。Dispense 5 parts by weight of this solution in an aluminum dish and mix at 70 ° C for 3
After vacuum drying for an hour, the solution contained about 25% by weight of solid matter, and it was confirmed from its infrared absorption spectrum that this solid matter was a polyvinyl butyral resin. The butyralization degree of the resin measured by the method of JIS K 6728 was about 10 mol%.
また、上記溶液中のナトリウムイオン濃度は、原子吸光
装置で測定した結果、2000ppm、イオンクロマトグラフ
イーで測定した塩素イオン濃度は約3000ppmであつた。Further, the sodium ion concentration in the above solution was measured by an atomic absorption spectrometer, and as a result, it was 2000 ppm, and the chloride ion concentration measured by ion chromatography was about 3000 ppm.
そこで、上記溶液500重量部を純水4500重量部に加え、
全体を5000重量部とし、これを撹拌しながら、95℃まで
加熱したところ、不透明で粘稠な上層と透明な下層とに
分離した。高温下で下層を分離し、粘稠な上層約500重
量部を得た。この層は、20℃まで冷却すると、透明な溶
液となつた。Therefore, add 500 parts by weight of the above solution to 4500 parts by weight of pure water,
When the whole was made into 5000 parts by weight and heated to 95 ° C. with stirring, an opaque and viscous upper layer and a transparent lower layer were separated. The lower layer was separated at high temperature to obtain about 500 parts by weight of a viscous upper layer. This layer became a clear solution when cooled to 20 ° C.
この溶液中の固形物の含有量を前述したと同様にして測
定したところ、23重量％であつて、この固形物は、ブチ
ラール化度約10モル％のポリビニルブチラール樹脂であ
つた。また、溶液中のナトリウムイオン濃度は約200pp
m、塩素イオン濃度は約310ppmにそれぞれ低減している
ことが確認された。The solid content in this solution was measured in the same manner as described above and found to be 23% by weight, and this solid was a polyvinyl butyral resin having a butyralization degree of about 10 mol%. The sodium ion concentration in the solution is about 200 pp.
It was confirmed that the m and chlorine ion concentrations were reduced to approximately 310 ppm, respectively.
実施例２ 重合度1000、ケン化度98.5モル％のポリビニルアルコー
ル255重量部を純水2700重量部に加え、90℃で約２時間
撹拌して、溶解させた。この後、45℃に冷却し、35重量
％塩酸20重量部を加えて、35℃まで冷却した。次いで、
これに純度99重量％のブチルアルデヒド16重量部を２時
間かけて滴下した後、35℃で３時間反応させたところ、
白濁した溶液を得た。Example 2 255 parts by weight of polyvinyl alcohol having a polymerization degree of 1000 and a saponification degree of 98.5 mol% was added to 2700 parts by weight of pure water, and the mixture was stirred at 90 ° C. for about 2 hours to be dissolved. Then, it cooled to 45 degreeC, 20 weight part of 35 weight% hydrochloric acid was added, and it cooled to 35 degreeC. Then
16 parts by weight of butyraldehyde having a purity of 99% by weight was added dropwise thereto over 2 hours and then reacted at 35 ° C. for 3 hours.
A cloudy solution was obtained.
撹拌下にこれに10重量％水酸化ナトリウム水溶液66重量
部を加え、中和した後、20℃まで冷却して、透明な溶液
を得た。While stirring, 66 parts by weight of a 10% by weight aqueous sodium hydroxide solution was added to neutralize the mixture and then cooled to 20 ° C. to obtain a transparent solution.
実施例１と同様にして、この溶液は、ブチラール化度約
８モル％のポリビニルブチラール樹脂を約８重量％含ん
でいることが確認された。また、溶液中のナトリウムイ
オン濃度は約1500ppm、塩素イオン濃度は約2200ppmであ
つた。In the same manner as in Example 1, it was confirmed that this solution contained about 8% by weight of polyvinyl butyral resin having a butyralization degree of about 8 mol%. The sodium ion concentration in the solution was about 1500 ppm, and the chloride ion concentration was about 2200 ppm.
