JP2000080126A - Boron-crosslinked poly(vinyl alcohol) molded article and preparation thereof - Google Patents
Boron-crosslinked poly(vinyl alcohol) molded article and preparation thereofInfo
- Publication number
- JP2000080126A JP2000080126A JP10248834A JP24883498A JP2000080126A JP 2000080126 A JP2000080126 A JP 2000080126A JP 10248834 A JP10248834 A JP 10248834A JP 24883498 A JP24883498 A JP 24883498A JP 2000080126 A JP2000080126 A JP 2000080126A
- Authority
- JP
- Japan
- Prior art keywords
- boron
- pva
- borate
- boric acid
- crosslinked
- 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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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリビニルアルコ
ールをホウ素により架橋したホウ素架橋ポリビニルアル
コールからなる成形物に関し、詳しくは、硬度が高く、
油や有機溶媒に対する耐性に優れたホウ素架橋ポリビニ
ルアルコール成形物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article made of boron-crosslinked polyvinyl alcohol obtained by crosslinking polyvinyl alcohol with boron.
The present invention relates to a boron-crosslinked polyvinyl alcohol molded article having excellent resistance to oils and organic solvents.
【０００２】[0002]
【従来の技術】ポリビニルアルコール（以後、ＰＶＡと
記す）は、安価で、耐油性などに優れ、ケン化度を調節
したり、ホルマール化、ブチラール化などの処理を行う
ことにより物性が様々に変化する優れた高分子であり、
既に、フィルム、パッキング、ベルト、繊維などの多く
の用途で使用されている。特に剛性に優れることから、
最近では、ゴム、プラスチック、セメント等の補強材や
リチウム電池用セパレータなどの分野への利用も期待さ
れており、より硬度の高いＰＶＡの開発が望まれてい
る。2. Description of the Related Art Polyvinyl alcohol (hereinafter referred to as PVA) is inexpensive, has excellent oil resistance and the like, and its physical properties are variously changed by adjusting the degree of saponification or by performing a treatment such as formalization or butyralization. Is an excellent polymer that
Already used in many applications such as films, packing, belts, fibers and the like. Especially because of its excellent rigidity,
Recently, it is expected to be used in fields such as reinforcing materials such as rubber, plastic, and cement, and separators for lithium batteries, and the development of PVA having higher hardness is desired.
【０００３】このようなＰＶＡ成形物を得る方法として
は、ＰＶＡにホウ酸またはホウ酸塩を添加し、ホウ素に
よる架橋によって、ＰＶＡ成形物の硬度を向上させる方
法が知られている。このようなホウ素架橋ＰＶＡ成形物
を得る方法としては、ホウ素架橋ＰＶＡ繊維を得る方法
が特開昭６２−８５０１３号公報、特開昭６２−１４９
９０９号公報、特開平７−２４３１２２号公報等に例示
されている。As a method for obtaining such a PVA molded product, there is known a method in which boric acid or a borate is added to PVA, and the hardness of the PVA molded product is improved by crosslinking with boron. As a method for obtaining such a boron-crosslinked PVA molded product, a method for obtaining a boron-crosslinked PVA fiber is disclosed in JP-A-62-85013 and JP-A-62-149.
