JP2000273229A - Production of hydrophilized hydrophobic substrate - Google Patents
Production of hydrophilized hydrophobic substrateInfo
- Publication number
- JP2000273229A JP2000273229A JP11082515A JP8251599A JP2000273229A JP 2000273229 A JP2000273229 A JP 2000273229A JP 11082515 A JP11082515 A JP 11082515A JP 8251599 A JP8251599 A JP 8251599A JP 2000273229 A JP2000273229 A JP 2000273229A
- Authority
- JP
- Japan
- Prior art keywords
- water
- mercury lamp
- pressure mercury
- substrate
- sheet
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Cell Separators (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、親水化した疎水性
基材の製造方法に関する。さらに詳しくは、電池の正極
負極間に配置されてこれらを隔離させる電池用セパレー
ター等として好適に用いられる親水化した疎水性基材の
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrophilic base material. More specifically, the present invention relates to a method for producing a hydrophilized hydrophobic base material which is preferably used as a battery separator or the like which is disposed between a positive electrode and a negative electrode of a battery and isolates them.
【０００２】[0002]
【従来の技術】疎水性基材を親水化する技術は、分離
膜、フィルター、電池用セパレーター等の分野におい
て、非常に重要である。最も簡単なのは、多孔質膜を界
面活性剤で処理する方法である。この方法により、水に
濡れない疎水性の多孔質膜を、水が透過する親水性の多
孔質膜に変換することが可能で、実際に上市されてい
る。また、このほかプラズマ処理、オゾン処理、スルホ
ン化処理、水溶性ビニルモノマーのグラフト重合等の方
法が知られている。2. Description of the Related Art A technique for making a hydrophobic substrate hydrophilic is very important in the fields of separation membranes, filters, battery separators and the like. The simplest method is to treat the porous membrane with a surfactant. By this method, it is possible to convert a hydrophobic porous membrane that does not get wet with water into a hydrophilic porous membrane that is permeable to water, and is actually on the market. In addition, methods such as plasma treatment, ozone treatment, sulfonation treatment, and graft polymerization of a water-soluble vinyl monomer are also known.
【０００３】界面活性剤処理による親水化は、確かに初
期の親水化に関しては有効で、疎水性で水が透過しない
多孔質膜を、短時間で水が透過するまでに親水性にする
ことができる。しかしながら、この親水化処理した多孔
質膜は、一旦水につけた後、取り出して乾燥し、再度水
につけるともはや水には濡れない。これは、界面活性剤
処理した後に水につけると、担持した界面活性剤が水中
に溶出し、多孔質膜から脱離してしまうためである。従
って、界面活性剤による親水化は、単に初期親水化でき
るだけにすぎない。[0003] Hydrophilization by treatment with a surfactant is effective for the initial hydrophilization, and it is possible to make a hydrophobic, water-impermeable porous membrane hydrophilic in a short time until water permeates. it can. However, once the porous membrane subjected to the hydrophilic treatment is soaked in water, taken out, dried, and soaked in water again, it is no longer wet with water. This is because, when immersed in water after the surfactant treatment, the supported surfactant is eluted in water and detached from the porous membrane. Therefore, the hydrophilization by the surfactant is merely an initial hydrophilization.
【０００４】また、プラズマ処理の方法では、基材表面
に共有結合によってつながった親水性基を生成させるた
め、処理後水に漬けて乾燥した後、再度水に漬けても、
十分親水性を示し、水に濡れる。しかし、高濃度のアル
カリ水溶液に漬けると、処理層が脱落してしまい、乾燥
後再度水に漬けるともはや水に濡れなくなる。従って、
高濃度アルカリ水溶液を電解液とするアルカリ二次電池
用セパレーターとしては、このようなプラズマ処理によ
り親水化した多孔質膜は使えない。オゾン処理による親
水化も、これに類似の挙動をし、オゾン処理直後の疎水
性多孔質膜は、水に漬けると直ちに濡れ、優れた親水性
を示すが、乾燥した後再度水に漬けると、もはや濡れな
くなる。プラズマ処理及びオゾン処理の場合は、処理表
面に下層との密着強度の弱い処理面が生成し、この面が
親水性を示すが、その後のプロセスでこの処理面が下の
基材表面から剥離してしまい、親水性を失ってしまうの
ではないかと推察される。In the plasma treatment method, a hydrophilic group is formed on the surface of the base material by covalent bonds. Therefore, the substrate is immersed in water after the treatment, dried, and then immersed again in water.
