JPH02263838A - Production of polyvinyl acetal-based sponge - Google Patents
Production of polyvinyl acetal-based spongeInfo
- Publication number
- JPH02263838A JPH02263838A JP8456589A JP8456589A JPH02263838A JP H02263838 A JPH02263838 A JP H02263838A JP 8456589 A JP8456589 A JP 8456589A JP 8456589 A JP8456589 A JP 8456589A JP H02263838 A JPH02263838 A JP H02263838A
- Authority
- JP
- Japan
- Prior art keywords
- sponge
- minutes
- solution
- heating
- acid
- 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
- 229920002554 vinyl polymer Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims description 11
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 title claims 2
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000006359 acetalization reaction Methods 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000005611 electricity Effects 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005187 foaming Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract 1
- 150000001241 acetals Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 101000939517 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 2 Proteins 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102100029643 Ubiquitin carboxyl-terminal hydrolase 2 Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 etc. are used Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリビニルアセタール系スポンジの製造方法
に関し、さらに詳しくは、ガーゼの代用品、電解質の保
持材料、化粧用パフ、事務用海綿、各種吸水材等に有用
な均一な気泡構造を有するポリビニルアセタール系スポ
ンジの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing polyvinyl acetal sponges, and more specifically, to gauze substitutes, electrolyte retention materials, cosmetic puffs, office sponges, and various other products. The present invention relates to a method for producing a polyvinyl acetal sponge having a uniform cell structure useful for water absorbing materials, etc.
（従来の技術）
従来、ポリビニルアセタール系゛スポジジの製造方法と
しては、ヨーロッパ及び米国で開発された起泡法、並び
に我国で発達した可溶性物質添加法に大別される。(Prior Art) Conventionally, methods for producing polyvinyl acetal posiposites are roughly divided into a foaming method developed in Europe and the United States, and a soluble substance addition method developed in Japan.
起泡法としては、反応液に不活性ガスを圧入し加熱発泡
させる方法（劃＠：ＵＳＰ２．０８３゜６２８）、反応
原液にサポニン等の起泡剤を加え、撹拌により泡立てた
後、アセタール化反応を行なう方法（参照： ＢＰ５７
３．６６６） 、反応原液に空気を吹き込んで泡状とし
、これをホルマール固定化させる方法（参照：ＵＳＰ２
．６０９゜３４７）等がある（参照二大野良夫はか、［
ポリビニルアルコール系多孔材」、工業材料、２５【２
〕、（１９７７））。Foaming methods include a method of pressurizing an inert gas into the reaction solution and heating and foaming it (劃@USP2.083゜628), adding a foaming agent such as saponin to the reaction stock solution, stirring to foam, and then acetalization. Method of carrying out the reaction (reference: BP57
3.666), a method of blowing air into the reaction stock solution to make it foamy and formalizing it (reference: USP2
．． 609゜347) etc. (see Yoshio Niohno, [
"Polyvinyl alcohol based porous material", Industrial materials, 25 [2
], (1977)).
我国で発達した可溶性物質添加法としては、ポリビニル
アルコールの水溶液にデンプンまたは、その懸濁水溶液
を加えて加熱混合し、アルデヒド及び酸を添加し、アセ
タール化反応を行ない、得られたアセタール化物から未
反応物、不純物を除去、水洗せしめる方法（参照：特公
昭４０−１５６５２号公報、特開昭４９−６３７５５号
公報、特開昭５０−６６６３号公報等）等がある。また
、孔径の均一化に関するものとして、アセタール化の際
の加熱をジュール熱により行なうもの（参照：特公昭３
３−３１９１号公報、特開昭６３−１７３６１４号公報
等）がある。A soluble substance addition method developed in Japan involves adding starch or its suspended aqueous solution to an aqueous solution of polyvinyl alcohol, heating and mixing, adding aldehyde and acid, and performing an acetalization reaction. There is a method of removing reactants and impurities and washing with water (see Japanese Patent Publication No. 15652/1980, Japanese Patent Application Laid-Open No. 63755/1982, Japanese Patent Application Laid-Open No. 6663/1989, etc.). In addition, regarding the uniformity of pore diameter, heating during acetalization is performed using Joule heat (see: Japanese Patent Publication No. 3
3-3191, JP-A-63-173614, etc.).