909 and JP-A-7-243122.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ホウ酸
またはホウ酸塩をＰＶＡ溶液に多量に添加すると、ＰＶ
Ａ溶液がゲル化してしまう問題があった。そのため、こ
れらの方法では、ホウ酸またはホウ酸塩の添加量を低く
抑えたゲル化していない紡糸原液や、ＰＶＡ溶液の濃度
やＰＶＡの重合度を低く抑えたゲル化していない紡糸原
液をノズルより押出し、押出後ゲル化させる必要があっ
た。あるいは、ホウ酸またはホウ酸塩を含有しないＰＶ
Ａ溶液を紡糸した後、これをホウ酸またはホウ酸塩溶液
に浸し、ホウ酸またはホウ酸塩を含浸させる必要があっ
た。このように、従来のホウ素架橋ＰＶＡ成形物の製造
方法では、ホウ酸またはホウ酸塩の添加量が微量であ
り、あるいは用いるＰＶＡの架橋度が低いため、得られ
るホウ素架橋ＰＶＡ成形物の硬度におのずと限界があっ
た。However, when a large amount of boric acid or borate is added to a PVA solution,
There was a problem that the solution A gelled. Therefore, in these methods, a non-gelled spinning dope in which the amount of boric acid or borate added is kept low, or a non-gelled spinning dope in which the concentration of the PVA solution or the degree of polymerization of PVA is kept low, is passed through the nozzle. It was necessary to extrude and gel after extrusion. Alternatively, PV without boric acid or borate
After spinning solution A, it was necessary to soak it in boric acid or borate solution to impregnate it with boric acid or borate. As described above, in the conventional method for producing a boron-crosslinked PVA molded article, since the amount of boric acid or borate added is very small, or the degree of crosslinking of the PVA used is low, the hardness of the obtained boron-crosslinked PVA molded article is reduced. There was a limit naturally.
【０００５】よって、本発明における課題は、従来のも
のよりも硬度が高く、ＰＶＡと同様に耐油性に優れたホ
ウ素架橋ＰＶＡ成形物、およびこのホウ素架橋ＰＶＡ成
形物を容易に得ることができる製造方法を提供すること
にある。[0005] Therefore, an object of the present invention is to provide a boron-crosslinked PVA molded product having a higher hardness than conventional ones and excellent oil resistance like PVA, and a process for easily obtaining the boron-crosslinked PVA molded product. It is to provide a method.
【０００６】[0006]
【課題を解決するための手段】かかる課題は、ホウ素架
橋ＰＶＡ成形物として、ポリビニルアルコール溶液にホ
ウ酸またはホウ酸塩を添加してゲル化し、乾燥してなる
ものを用い、ホウ素架橋ＰＶＡ成形物の製造方法とし
て、ポリビニルアルコール溶液にホウ酸またはホウ酸塩
を添加してゲル化し、ついで、このゲルを成形し、乾燥
する方法を用いることによって解決される。本発明のホ
ウ素架橋ＰＶＡ成形物の製造方法は、微量のホウ酸また
はホウ酸塩を添加したＰＶＡ溶液を、成形後ゲル化させ
る従来の製造方法とは異なり、ＰＶＡ溶液に多量のホウ
酸またはホウ酸塩を添加してゲル化させ、このゲルを成
形することを特徴としている。また、上記ホウ酸または
ホウ酸塩の添加量は、ポリビニルアルコール１００重量
部に対し、１〜３０重量部とすることが好ましい。An object of the present invention is to provide a boron-crosslinked PVA molded product which is obtained by adding boric acid or borate to a polyvinyl alcohol solution, gelling the resulting product, and drying. Is solved by adding boric acid or borate to a polyvinyl alcohol solution to form a gel, and then forming and drying this gel. The method for producing a boron-crosslinked PVA molded article of the present invention is different from the conventional production method in which a PVA solution containing a small amount of boric acid or borate is gelled after molding, and a large amount of boric acid or boric acid is added to the PVA solution. It is characterized in that the gel is formed by adding an acid salt to form a gel. The amount of the boric acid or borate is preferably 1 to 30 parts by weight based on 100 parts by weight of polyvinyl alcohol.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳しく説明する。
本発明に用いられるＰＶＡとしては、例えば、粘度法で
求めた平均重合度が約２０００で、ケン化度が９９％以
上のものが用いられる。ＰＶＡの平均重合度が高いほ
ど、硬度の高い成形物が得やすくなり、好ましくは１０
００以上である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As the PVA used in the present invention, for example, those having an average degree of polymerization of about 2,000 determined by a viscosity method and a degree of saponification of 99% or more are used. The higher the average degree of polymerization of PVA, the easier it is to obtain a molded product having high hardness.
00 or more.