Shows sufficient hydrophilicity and gets wet with water. However, when immersed in a high-concentration alkaline aqueous solution, the treated layer falls off, and when immersed again in water after drying, it is no longer wet with water. Therefore,
As a separator for an alkaline secondary battery using a high-concentration alkaline aqueous solution as an electrolytic solution, a porous membrane hydrophilized by such a plasma treatment cannot be used. Hydrophilization by ozone treatment also behaves similarly to this, and the hydrophobic porous membrane immediately after ozone treatment wets immediately when immersed in water and shows excellent hydrophilicity, but when immersed again in water after drying, No longer wet. In the case of plasma treatment and ozone treatment, a treated surface with low adhesion strength to the lower layer is generated on the treated surface, and this surface shows hydrophilicity, but this treated surface peels from the underlying substrate surface in the subsequent process. It is presumed that they lose hydrophilicity.
【０００５】一方、これらの方法に比較して、スルホン
化による親水化は、プラスチック製基材表面に、共有結
合にて強固に付いたスルホン酸基による親水化であるた
め、乾燥と水再浸漬を何回繰り返しても、親水性は変化
せず、高濃度アルカリ水溶液に浸漬しても、親水性は全
く変化しない。しかしながら、このスルホン化処理は、
発煙硫酸や無水硫酸などの非常に反応性の高い試薬によ
る処理であるため、強く処理すると基材のプラスチック
材料の分子鎖切断まで引き起こし、基材シートの強度低
下等をもたらし、工業用途に適用する際、強度ダメージ
による不具合が発生する可能性が高い。さらに、処理プ
ロセスから排出される廃酸の処理コストもかなり高くな
り、容易にスルホン化処理設備を拡充できる環境にはな
いと言わざるを得ない。On the other hand, in comparison with these methods, the hydrophilization by sulfonation is a hydrophilization by sulfonic acid groups firmly attached by covalent bonds to the surface of a plastic substrate, so that it is dried and re-immersed in water. No matter how many times is repeated, the hydrophilicity does not change, and even when immersed in a high-concentration aqueous alkali solution, the hydrophilicity does not change at all. However, this sulfonation treatment
Because it is a treatment with a highly reactive reagent such as fuming sulfuric acid or sulfuric anhydride, if it is strongly treated, it may even cause molecular chain scission of the plastic material of the base material, resulting in a decrease in the strength of the base material sheet, etc. At this time, there is a high possibility that a defect due to the strength damage occurs. Furthermore, the cost of treating waste acid discharged from the treatment process also becomes considerably high, and it cannot be said that there is no environment in which sulfonation treatment equipment can be easily expanded.
【０００６】また、グラフト重合による親水化は、水溶
性モノマーを共有結合によって基材と強固に結合させる
親水化方法であり、その能力は極めて高く、特性も良好
である。従って、アクリル酸、メタクリル酸等の水溶性
ビニルモノマーを用いたグラフト重合処理は、疎水性基
材を親水化させる方法として用いられている。しかしな
がら、前記水溶性ビニルモノマーは、カルボン酸タイプ
であるために、強い酸化雰囲気下では酸化分解の恐れが
ある。このため酸化還元分野、たとえば二次電池用セパ
レーター用途などへの適用は制限されている。[0006] The hydrophilization by graft polymerization is a method of hydrophilization in which a water-soluble monomer is firmly bonded to a substrate by a covalent bond, and has a very high ability and good characteristics. Therefore, a graft polymerization treatment using a water-soluble vinyl monomer such as acrylic acid or methacrylic acid is used as a method for hydrophilizing a hydrophobic substrate. However, since the water-soluble vinyl monomer is of a carboxylic acid type, it may be oxidatively decomposed in a strong oxidizing atmosphere. For this reason, application to the field of oxidation-reduction, for example, as a separator for a secondary battery, and the like, is limited.