しかし、このような従来の起泡法によるものは、気泡が
大きいことが欠点である。これは気泡が生じた後、アセ
タール化による固化に数時間かかり、微細な気泡が集ま
って大きな気泡になるためである。However, the drawback of such conventional foaming methods is that the bubbles are large. This is because after bubbles are generated, it takes several hours for them to solidify due to acetalization, and fine bubbles gather to form large bubbles.
一方、我国で発達した可溶性物質添加法は、デンプン等
の可溶性物質を大量に添加し、成形後抽出するので、抽
出工程を要し、かつデンプンを含有した廃水処理に多額
の費用がかかることが欠点であった。On the other hand, the soluble substance addition method developed in Japan involves adding a large amount of soluble substances such as starch and extracting them after molding, which requires an extraction process and requires a large amount of cost to treat wastewater containing starch. It was a drawback.
上記問題点を解決するため１本出願人は、ポリビニルア
ルコール混合液に機械的発泡を行ない。In order to solve the above problems, the present applicant mechanically foams the polyvinyl alcohol mixture.
ついで電離性放射線を照射して、均一にゲル化せしめる
方法を開発した。（特願昭６３−２６２０３９号）。They then developed a method to uniformly gel the material by irradiating it with ionizing radiation. (Patent Application No. 63-262039).
（発明が解決しようとする課題）
前記した本出願人の方法によれば、均一な気泡構造を有
するポリビニルアセタール系スポンジを得ることができ
る。また、可溶性物質の抽出工程が不必要で、廃水処理
の問題もない。(Problems to be Solved by the Invention) According to the method of the present applicant described above, a polyvinyl acetal sponge having a uniform cell structure can be obtained. Furthermore, there is no need for an extraction step for soluble substances, and there are no problems with wastewater treatment.
しかしながら、電離性放射線による架橋は、被照射物の
厚みに限界がある。また、電離性放射線の設備は多額の
費用がかかり、小規模の生産に適さない等の欠点があっ
た。However, crosslinking using ionizing radiation has a limit on the thickness of the object to be irradiated. Additionally, ionizing radiation equipment costs a lot of money and has disadvantages such as being unsuitable for small-scale production.
従って、本発明の目的は、前記したような従来の方法の
欠点を解消し、均一な気泡構造を有する厚物のポリビニ
ルアセクール系スポンジを経済的かつ能率的に製造する
方法を提供することにある（課題を解決するための手段
）
本発明の方法によれば、前記目的を達成するため、基本
的には、機械的発泡を行なった後にジュール熱によって
加熱して、アセタール化せしめることを特徴とする。Therefore, an object of the present invention is to provide an economical and efficient method for producing a thick polyvinyl acecool sponge having a uniform cell structure by eliminating the drawbacks of the conventional methods as described above. (Means for Solving the Problem) According to the method of the present invention, in order to achieve the above-mentioned object, basically, after performing mechanical foaming, heating is performed using Joule heat to acetalize the foam. shall be.
すなわち１本発明の方法は、ポリビニルアルコール水溶
液を界面活性剤の存在下で機械的に発泡させた後、アル
デヒド及び酸を加えてスポンジ生成液を調整し、一対の
電極板を該生成液中に装置し、該電極板間に電気を通ず
ることによって該生成液を均一に加熱して、アセタール
化反応を行なうことを特徴とする。Namely, in the method of the present invention, a polyvinyl alcohol aqueous solution is mechanically foamed in the presence of a surfactant, an aldehyde and an acid are added to prepare a sponge solution, and a pair of electrode plates are placed in the solution. The device is characterized in that the produced liquid is uniformly heated by passing electricity between the electrode plates to carry out the acetalization reaction.