【０００８】ＰＶＡ溶液に用いられる溶媒としては、例
えば、エチレングリコール、ジエチレングリコール、ト
リエチレングリコールなどの多価アルコール、ジメチル
スルホキシド、水などが挙げられる。中でも、ホウ素架
橋ＰＶＡゲルの成形、例えばキャスト後の乾燥のしやす
さを考慮して、水を用いることが望ましい。Examples of the solvent used for the PVA solution include polyhydric alcohols such as ethylene glycol, diethylene glycol and triethylene glycol, dimethyl sulfoxide, water and the like. Above all, it is preferable to use water in consideration of the easiness of forming the boron-crosslinked PVA gel, for example, drying after casting.
【０００９】ＰＶＡ溶液の濃度は、用いる溶媒等によっ
て設定されるものであり、特に限定はされないが、例え
ば１〜１５重量％、好ましくは３〜１０重量％とされ
る。ＰＶＡ溶液の濃度が１重量％未満では、ホウ酸また
はホウ酸塩を添加してもゲル化しにくいので好ましくな
い。また、１５重量％を越えるとＰＶＡが溶媒に溶解し
にくくなる。[0009] The concentration of the PVA solution is determined depending on the solvent used and the like, and is not particularly limited, but is, for example, 1 to 15% by weight, preferably 3 to 10% by weight. If the concentration of the PVA solution is less than 1% by weight, gelation is difficult even when boric acid or borate is added, which is not preferable. On the other hand, if it exceeds 15% by weight, PVA becomes difficult to dissolve in the solvent.
【００１０】本発明で用いられるホウ酸塩は、ＰＶＡ分
子間を架橋し、ＰＶＡの剛性を高めるものである。ホウ
酸塩としては、例えば、メタホウ酸、四ホウ酸などホウ
酸の金属塩、アンモニウム塩などが挙げられる。これら
ホウ酸塩の中でも、水に対する溶解度の良好なメタホウ
酸のアルカリ金属塩が好適に用いられる。The borate used in the present invention crosslinks between PVA molecules to increase the rigidity of PVA. Examples of the borate include metal salts of boric acid such as metaboric acid and tetraboric acid, and ammonium salts. Among these borates, alkali metal salts of metaboric acid having good solubility in water are preferably used.
【００１１】ホウ酸またはホウ酸塩の添加量は、ＰＶＡ
１００重量部に対して０．５〜３０重量部であり、好ま
しくは１〜３０重量部であり、より好ましくは１０〜３
０重量部である。ホウ酸またはホウ酸塩の添加量が１重
量部未満では、ＰＶＡ溶液がゲル化しにくく、得られる
ホウ素架橋ＰＶＡ成形物の剛性（硬度）が不十分とな
り、また、３０重量部を越えると未反応のホウ酸または
ホウ酸塩が増加するので、コストの面で好ましくなく、
また、未反応物が残るため、純度の面でも不利である。The amount of boric acid or borate added is PVA.
It is 0.5 to 30 parts by weight, preferably 1 to 30 parts by weight, more preferably 10 to 3 parts by weight per 100 parts by weight.
0 parts by weight. If the amount of boric acid or borate is less than 1 part by weight, the PVA solution is less likely to gel, and the rigidity (hardness) of the resulting boron-crosslinked PVA molded product becomes insufficient. The amount of boric acid or borate increases, which is undesirable in terms of cost.
Further, since unreacted substances remain, it is disadvantageous in terms of purity.
【００１２】また、ＰＶＡ溶液には、必要に応じて、改
質剤、着色剤、酸化防止剤などの添加剤を、得られる成
形物の特性を損なわない範囲で添加することも可能であ
り、ＰＶＡ溶液にホウ酸またはホウ酸塩を添加して得ら
れるゲルに、ポリエーテル、ポリフッ化ビニリデン（Ｐ
ＶＤＦ）、ポリアクリロニトリル（ＰＡＮ）などの他の
樹脂を添加してもよい。[0012] If necessary, additives such as a modifier, a colorant, and an antioxidant can be added to the PVA solution within a range that does not impair the properties of the obtained molded product. Gels obtained by adding boric acid or borate to a PVA solution are mixed with polyether, polyvinylidene fluoride (P
Other resins such as VDF) and polyacrylonitrile (PAN) may be added.