【０００７】[0007]
【発明が解決しようとする課題】従って、本発明の目的
は、電池用セパレーター等として好適に用いられる親水
化した疎水性基材を製造する方法を提供することを目的
とする。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing a hydrophilic base material which is suitably used as a battery separator or the like.
【０００８】[0008]
【課題を解決するための手段】本発明の要旨は、疎水性
プラスチック製基材を低圧水銀ランプにより紫外線照射
した後、水素引き抜き型光重合開始剤溶液に接触させ、
乾燥させた後、水溶性ビニルモノマー水溶液に接触さ
せ、酸素が実質的に存在しない条件下で高圧水銀ランプ
により紫外線照射する工程を有することを特徴とする、
親水化した疎水性基材の製造方法に関する。The gist of the present invention is that a hydrophobic plastic substrate is irradiated with ultraviolet light by a low-pressure mercury lamp and then brought into contact with a hydrogen abstraction type photopolymerization initiator solution.
After drying, it is contacted with an aqueous solution of a water-soluble vinyl monomer, and has a step of irradiating ultraviolet rays with a high-pressure mercury lamp under the condition that oxygen is substantially absent.
The present invention relates to a method for producing a hydrophilic base material.
【０００９】[0009]
【発明の実施の形態】本発明では、まず、疎水性プラス
チック製基材を低圧水銀ランプにより紫外線照射する。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, first, a hydrophobic plastic substrate is irradiated with ultraviolet rays by a low-pressure mercury lamp.
【００１０】本発明で用いる疎水性プラスチック製基材
の材質としては、特に限定されないが、強い酸化還元雰
囲気下で用いるような、たとえばアルカリ二次電池用セ
パレーターのような用途では、特定の官能基を持たない
ポリオレフィン等が好適に用いられる。かかるポリオレ
フィンとしては、エチレン、プロピレン、１−ブテン、
４−メチル−１−ペンテン、１−ヘキセン等のオレフィ
ンの単独重合体、共重合体、およびこれらのブレンド物
等が挙げられ、これらの中ではポリエチレンが好まし
く、特に重量平均分子量が１×１０6 以上の超高分子量
ポリエチレンが好ましい。[0010] The material of the hydrophobic plastic substrate used in the present invention is not particularly limited. For example, when used in a strong oxidation-reduction atmosphere, such as a separator for an alkaline secondary battery, a specific functional group may be used. Is preferably used. Such polyolefins include ethylene, propylene, 1-butene,
Examples thereof include homopolymers and copolymers of olefins such as 4-methyl-1-pentene and 1-hexene, and blends thereof. Of these, polyethylene is preferable, and particularly, the weight average molecular weight is 1 × 10 6. The above ultrahigh molecular weight polyethylene is preferred.
【００１１】また、疎水性プラスチック製基材の形状と
しては、フィルム、板、成型物等あらゆるものが含まれ
るが、これらの中では、透過膜、フィルター、分離膜、
セパレーター等の分野で有用な多孔質膜が好ましい。多
孔質膜としては、あらゆるものを用いることができ、孔
径や空孔率等は特に限定されない。[0011] The shape of the hydrophobic plastic substrate includes all shapes such as a film, a plate, and a molded product. Among them, a permeable membrane, a filter, a separation membrane,
A porous membrane useful in the field such as a separator is preferred. As the porous membrane, any one can be used, and the pore diameter, the porosity, and the like are not particularly limited.