（発明の作用及び態様）
すなわち、本発明の方法は、機械的に発泡させた後に、
アルデヒド及び酸を加えたスポンジ生成液にジュール熱
を加えて内部からの加熱を促進して均一にアセタール化
反応を行なうことによって、短時間にポリビニルアルコ
ールを固化させることを特徴とする。すなわち、スポン
ジ生成液中の気泡を短時間に固めて、均一な気泡構造を
形成せしめるものである。(Operations and aspects of the invention) That is, the method of the present invention includes, after mechanically foaming,
It is characterized by solidifying polyvinyl alcohol in a short period of time by applying Joule heat to the sponge product solution containing aldehyde and acid to promote internal heating and uniformly carrying out the acetalization reaction. That is, the bubbles in the sponge production liquid are solidified in a short time to form a uniform bubble structure.
以下、本発明に係るポリビニルアセクール系スポンジの
製造方法について具体的に説明する。Hereinafter, the method for producing a polyvinyl acecool sponge according to the present invention will be specifically explained.
まず、ポリビニルアルコール水溶液に界面活性剤を添加
し、混合して該水溶液中に空気を混入し、均一に分散さ
せることによって、気泡を形成させる。気泡を含んだ水
溶液の体積は、混合前の該水溶液の体積の１５０〜４５
０％が好ましい。First, a surfactant is added to an aqueous polyvinyl alcohol solution and mixed to mix air into the aqueous solution and uniformly disperse it to form air bubbles. The volume of the aqueous solution containing air bubbles is 150 to 45% of the volume of the aqueous solution before mixing.
0% is preferred.
ついで、気泡を含んだ水溶液にアルデヒド及び酸、必要
に応じて他の添加剤を加え、均一に混合して、スポンジ
生成液をＷＲ整する。Next, aldehyde and acid, and other additives as necessary, are added to the bubble-containing aqueous solution and mixed uniformly to prepare the sponge product liquid for WR.
得られた生成液を２個の電極を装置した容器中に入れ、
該電極間に一定電圧で通電する。通電時の電圧は、好ま
しくは１０〜１００Ｖ、特に好ましくは２０〜５０Ｖの
電気を、好ましくは１〜６０分間、特に好ましくは２０
〜５０分間通じて、ジュール熱によって、該生成液を加
熱する。ここで電圧が１００Ｖを超えると短時間でスポ
ンジ生成液が昇温するので、温度の調整が困難である。The obtained product liquid is placed in a container equipped with two electrodes,
A constant voltage is applied between the electrodes. The voltage during energization is preferably 10 to 100 V, particularly preferably 20 to 50 V, preferably for 1 to 60 minutes, particularly preferably 20 V.
Heat the product liquid with Joule heat for ˜50 minutes. If the voltage exceeds 100V, the temperature of the sponge production liquid increases in a short period of time, making it difficult to adjust the temperature.
一方、１０Ｖ未満では、ジュール熱が不足してアセター
ル化反応が遅れ、均一な気泡構造が得られない。加熱時
間の範囲についても、電圧と同じ現象が生じる。この通
電による加熱において、ポリビニルアルコールのアセタ
ール化反応は、均一な気泡構造を保持できる程度に達成
されている。On the other hand, if the voltage is less than 10 V, Joule heat is insufficient, the acetalization reaction is delayed, and a uniform cell structure cannot be obtained. The same phenomenon as the voltage occurs for the heating time range. In this heating by electricity supply, the acetalization reaction of polyvinyl alcohol is achieved to the extent that a uniform cell structure can be maintained.
つぎに、該生成液をスポンジとしての型上がりを良くす
るために、前記通電加熱より低い条件で加熱する。この
加熱はジュール熱でも良いし、外部からの加熱でも良い
。Next, in order to improve the molding of the resulting liquid into a sponge, it is heated under conditions lower than the electrical heating described above. This heating may be done by Joule heat or external heating.
ジュール熱による加熱の場合は、好ましくは１〜２０Ｖ
、特に好ましくは５〜１５Ｖの電気を、好ましくは１０
〜１２０分間、特に好ましくは３０〜６０分間通じる。In the case of heating by Joule heat, preferably 1 to 20V
, particularly preferably electricity of 5 to 15 V, preferably 10
It lasts for ~120 minutes, particularly preferably from 30 to 60 minutes.