【００１３】次に、本発明のホウ素架橋ＰＶＡ成形物の
製造方法について説明する。本発明のホウ素架橋ＰＶＡ
成形物は、ＰＶＡ溶液にホウ酸またはホウ酸塩を添加し
てゲル化させ、ついで、このゲルを型にキャストするな
どして成形し、乾燥することによって得られる。また、
ＰＶＡ溶液にホウ酸またはホウ酸塩を添加して得られる
ゲルと、他の樹脂等を混合して、この混合物を成形し、
乾燥させる方法を用いてもよい。さらに、上述の方法の
以外に、ＰＶＡ溶液にホウ酸またはホウ酸塩を添加して
得られたゲルを適当な形に成形して乾燥し、得られたホ
ウ素架橋ＰＶＡ塊を押出機、ペレタイザ等を用いてペレ
ット状にし、これを押出成形法や射出成形法などによっ
て成形して、ホウ素架橋ＰＶＡ成形物を得ることも可能
である。Next, a method for producing the boron-crosslinked PVA molded product of the present invention will be described. Boron-crosslinked PVA of the present invention
A molded article is obtained by adding boric acid or a borate to a PVA solution to form a gel, then molding the gel by casting it into a mold or the like, and drying the gel. Also,
A gel obtained by adding boric acid or borate to a PVA solution is mixed with another resin or the like, and this mixture is molded.
A method of drying may be used. Further, in addition to the above-mentioned method, a gel obtained by adding boric acid or a borate to a PVA solution is formed into an appropriate shape and dried, and the obtained boron-crosslinked PVA mass is extruded, a pelletizer, or the like. It is also possible to obtain a boron-crosslinked PVA molded product by forming into a pellet using an extrusion molding method or an injection molding method.
【００１４】ＰＶＡ溶液にホウ酸またはホウ酸塩を添加
する方法としては、例えば、ホウ酸またはホウ酸塩の粉
末をＰＶＡ溶液に加え、溶解させる方法、ホウ酸または
ホウ酸塩の溶液をＰＶＡ溶液に加える方法などが挙げら
れるが、中でもホウ素架橋ＰＶＡの架橋密度を均一にす
るために、ホウ酸またはホウ酸塩の溶液をＰＶＡ溶液に
加える方法を用いることが好ましい。また、上記ホウ酸
またはホウ酸塩の溶液の濃度は、特に限定はされない
が、例えば、１〜３重量％とされ、また、使用される溶
剤としては、水を用いるのが好ましい。As a method of adding boric acid or borate to a PVA solution, for example, a method of adding boric acid or borate powder to a PVA solution and dissolving it, a method of adding a boric acid or borate solution to a PVA solution, In particular, it is preferable to use a method of adding a boric acid or borate solution to the PVA solution in order to make the crosslink density of the boron-crosslinked PVA uniform. The concentration of the boric acid or borate solution is not particularly limited, but is, for example, 1 to 3% by weight, and water is preferably used as a solvent.
【００１５】本発明におけるＰＶＡ溶液のゲル化は、ホ
ウ酸またはホウ酸塩の添加と同時に起こり、通常、常温
常圧下で行われる。また、本発明におけるキャストと
は、ＰＶＡ溶液にホウ酸塩を添加して得られるゲルを型
に注入し、所望の形状する操作のことであり、必要に応
じて、加圧、加熱、冷却などを行うことも可能である。
また、キャストに用いられる型は、特には限定はされ
ず、様々な型を用いることで多用な形状の成形物を得る
ことが可能である。The gelation of the PVA solution in the present invention occurs simultaneously with the addition of boric acid or a borate, and is usually carried out at normal temperature and normal pressure. The cast in the present invention is an operation of injecting a gel obtained by adding a borate to a PVA solution into a mold and shaping the gel into a desired shape, and if necessary, pressurizing, heating, cooling, etc. It is also possible to do.
The mold used for casting is not particularly limited, and a variety of shapes can be obtained by using various molds.