【００１２】本発明で疎水性プラスチック製基材として
特に好適に用いられる超高分子量ポリエチレンを用いた
多孔質膜は、常法により調製することができ、例えば下
記のようにして作製できる。A porous membrane using ultrahigh molecular weight polyethylene, which is particularly preferably used as a hydrophobic plastic substrate in the present invention, can be prepared by a conventional method, and can be produced, for example, as follows.
【００１３】超高分子量ポリエチレン粒子を保形具に充
填し、次いでこれを該樹脂の融点以上の温度に加熱され
た水蒸気雰囲気中で焼結させた後冷却することによりブ
ロック状の多孔質体が得られる。その後この多孔質体を
所定厚さに切削することにより多孔質膜を調製すること
ができる。得られた多孔性ポリエチレンシートは、空孔
率３０〜７０％、引っ張り強度２０〜１５０ｋｇ／ｃｍ
2 、通気性１×１０-4〜５×１０-3ｃｍ3 ・ｃｍ／ｃｍ
2 ・Ｐａ・ｓｅｃ、ＫＣｌ透過性１〜４×１０ -3ｃｍ2
／ｓｅｃの多孔性シート特性を有することが好ましい。[0013] The ultra-high molecular weight polyethylene particles are
And then heated to a temperature above the melting point of the resin.
After sintering in a steam atmosphere,
A lock-shaped porous body is obtained. Then this porous body
Preparing a porous membrane by cutting to a predetermined thickness
Can be. The resulting porous polyethylene sheet has pores
30-70%, tensile strength 20-150kg / cm
Two, Breathable 1 × 10-Four~ 5 × 10-3cmThree・ Cm / cm
Two・ Pa · sec, KCl permeability 1-4 × 10 -3cmTwo
/ Sec.
【００１４】本発明で用いる低圧水銀ランプは、内圧が
１ｍｍＨｇ以下で短波長の紫外線、特に１８４．９ｎｍ
及び／又は２５３．７ｎｍの紫外線を多く含む低圧水銀
ランプが望ましい。かかる低圧水銀ランプを用いて紫外
線照射をすると、照射系に酸素が共存する場合には、１
８４．９ｎｍの光により、次式のようにしてオゾンが発
生する。 Ｏ2 →Ｏ＋Ｏ， Ｏ＋Ｏ2 →Ｏ3 （オゾン）The low-pressure mercury lamp used in the present invention has an internal pressure of 1 mmHg or less and has a short wavelength of ultraviolet light, particularly 184.9 nm.
And / or a low-pressure mercury lamp containing a large amount of ultraviolet light of 253.7 nm is desirable. When ultraviolet irradiation is performed using such a low-pressure mercury lamp, if oxygen coexists in the irradiation system, 1
Ozone is generated by the light of 84.9 nm as in the following equation. O 2 → O + O, O + O 2 → O 3 (ozone)
【００１５】一方、２５３．７ｎｍの光は、オゾンを分
解し、原子状の酸素が発生し、この酸素が強い酸化力を
有する。これらの原子状酸素、オゾン等により、疎水性
プラスチック製基材表面の炭化水素基が酸化され、水酸
基、カルボニル基、カルボキシル基、エーテル結合等が
生成し、基材表面が親水化されるものと考えられる。し
かしながら、この低圧水銀ランプから出る紫外線照射だ
けによる親水化では、たとえば水の接触角でせいぜい１
００度程度までしか下がらない。On the other hand, light of 253.7 nm decomposes ozone to generate atomic oxygen, which has a strong oxidizing power. Hydrocarbon groups on the surface of the hydrophobic plastic substrate are oxidized by these atomic oxygen, ozone, etc., and a hydroxyl group, a carbonyl group, a carboxyl group, an ether bond, etc. are generated, and the surface of the substrate is made hydrophilic. Conceivable. However, in the case of hydrophilization only by ultraviolet irradiation emitted from the low-pressure mercury lamp, for example, the contact angle of water is at most 1
It can only go down to about 00 degrees.