外部による加熱の場合は、オーブン、水蒸気等によるジ
ャケット式加熱によって、該生成液の温度が４０〜．７
０℃の範囲になるように、１０−１２０分間加熱する。In the case of external heating, the temperature of the produced liquid is raised to 40 - 40°C by jacket heating using an oven, steam, etc. 7
Heat for 10-120 minutes to a temperature in the 0°C range.
このように二段階で加熱することによって、アセタール
化反応を完了せしめる。このようにして得られたポリビ
ニルアセタール系スポンジは、水洗によって、スポンジ
内部の未反応物及び不純物を除去し、最終製品となる。By heating in two stages in this way, the acetalization reaction is completed. The thus obtained polyvinyl acetal sponge is washed with water to remove unreacted substances and impurities inside the sponge, and becomes a final product.
得られたスポンジは、均一な気泡構造を有し、その表面
が極めて平滑で肌触の細かいものとなる本発明の方法で
用いる各試剤の種類、配合量並びに反応条件等について
は、前記した従来の方法がそのまま適用できる。The obtained sponge has a uniform cell structure, and its surface is extremely smooth and has a fine texture.The types, amounts, and reaction conditions of each reagent used in the method of the present invention are as per the conventional methods described above. The method can be applied as is.
本発明で用いるアルデヒドとしては、ホルムアルデヒド
、アセトアルデヒド、ベンズアルデヒド、アセトアルデ
ヒド、グリオキザール、ノニルアルデヒド等各種のアル
デヒド類が使用できるが、通常コスト等の点からホルム
アルデヒドが多用される。また、アセタール化反応の触
媒としての酸も、硫酸、塩酸、燐酸、臭化水素酸、アセ
ト酢酸等、通常アセタール化反応に用いられるものはい
ずれも使用できる。As the aldehyde used in the present invention, various aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, acetaldehyde, glyoxal, and nonylaldehyde can be used, but formaldehyde is usually used frequently from the viewpoint of cost. Further, as the acid as a catalyst for the acetalization reaction, any acid commonly used in the acetalization reaction can be used, such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, and acetoacetic acid.
また、本発明で用いられる界面活性剤としては、陰イオ
ン界面活性剤、両性界面活性剤、非イオン界面活性剤等
が用いられるが、陰イオン界面活性剤が特に好ましい。Further, as the surfactant used in the present invention, anionic surfactants, amphoteric surfactants, nonionic surfactants, etc. are used, and anionic surfactants are particularly preferred.
以下に実施例を挙げて本発明についてさらに具体的に説
明するが、本発明は下記実施例により何ら限定されるも
のではない。EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the Examples below.
実施例１
ポリビニルアルコール（日本合成化学工業■製、ゴーセ
ノール（ＮＨ−２０））の１２％水溶液２００ｇに界面
活性剤（三洋化成工業■製、サンデッドＥＮ）４ｇを添
加し、撹拌機で撹拌し、体積が８００ｍ１になるまで泡
立てた０次にこの気泡を含んだ液に、３７％ホルマリン
４０−１と５０％硫ｌ！！２４０ ｇを加え、混合した
。得られた混合液を上面が開口した塩化ビニルのケース
（縦１５０糟−１横１５０＋ａａ＋、高さ２００■■）
に移す０次に該ケースの両端にステンレス製の電極板を
置き、可変抵抗器により電圧を２５Ｖに設定し、２００
分間通電る。２０分間通１後の該混合液の温度は５５℃
であった。その後、電圧をＩＯＶに下げ、１時間通電し
、アセタール化反応を完了せしめた。Example 1 4 g of a surfactant (Sanded EN, manufactured by Sanyo Chemical Industries, Ltd.) was added to 200 g of a 12% aqueous solution of polyvinyl alcohol (Gohsenol (NH-20), manufactured by Nippon Gosei Kagaku Kogyo ■), and the mixture was stirred with a stirrer. Add 37% formalin 40-1 and 50% sulfur to this bubble-containing liquid that was bubbled until the volume reached 800ml! ! 240 g was added and mixed. The resulting mixed solution was placed in a vinyl chloride case with an open top (length: 150mm-1 width: 150+aa+, height: 200mm)
Next, place stainless steel electrode plates on both ends of the case, set the voltage to 25V with a variable resistor, and turn the voltage to 200V.