【００１６】本発明における乾燥とは、キャストされた
ゲルから溶媒を除去し、成形物を得る操作のことであ
り、その方法としては、例えば、加熱による方法、減圧
加熱による方法、真空乾燥による方法などが挙げられ
る。The drying in the present invention is an operation of removing a solvent from a cast gel to obtain a molded product. Examples of the method include a method by heating, a method by heating under reduced pressure, and a method by vacuum drying. And the like.
【００１７】本発明のホウ素架橋ＰＶＡ成形物の形状と
しては、特に限定されるものではないが、例えば、フィ
ルム、チューブ、繊維など、成形法に応じて多様な形状
とすることが可能である。The shape of the boron-crosslinked PVA molded article of the present invention is not particularly limited, but various shapes such as a film, a tube, and a fiber can be employed depending on the molding method.
【００１８】このようして得られたホウ素架橋ＰＶＡ成
形物にあっては、ＰＶＡ溶液に多量のホウ酸またはホウ
酸塩を添加し、ＰＶＡ分子間を多くのホウ素が架橋して
いるため、硬度が高く、耐油性に優れるという特性を持
ち、ホウ酸またはホウ酸塩の添加量の設定により、その
硬度等を容易に調整することができる。また、上記ホウ
素架橋ＰＶＡ成形物は、ＰＶＡ溶液をホウ酸またはホウ
酸塩でゲル化し、このゲルを成形し、乾燥することで容
易に製造できる。さらに、原料には環境に悪影響を与え
る物質を使用せず、得られる成形物は可燃性であるの
で、成形物の廃棄に関しても特に問題を生じない。In the boron-crosslinked PVA molded article thus obtained, since a large amount of boric acid or borate is added to the PVA solution and a large amount of boron is crosslinked between PVA molecules, the hardness is high. , And excellent in oil resistance, and its hardness and the like can be easily adjusted by setting the amount of boric acid or borate added. The boron-crosslinked PVA molded article can be easily produced by gelling a PVA solution with boric acid or a borate, molding the gel, and drying the gel. Furthermore, since no material that has an adverse effect on the environment is used as the raw material and the obtained molded product is flammable, there is no particular problem regarding disposal of the molded product.
【００１９】また、ホウ酸のアルカリ金属塩の添加によ
って得られるホウ素架橋ＰＶＡ成形物は、リチウムやナ
トリウムなどのアルカリ金属イオンを含有するため、シ
ングルイオン伝導体になるという特性を持っている。特
に、細孔を生じさせた膜状のホウ素架橋ＰＶＡ成形物
は、近年開発が進んでいるリチウム電池のセパレーター
等として利用が可能である。The boron-crosslinked PVA molded product obtained by adding an alkali metal salt of boric acid has the property of being a single ion conductor since it contains an alkali metal ion such as lithium and sodium. In particular, a film-shaped boron-crosslinked PVA molded product having pores can be used as a separator of a lithium battery, which has been recently developed.
【００２０】以下、実施例を示す。また、特に断りがな
い限り、「部」は「重量部」を、「％」は「重量％」を
示す。Hereinafter, examples will be described. Unless otherwise specified, “parts” indicates “parts by weight” and “%” indicates “% by weight”.
【００２１】本実施例における各物性の測定および評価
は、以下の方法を用いて行った。硬度の測定はＡＳＴＭ
ショアＡ形で行った。また、イオン伝導率は交流インピ
ーダンス法により測定した。The measurement and evaluation of each physical property in this example were performed using the following methods. ASTM for hardness measurement
Performed in Shore A form. The ionic conductivity was measured by an AC impedance method.
【００２２】（耐溶剤性の評価）得られたホウ素架橋Ｐ
ＶＡ成形物の粉末１部を、表１に示す水および有機溶剤
それぞれ１０部に添加し、その耐性を目視と重量変化に
て評価した。まったく変化が現れず、重量変化３％未満
のものを○、ゲル化したものを×とした。(Evaluation of solvent resistance)
One part of the powder of the VA molded product was added to each of 10 parts of water and an organic solvent shown in Table 1, and the resistance was evaluated by visual observation and weight change.変 化 indicates no change and less than 3% weight change, and × indicates gelled.