【００１６】低圧水銀ランプによる紫外線照射の時間
は、通常、１分〜２時間程度であることが好ましい。The irradiation time of the ultraviolet ray by the low-pressure mercury lamp is usually preferably about 1 minute to 2 hours.
【００１７】次に、紫外線照射した疎水性プラスチック
製基材を水素引き抜き型光重合開始剤溶液に接触させ、
乾燥させて、該疎水性プラスチック製基材の表面に水素
引き抜き型光重合開始剤を付着させる。Next, the ultraviolet-irradiated hydrophobic plastic substrate is brought into contact with a hydrogen abstraction type photopolymerization initiator solution,
After drying, a hydrogen abstraction type photopolymerization initiator is attached to the surface of the hydrophobic plastic substrate.
【００１８】本発明で用いる水素引き抜き型光重合開始
剤としては、ベンゾフェノン、各種置換基を有するベン
ゾフェノン等のベンゾフェノン系光重合開始剤、２，４
−ジエチルチオキサントン、２−クロロチオキサントン
等のチオキサントン系光重合開始剤等を挙げられ、これ
らの中では、ガラスの吸収帯域より長波長の３３４ｎｍ
に吸収極大を有し、酸素遮断用カバー材として安価なガ
ラスを用いることができるという観点から、ベンゾフェ
ノン系光重合開始剤が好ましい。Examples of the hydrogen abstraction type photopolymerization initiator used in the present invention include benzophenone-based photopolymerization initiators such as benzophenone and benzophenone having various substituents;
Thioxanthone-based photopolymerization initiators such as -diethylthioxanthone and 2-chlorothioxanthone; among these, 334 nm having a longer wavelength than the absorption band of glass.
A benzophenone-based photopolymerization initiator is preferred from the viewpoint that it has an absorption maximum and that an inexpensive glass can be used as a cover material for blocking oxygen.
【００１９】前記水素引き抜き型光重合開始剤は、適量
の溶媒に溶解させた溶液として用いるが、かかる溶媒と
しては、例えば、アセトン、メチルエチルケトン、トル
エン、メタノール、エタノール等が挙げられる。水素引
き抜き型光重合開始剤の使用量は、溶媒１００重量部に
対して、通常、０．５〜１０重量部程度であることが好
ましい。The hydrogen abstraction type photopolymerization initiator is used as a solution dissolved in an appropriate amount of a solvent. Examples of such a solvent include acetone, methyl ethyl ketone, toluene, methanol and ethanol. Usually, the amount of the hydrogen abstraction type photopolymerization initiator to be used is preferably about 0.5 to 10 parts by weight based on 100 parts by weight of the solvent.
【００２０】疎水性プラスチック製基材を水素引き抜き
型光重合開始剤溶液に接触させる方法としては、特に限
定されないが、例えば、水素引き抜き型光重合開始剤溶
液中に浸漬する方法等が挙げられる。The method of bringing the hydrophobic plastic substrate into contact with the hydrogen-abstraction-type photopolymerization initiator solution is not particularly limited, and includes, for example, a method of immersing the substrate in the hydrogen-abstraction-type photopolymerization initiator solution.
【００２１】また、水素引き抜き型光重合開始剤溶液に
接触させた疎水性プラスチック製基材を乾燥させる方法
としては、特に限定されないが、例えば、熱風循環式乾
燥機等を用いて風乾させる方法等が挙げられる。The method of drying the hydrophobic plastic substrate that has been brought into contact with the hydrogen abstraction type photopolymerization initiator solution is not particularly limited. For example, a method of air-drying using a hot-air circulation dryer or the like. Is mentioned.