Power on for minutes. The temperature of the mixed solution after passing for 20 minutes was 55°C.
Met. Thereafter, the voltage was lowered to IOV and current was applied for 1 hour to complete the acetalization reaction.
この時、該混合液の温度は５５℃に維持されていた。こ
のようにして得られたポリビニルアセクール系スポンジ
は、均一な気泡構造を有し、弾性に優れ、みかけ密度は
約０．０３ｇ／ａｍ”であった比較例１
実施例１と全く同じ配合及び方法によって得られた混合
液を２実施例１と全（同じ寸法及び形状の塩化ビニルの
ケースに入れた。次にケースの両端に設けたステンレス
製の電極板間に電圧を５ｖに設定した電気を２時間通電
し、ジュール熱により、アセタール化せしめた。得られ
たポリビニルアセタール系スポンジは、内部の気泡が粗
く、均一な気泡構造を有していなかった。At this time, the temperature of the liquid mixture was maintained at 55°C. The polyvinyl acecool sponge thus obtained had a uniform cell structure, excellent elasticity, and an apparent density of approximately 0.03 g/am. The mixed solution obtained by this method was placed in a vinyl chloride case of the same size and shape as in Example 1. Next, an electric current was applied between stainless steel electrode plates provided at both ends of the case with a voltage set to 5V. was energized for 2 hours to acetalize it using Joule heat.The resulting polyvinyl acetal sponge had coarse internal cells and did not have a uniform cell structure.
実施例２
実施例１において、第１回目の通電時の電圧を４０Ｖに
設定し、１５分間通電した以外は、実施例１と全く同じ
配合及び方法によって、ポリビニルアセクール系スポン
ジを得た。得られたスポンジは、実施例１と全く同じ物
性及び外観を有していた。Example 2 A polyvinyl acecool sponge was obtained using the same formulation and method as in Example 1, except that the voltage during the first energization was set to 40 V and the energization was conducted for 15 minutes. The obtained sponge had exactly the same physical properties and appearance as Example 1.
実施例３
実施例１において、第１回目の通電時の電圧を９０Ｖに
設定し、３分間通電した以外は、実施例１と全く同じ配
合及び方法によって、ポリビニルアセクール系スポンジ
を得た。得られたスポンジは、実施例１と全（同じ物性
及び外観を有していた。Example 3 A polyvinyl acecool sponge was obtained using exactly the same formulation and method as in Example 1, except that the voltage during the first energization was set to 90 V and energized for 3 minutes. The obtained sponge had all the same physical properties and appearance as Example 1.
実施例４
実施例１と、全く同じ配合及び方法によって混合液を得
、全く同じ条件で第１回目の通電を行った後、水蒸気に
よるジャケット式加熱によって、該混合液の温度を５５
℃に維持しながら、１時間加熱した。得られたポリビニ
ルアセタール系スポンジは、実施例１と全く同じ物性、
外観を有していた。Example 4 A mixed solution was obtained using exactly the same formulation and method as in Example 1, and after the first energization was performed under exactly the same conditions, the temperature of the mixed solution was raised to 55% by jacket heating with water vapor.
The mixture was heated for 1 hour while maintaining the temperature at ℃. The obtained polyvinyl acetal sponge had exactly the same physical properties as Example 1,
It had an appearance.
実施例５
実施例４において、第１回目の通電時の電圧を４０Ｖに
変えた以外は、全く同じ配合及び方法によって、ポリビ
ニルアセタール系スポンジを得た、得られたスポンジは
、実施例４と全く同じ物性及び外観を有していた。Example 5 A polyvinyl acetal sponge was obtained using the same formulation and method as in Example 4, except that the voltage during the first energization was changed to 40 V. The obtained sponge was completely the same as in Example 4. They had the same physical properties and appearance.