【００２３】（イオン伝導度の測定）得られたホウ素架
橋ＰＶＡ成形物から、直径２０ｍｍ、厚さ０．１ｍｍの
円形薄膜状試料を切り出した。これら試料の両面に、試
料と同一形状のステンレス板を圧着して電極とし、室温
でのイオン伝導度を測定した。(Measurement of Ion Conductivity) A circular thin film sample having a diameter of 20 mm and a thickness of 0.1 mm was cut out from the obtained boron-crosslinked PVA molded product. A stainless steel plate having the same shape as the sample was crimped on both surfaces of these samples to form electrodes, and the ionic conductivity at room temperature was measured.
【００２４】（実施例１〜８）粘度平均重合度２０００
のＰＶＡ１０部を水１０００部に溶解してＰＶＡ水溶液
とした。ついで、メタホウ酸リチウム（ＬｉＢＯ2 ）も
しくはメタホウ酸ナトリウム（ＮａＢＯ2 ）を水に溶解
して３％のホウ酸塩水溶液とした。次に、ＰＶＡ水溶液
にホウ酸塩水溶液を、ホウ酸塩の配合量が表１に示した
量（ＰＶＡ１０００部に対する量）となるように加え、
ゲル化させ、このゲルを直径１０ｃｍの円形のシャーレ
にキャストし、恒温層を用いて５０℃で５０時間乾燥
し、さらに真空中にて１１０℃で５０時間乾燥し、ゲル
から水を完全に除去し、直径１０ｃｍ、厚さ０．１ｍｍ
のホウ素架橋ＰＶＡ成形物を得た。得られたホウ素架橋
ＰＶＡ成形物の硬度、イオン伝導度を測定し、耐溶剤性
を評価した。結果を表１に示す。(Examples 1 to 8) Viscosity average degree of polymerization 2000
Was dissolved in 1000 parts of water to obtain a PVA aqueous solution. Then, lithium metaborate (LiBO 2 ) or sodium metaborate (NaBO 2 ) was dissolved in water to obtain a 3% borate aqueous solution. Next, an aqueous borate solution was added to the aqueous PVA solution so that the compounding amount of the borate became the amount shown in Table 1 (the amount based on 1000 parts of PVA).
This gel is gelled, and the gel is cast on a circular Petri dish having a diameter of 10 cm, and dried at 50 ° C. for 50 hours using a thermostatic layer, and further dried at 110 ° C. for 50 hours in a vacuum to completely remove water from the gel. And diameter 10cm, thickness 0.1mm
Was obtained. The hardness and ionic conductivity of the obtained boron-crosslinked PVA molded product were measured, and the solvent resistance was evaluated. Table 1 shows the results.
【００２５】（比較例１、２）粘度平均重合度２０００
のＰＶＡ１０部を水１０００部に溶解してＰＶＡ水溶液
とした。ついで、メタホウ酸リチウム（ＬｉＢＯ2 ）を
水に溶解して３％のホウ酸塩水溶液とした。次に、ＰＶ
Ａ水溶液にホウ酸塩水溶液を、ホウ酸塩の配合量が表１
に示した量（ＰＶＡ１０００部に対する量）となるよう
に加え、この混合溶液を直径１０ｃｍの円形のシャーレ
にキャストし、恒温層を用いて５０℃で５０時間乾燥
し、さらに真空中にて１１０℃で５０時間乾燥し、ゲル
から水を完全に除去し、直径１０ｃｍ、厚さ０．１ｍｍ
のホウ素架橋ＰＶＡ成形物を得た。得られたホウ素架橋
ＰＶＡ成形物の硬度、イオン伝導度を測定し、耐溶剤性
を評価した。結果を表１に示す。Comparative Examples 1 and 2 Viscosity average degree of polymerization 2000
Was dissolved in 1000 parts of water to obtain a PVA aqueous solution. Next, lithium metaborate (LiBO 2 ) was dissolved in water to obtain a 3% borate aqueous solution. Next, PV
A aqueous solution of borate was added to aqueous solution A, and the amount of borate was as shown in Table 1.