【００２２】次に、上記の工程により水素引き抜き型光
重合開始剤の付着した疎水性プラスチック製基材を水溶
性ビニルモノマー水溶液に接触させ、高圧水銀ランプに
より紫外線照射して、疎水性プラスチック製基材の表面
に、水溶性ビニルモノマーをグラフト重合させる。Next, the hydrophobic plastic substrate to which the hydrogen-abstraction type photopolymerization initiator has been adhered in the above process is brought into contact with a water-soluble vinyl monomer aqueous solution, and irradiated with ultraviolet light from a high-pressure mercury lamp to form a hydrophobic plastic substrate. A water-soluble vinyl monomer is graft-polymerized on the surface of the material.
【００２３】即ち、この工程では、内圧１〜数ａｔｍの
高圧水銀ランプにより紫外線照射することによって、疎
水性プラスチック製基材に付着した水素引き抜き型光重
合開始剤が励起され、カルボニル基がバイラジカル状態
になり、Ｏラジカルサイトが、周囲の疎水性プラスチッ
クの炭化水素基から水素を引き抜き、水素を引き抜かれ
たプラスチックに生成した炭素ラジカルが、系中の水溶
性ビニルモノマーに付加して、グラフト重合が開始され
るものと考えられている。That is, in this step, the hydrogen abstraction type photopolymerization initiator attached to the hydrophobic plastic substrate is excited by irradiating ultraviolet rays from a high-pressure mercury lamp having an internal pressure of 1 to several atm, and the carbonyl group becomes a biradical. O-radical sites are extracted, and hydrogen is extracted from the hydrocarbon groups of the surrounding hydrophobic plastic, and the carbon radicals generated in the hydrogen-extracted plastic are added to the water-soluble vinyl monomer in the system, resulting in graft polymerization. Is believed to be launched.
【００２４】水溶性ビニルモノマーとしては、例えば、
ビニルスルホン酸、ビニルスルホン酸ナトリウム、ビニ
ルスルホン酸カリウム等のビニルスルホン酸塩、スチレ
ンスルホン酸、スチレンスルホン酸ナトリウム、スチレ
ンスルホン酸カリウム等のスチレンスルホン酸塩、アク
リル酸、メタクリル酸等が挙げられ、これらの中では、
酸化分解に強く、酸化還元雰囲気下での使用にも問題が
生じにくいことから、ビニルスルホン酸、ビニルスルホ
ン酸塩、スチレンスルホン酸及びスチレンスルホン酸塩
が好ましい。Examples of the water-soluble vinyl monomer include, for example,
Vinyl sulfonic acid, sodium vinyl sulfonate, vinyl sulfonate such as potassium vinyl sulfonate, styrene sulfonic acid, sodium styrene sulfonate, styrene sulfonate such as potassium styrene sulfonate, acrylic acid, methacrylic acid and the like, Among these,
Vinyl sulfonic acid, vinyl sulfonic acid salt, styrene sulfonic acid and styrene sulfonic acid salt are preferable because they are resistant to oxidative decomposition and hardly cause a problem in use in a redox atmosphere.
【００２５】なお、前記水溶性ビニルモノマーは、適量
の水に溶解させた水溶液として用いる。水溶性ビニルモ
ノマーの使用量は、水１００重量部に対して、通常、１
０〜１５０重量部、好ましくは２５〜１００重量部程度
であることが望ましい。The water-soluble vinyl monomer is used as an aqueous solution dissolved in an appropriate amount of water. The amount of the water-soluble vinyl monomer is usually 1 to 100 parts by weight of water.
It is desirably about 0 to 150 parts by weight, preferably about 25 to 100 parts by weight.
【００２６】疎水性プラスチック製基材を水溶性ビニル
モノマー水溶液と接触させる方法としては、特に限定さ
れないが、例えば、水溶性ビニルモノマー水溶液中に浸
漬する方法等が挙げられる。The method of bringing the hydrophobic plastic substrate into contact with the aqueous vinyl monomer aqueous solution is not particularly limited, and includes, for example, a method of immersing the substrate in the aqueous vinyl monomer aqueous solution.