そこで、上記溶液500重量部を純水4500重量部に加え、
全体を5000重量部とし、これを撹拌しながら、95℃まで
加熱したところ、不透明で粘稠な上層と透明な下層とに
分離した。高温下で下層を分離し、粘稠な上層約200重
量部を得た。この層は、20℃まで冷却すると、透明な溶
液となつた。Therefore, add 500 parts by weight of the above solution to 4500 parts by weight of pure water,
When the whole was made into 5000 parts by weight and heated to 95 ° C. with stirring, an opaque and viscous upper layer and a transparent lower layer were separated. The lower layer was separated under high temperature to obtain about 200 parts by weight of a viscous upper layer. This layer became a clear solution when cooled to 20 ° C.
この溶液中の固形物の含有量を前述したと同様にして測
定したところ、約21重量％であつて、この固形物は、ブ
チラール化度約８モル％のポリビニルブチラール樹脂で
あつた。また、溶液中のナトリウムイオン濃度は約60pp
m、塩素イオン濃度は約90ppmにそれぞれ低減しているこ
とが確認された。The solid content in this solution was measured in the same manner as described above, and it was about 21% by weight, and this solid was a polyvinyl butyral resin having a butyralization degree of about 8 mol%. The sodium ion concentration in the solution is about 60 pp.
It was confirmed that the m and chloride ion concentrations were reduced to about 90 ppm.
Claims (1)
を加熱して、水溶性ポリビニルアセタールの濃厚水溶液
層と水層とを形成し、この水層を前記ポリビニルアセタ
ールの濃厚水溶液から分離することを特徴とする水溶性
ポリビニルアセタールの精製方法。1. An aqueous solution containing a water-soluble polyvinyl acetal is heated to form a concentrated aqueous solution layer of water-soluble polyvinyl acetal and an aqueous layer, and the aqueous layer is separated from the concentrated aqueous solution of polyvinyl acetal. A method for purifying a water-soluble polyvinyl acetal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34054889A JPH0699499B2 (en) | 1989-12-28 | 1989-12-28 | Purification method of water-soluble polyvinyl acetal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34054889A JPH0699499B2 (en) | 1989-12-28 | 1989-12-28 | Purification method of water-soluble polyvinyl acetal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200805A JPH03200805A (en) | 1991-09-02 |
| JPH0699499B2 true JPH0699499B2 (en) | 1994-12-07 |
Family
ID=18338043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34054889A Expired - Lifetime JPH0699499B2 (en) | 1989-12-28 | 1989-12-28 | Purification method of water-soluble polyvinyl acetal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699499B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040157078A1 (en) * | 2001-01-25 | 2004-08-12 | Takahiro Yoshida | Polyvinyl acetal, polyvinyl acetal composition, ink coating material, dispersant, heat-developable photosensitive material,ceramic green sheet, primer for plastic lens, recording agent for water-based ink and adhesive for metal foil |
| DE60233513D1 (en) | 2001-09-21 | 2009-10-08 | Sekisui Chemical Co Ltd | MODIFIED POLYVINYL ACETAL RESIN |
| JP4012480B2 (en) | 2003-03-28 | 2007-11-21 | Ａｚエレクトロニックマテリアルズ株式会社 | Fine pattern formation aid and process for producing the same |
| US7923200B2 (en) | 2007-04-09 | 2011-04-12 | Az Electronic Materials Usa Corp. | Composition for coating over a photoresist pattern comprising a lactam |
| JP4610578B2 (en) * | 2007-04-24 | 2011-01-12 | Ａｚエレクトロニックマテリアルズ株式会社 | Fine pattern formation aid |
| US7745077B2 (en) | 2008-06-18 | 2010-06-29 | Az Electronic Materials Usa Corp. | Composition for coating over a photoresist pattern |
| CN103765608B (en) * | 2011-06-28 | 2016-05-18 | 株式会社可乐丽 | Encapsulant used for solar batteries and intermediate film for laminated glasses |
-
1989
- 1989-12-28 JP JP34054889A patent/JPH0699499B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03200805A (en) | 1991-09-02 |
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