(The amount based on 1000 parts of PVA), and the mixed solution was cast on a circular petri dish having a diameter of 10 cm, dried at 50 ° C. for 50 hours using a thermostat, and further dried at 110 ° C. in vacuum. For 50 hours, completely remove water from the gel, diameter 10 cm, thickness 0.1 mm
Was obtained. The hardness and ionic conductivity of the obtained boron-crosslinked PVA molded product were measured, and the solvent resistance was evaluated. Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】上記の実施例１〜８のホウ素架橋ＰＶＡ成
形物はいずれも、比較例のホウ素架橋ＰＶＡ成形物より
も高い硬度を有していた。また、メタホウ酸塩の配合量
が多いほど硬度の高い成形物が得られた。また、メタホ
ウ酸塩の配合量が多いほどイオン伝導度の高い成形物が
得られ、また、メタホウ酸リチウムを添加した成形物よ
りもメタホウ酸ナトリウムを添加した成形物の方が高い
イオン伝導度を有していた。さらに、実施例１〜８の成
形物は、水を加えると再びゲル化したが、有機溶剤に対
しては優れた耐性を有していた。Each of the boron-crosslinked PVA molded products of Examples 1 to 8 had a higher hardness than the boron-crosslinked PVA molded product of the comparative example. In addition, a molded product having higher hardness was obtained as the amount of the metaborate was increased. In addition, as the amount of the metaborate compounded is larger, a molded article having higher ion conductivity is obtained, and a molded article to which sodium metaborate is added has a higher ion conductivity than a molded article to which lithium metaborate is added. Had. Furthermore, the molded products of Examples 1 to 8 gelled again when water was added, but had excellent resistance to organic solvents.
【００２８】[0028]
【発明の効果】以上説明したように、本発明のホウ素架
橋ＰＶＡ成形物にあっては、従来のホウ素架橋ＰＶＡ成
形物に比べ、硬度が高く、耐油性に優れ、その製造方法
は容易である。このようなホウ素架橋ＰＶＡ成形物は、
ゴム、プラスチック、セメント等の補強材として有用で
ある。また、ホウ酸のアルカリ金属塩を添加して得られ
る成形物は、シングルイオン伝導体になるという特性を
持っており、リチウム電池のセパレーター等として利用
可能である。As described above, the boron-crosslinked PVA molded article of the present invention has higher hardness, excellent oil resistance, and is easy to produce compared to conventional boron-crosslinked PVA molded articles. . Such a boron-crosslinked PVA molded product is:
It is useful as a reinforcing material for rubber, plastic, cement and the like. Further, a molded product obtained by adding an alkali metal salt of boric acid has a property of being a single ion conductor, and can be used as a separator of a lithium battery or the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｄ０１Ｆ 6/50 Ｄ０１Ｆ 6/50 Ｚ (72)発明者 宮田 裕之 東京都江東区木場１丁目５番１号 株式会 社フジクラ内 (72)発明者 渡辺 正義 神奈川県横浜市西区老松町30−３−401 Ｆターム(参考） 4F070 AA26 AB01 AC11 AC18 AE08 GA10 GB05 GB10 4J002 BE011 BE021 DK006 FD146 4J100 AD02P CA01 HA53 HB63 4L035 HH10 JJ01 KK05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) D01F 6/50 D01F 6/50 Z (72) Inventor Hiroyuki Miyata 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Co., Ltd. JJ01 KK05
Claims (3)
はホウ酸塩を添加してゲル化し、乾燥してなるホウ素架
橋ポリビニルアルコール成形物。1. A boron-crosslinked polyvinyl alcohol molded article obtained by adding boric acid or a borate to a polyvinyl alcohol solution, gelling and drying.
ポリビニルアルコール１００重量部に対し、１〜３０重
量部であることを特徴とする請求項１記載のホウ素架橋
ポリビニルアルコール成形物。2. The amount of boric acid or borate added is:
The boron-crosslinked polyvinyl alcohol molded product according to claim 1, wherein the amount is 1 to 30 parts by weight based on 100 parts by weight of the polyvinyl alcohol.