【００２７】本発明では、予め、疎水性プラスチック製
基材を低圧水銀ランプにより紫外線照射してある程度親
水化させているため、疎水性プラスチック製基材を水溶
性ビニルモノマー水溶液と接触させて、基材の表面にか
かるモノマーをグラフト重合させることが可能となる。In the present invention, since the hydrophobic plastic substrate is previously irradiated with ultraviolet rays by a low-pressure mercury lamp to make it hydrophilic to some extent, the hydrophobic plastic substrate is brought into contact with a water-soluble vinyl monomer aqueous solution to form a base. It becomes possible to graft-polymerize such a monomer on the surface of the material.
【００２８】高圧水銀ランプによる紫外線照射は、実質
的に酸素の存在しない条件下で行う必要がある。ここで
実質的に酸素の存在しない条件下とは、グラフト重合を
開始する疎水性プラスチック製基材上の炭化水素基か
ら、水素引き抜き型光重合開始剤への高圧水銀ランプか
らの紫外線照射により励起されて生じたＯラジカルによ
り水素が引き抜かれて、プラスチック上に生成した炭素
ラジカルが酸素と反応して水溶性ビニルモノマーに対す
るグラフト重合活性を失ってしまわない程度に酸素が存
在しない条件下を意味し、必ずしも完全に酸素がゼロで
あるということではない。従って、紫外線照射の方法と
しては、例えば、水溶性ビニルモノマー水溶液を含浸さ
せた疎水性プラスチック製基材を、ガラス、ポリエチレ
ンテレフタレートフィルム等からなる板で両面をはさ
み、なるべく気泡を追い出すようにして、板同士をクリ
ップ等で挟み、圧着して、紫外線を照射する方法、ある
いは完全に窒素等の不活性ガスにて置換された容器内に
疎水性プラスチック製基材を入れて高圧水銀ランプから
の紫外線を照射する方法等が挙げられる。Irradiation of ultraviolet rays by a high-pressure mercury lamp needs to be performed under conditions substantially free of oxygen. Here, the condition in which substantially no oxygen is present means that the hydrogen-extracting photopolymerization initiator is excited by ultraviolet irradiation from a high-pressure mercury lamp from a hydrocarbon group on a hydrophobic plastic substrate that initiates graft polymerization. Hydrogen is extracted by the generated O radical, and the carbon radical generated on the plastic does not react with oxygen to lose the graft polymerization activity to the water-soluble vinyl monomer. However, this does not necessarily mean that oxygen is completely zero. Therefore, as a method of ultraviolet irradiation, for example, a hydrophobic plastic substrate impregnated with a water-soluble vinyl monomer aqueous solution, glass, sandwiched on both sides with a plate made of polyethylene terephthalate film and the like, to expel air bubbles as much as possible, A method of irradiating ultraviolet rays by sandwiching the plates with clips or the like and pressing, or placing a hydrophobic plastic base material in a container completely replaced with an inert gas such as nitrogen and applying ultraviolet light from a high-pressure mercury lamp. And the like.
【００２９】高圧水銀ランプによる紫外線照射の時間
は、通常、１分〜２時間程度であることが好ましい。The irradiation time of the ultraviolet ray by the high-pressure mercury lamp is usually preferably about 1 minute to 2 hours.
【００３０】なお、高圧水銀ランプによる紫外線照射後
は、例えば、イオン交換水中に、親水化した疎水性基材
を浸漬することにより、基材を水洗して、基材表面に残
存する水溶液ビニルモノマーのホモポリマーを除去する
ことが好ましい。After the ultraviolet irradiation by the high-pressure mercury lamp, the base material is rinsed with water by, for example, immersing the hydrophilic base material in ion-exchanged water, and the aqueous vinyl monomer remaining on the base surface is washed. Is preferably removed.