（発明の効果）
以上のように、本発明の方法によれば、機械発泡させた
後、ジエール熱によって、ポリビニルアルコールをアセ
タール化せしめることによって、均一な気泡構造を有し
、弾性に優れたポリビニルアセタール系スポンジを得る
ことができる。また廃水処理の設備が不要であり、簡単
な設備で経済的かつ能率的に生産できる。得られるスポ
ンジは、厚みが制限されず、医療用海綿、化粧用パフ、
各種吸水材等の素材として極めて有用である。(Effects of the Invention) As described above, according to the method of the present invention, polyvinyl alcohol is acetalized by Zier heat after mechanical foaming, thereby producing polyvinyl alcohol having a uniform cell structure and excellent elasticity. Acetal sponge can be obtained. Furthermore, wastewater treatment equipment is not required, and production can be performed economically and efficiently using simple equipment. The resulting sponge has no thickness restrictions and can be used as medical sponges, cosmetic puffs,
It is extremely useful as a material for various water-absorbing materials.
Claims (3)
下で機械的に発泡させた後、アルデヒド及び酸を加えて
スポンジ生成液を調整し、一対の電極板を該生成液中に
装置し、該電極板間に電気を通ずることによって、該生
成液を均一に加熱して、アセタール化反応を行なうこと
を特徴とするポリビニルアセタール系スポンジの製造方
法。(1) After mechanically foaming a polyvinyl alcohol aqueous solution in the presence of a surfactant, aldehyde and acid are added to prepare a sponge production solution, a pair of electrode plates is placed in the production solution, and the electrode A method for producing a polyvinyl acetal sponge, which comprises uniformly heating the produced liquid by passing electricity between plates to carry out an acetalization reaction.
１〜６０分間通じた後、電圧１〜２０Ｖの電気を１０〜
１２０分間通じることを特徴とする請求項１記載の方法
。(2) After passing electricity at a voltage of 10 to 100V between a pair of electrode plates for 1 to 60 minutes, electricity at a voltage of 1 to 20V is passed for 10 to 60 minutes.
A method according to claim 1, characterized in that it lasts for 120 minutes.
１〜６０分間通じた後、外部加熱によって生成液を４０
〜７０℃に１０〜１２０分間維持せしめることを特徴と
する請求項１記載の方法。(3) After passing electricity at a voltage of 10 to 100 V for 1 to 60 minutes between a pair of electrode plates, the generated liquid is heated for 40 minutes by external heating.
A method according to claim 1, characterized in that the temperature is maintained at ~70°C for 10-120 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8456589A JPH02263838A (en) | 1989-04-03 | 1989-04-03 | Production of polyvinyl acetal-based sponge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8456589A JPH02263838A (en) | 1989-04-03 | 1989-04-03 | Production of polyvinyl acetal-based sponge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02263838A true JPH02263838A (en) | 1990-10-26 |
Family
ID=13834180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8456589A Pending JPH02263838A (en) | 1989-04-03 | 1989-04-03 | Production of polyvinyl acetal-based sponge |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02263838A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4920271A (en) * | 1972-06-17 | 1974-02-22 | ||
| JPS4943112A (en) * | 1972-09-02 | 1974-04-23 | ||
| JPS4963755A (en) * | 1972-10-24 | 1974-06-20 | ||
| JPS4964656A (en) * | 1972-10-25 | 1974-06-22 | ||
| JPS5887133A (en) * | 1981-10-31 | 1983-05-24 | ヘキスト・アクチエンゲゼルシヤフト | Open-pore porous formed body based on polyvinyl acetate and manufacture of same |
-
1989
- 1989-04-03 JP JP8456589A patent/JPH02263838A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4920271A (en) * | 1972-06-17 | 1974-02-22 | ||
| JPS4943112A (en) * | 1972-09-02 | 1974-04-23 | ||
| JPS4963755A (en) * | 1972-10-24 | 1974-06-20 | ||
| JPS4964656A (en) * | 1972-10-25 | 1974-06-22 | ||
| JPS5887133A (en) * | 1981-10-31 | 1983-05-24 | ヘキスト・アクチエンゲゼルシヤフト | Open-pore porous formed body based on polyvinyl acetate and manufacture of same |
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