はホウ酸塩を添加してゲル化し、ついでこのゲルを成形
し、乾燥することを特徴とするホウ素架橋ポリビニルア
ルコール成形物の製造方法。3. A method for producing a boron-crosslinked polyvinyl alcohol molded article, comprising adding boric acid or a borate to a polyvinyl alcohol solution to form a gel, and then forming and drying the gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10248834A JP2000080126A (en) | 1998-09-02 | 1998-09-02 | Boron-crosslinked poly(vinyl alcohol) molded article and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10248834A JP2000080126A (en) | 1998-09-02 | 1998-09-02 | Boron-crosslinked poly(vinyl alcohol) molded article and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000080126A true JP2000080126A (en) | 2000-03-21 |
Family
ID=17184126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10248834A Withdrawn JP2000080126A (en) | 1998-09-02 | 1998-09-02 | Boron-crosslinked poly(vinyl alcohol) molded article and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000080126A (en) |
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|---|---|---|---|---|
| JP2008539320A (en) * | 2005-04-28 | 2008-11-13 | モノソル エルエルシー | Water-soluble composition and structure, and method for producing and using the same |
| JP2010156894A (en) * | 2008-12-30 | 2010-07-15 | Hitoo Okano | Internal organ model |
| WO2010126018A1 (en) * | 2009-04-28 | 2010-11-04 | 有限会社聖和デンタル | Organ model |
| JP2011075907A (en) * | 2009-09-30 | 2011-04-14 | Hitoo Okano | Blood vessel model |
| JP2013124317A (en) * | 2011-12-15 | 2013-06-24 | Kuraray Co Ltd | Polyvinyl alcohol-based polymer and method for producing hydrolyzable cellulose using the same |
| JP2017043661A (en) * | 2015-08-24 | 2017-03-02 | 日本酢ビ・ポバール株式会社 | Manufacturing method of hydrogel |
| JP2018538398A (en) * | 2015-12-22 | 2018-12-27 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Droplets dispersed in an aqueous medium |
-
1998
- 1998-09-02 JP JP10248834A patent/JP2000080126A/en not_active Withdrawn
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008539320A (en) * | 2005-04-28 | 2008-11-13 | モノソル エルエルシー | Water-soluble composition and structure, and method for producing and using the same |
| JP2010156894A (en) * | 2008-12-30 | 2010-07-15 | Hitoo Okano | Internal organ model |
| JP4675414B2 (en) * | 2008-12-30 | 2011-04-20 | 仁夫 岡野 | Organ model |
| US11315441B2 (en) * | 2009-04-28 | 2022-04-26 | Yuugengaisha Seiwadental | Organ model |
| WO2010126018A1 (en) * | 2009-04-28 | 2010-11-04 | 有限会社聖和デンタル | Organ model |
| US20120045743A1 (en) * | 2009-04-28 | 2012-02-23 | Yuugengaisha Seiwadental | Organ model |
| JP2011075907A (en) * | 2009-09-30 | 2011-04-14 | Hitoo Okano | Blood vessel model |
| US8758797B2 (en) | 2009-09-30 | 2014-06-24 | Yuugengaisha Seiwadental | PVA and silica particle blood vessel model |
| US9202389B2 (en) | 2009-09-30 | 2015-12-01 | Yuugengaisha Seiwadental | Blood vessel model comprising polyvinyl alcohol and silica particles |
| JP2013124317A (en) * | 2011-12-15 | 2013-06-24 | Kuraray Co Ltd | Polyvinyl alcohol-based polymer and method for producing hydrolyzable cellulose using the same |
| WO2017033892A1 (en) * | 2015-08-24 | 2017-03-02 | 日本酢ビ・ポバール株式会社 | Method for producing hydrogel |
| JP2017043661A (en) * | 2015-08-24 | 2017-03-02 | 日本酢ビ・ポバール株式会社 | Manufacturing method of hydrogel |
| JP2018538398A (en) * | 2015-12-22 | 2018-12-27 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Droplets dispersed in an aqueous medium |
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