【００３１】このようにして得られる親水化した疎水性
基材は、低いグラフト重合率で、水の接触角を著しく低
下させることができるため、優れた親水性を示し、また
グラフト重合率が低いため、基材の膨潤による寸法変形
を抑えることが可能となり、電池用セパレーター等の用
途に適する。The thus obtained hydrophilicized hydrophobic base material has a low graft polymerization rate and can remarkably lower the contact angle of water, so that it exhibits excellent hydrophilicity and a low graft polymerization rate. Therefore, dimensional deformation due to swelling of the base material can be suppressed, which is suitable for applications such as battery separators.
【００３２】[0032]
【実施例】以下、実施例および比較例を挙げてさらに詳
細に説明するが、本発明はこれらの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 with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００３３】シート製造例 重量平均分子量が５００万で融点が１３５℃、平均粒径
が約３０μｍ（メッシュ分級品）の超高分子量ポリエチ
レン粉末を、多数の孔が開けられた円筒型の金属板にポ
リテトラフルオロエチレン多孔質フィルムを内側に貼っ
た金型を外周に配し、底面にその外金型を固定できる金
型からなる保形具に充填した。この金型を金属製耐熱耐
圧容器（水蒸気の導入管及びその開閉バルブを備える）
に入れ、真空ポンプにより雰囲気圧を１０ｔｏｒｒとし
た。この時に要した時間は３０分であった。そして、ポ
ンプを停止後、バルブを開き、水蒸気（温度：１６０
℃、圧力：５ｋｇ／ｃｍ2 ）を導入し、このまま１時間
加熱焼結した後、冷却させ、円筒状の多孔質体を得た。
得られた多孔質体を切削旋盤により厚さ２００μｍに切
削し、空孔率５５％の超高分子量ポリエチレン製の多孔
性シートを得た。この多孔性シートについて水の接触角
を測定したところ１３４度であり、疎水性であった。Sheet Production Example Ultra-high molecular weight polyethylene powder having a weight average molecular weight of 5,000,000, a melting point of 135 ° C. and an average particle size of about 30 μm (mesh classified product) was applied to a cylindrical metal plate having a large number of holes. A mold having a polytetrafluoroethylene porous film adhered on the inside was arranged on the outer periphery, and the mold was filled in a shape retainer made of a mold capable of fixing the outer mold on the bottom surface. This mold is placed in a metal heat-resistant and pressure-resistant container (provided with a steam inlet pipe and an on-off valve).
And the atmospheric pressure was adjusted to 10 torr by a vacuum pump. The time required at this time was 30 minutes. Then, after stopping the pump, the valve is opened and steam (temperature: 160
C., pressure: 5 kg / cm 2 ), and after heating and sintering for 1 hour as it was, it was cooled to obtain a cylindrical porous body.
The obtained porous body was cut to a thickness of 200 μm by a cutting lathe to obtain a porous sheet made of ultrahigh molecular weight polyethylene having a porosity of 55%. When the contact angle of water was measured for this porous sheet, it was 134 degrees and it was hydrophobic.
【００３４】実施例１ シート製造例で得られた多孔性シートを、１５ｃｍ×２
０ｃｍの大きさに切断し、出力６５０Ｗの低圧水銀ラン
プ（オーク株式会社製、ＶＵＶ−６５Ｂ−２２−２１、
波長：１８５ｎｍ、２５４ｎｍ）で、ランプからの距離
１０ｃｍにシートを支持し、１０分ずつ両面照射した。
処理面の水の接触角は、１０５〜１１４度であった。こ
のシートを５％ベンゾフェノン／アセトン溶液に１０分
間浸漬後取り出し、１５分間風乾した。シリンダー状ガ
ラス製容器に、４０重量％ビニルスルホン酸ナトリウム
水溶液を２００ｍｌ入れ、その中に前記シートを浸漬
し、大型ベルジャー内にシリンダー状容器を入れ、アス
ピレータにて２０〜４０ｔｏｒｒ程度まで減圧した。減
圧すると、シートから泡が多数出た。モノマー溶液が含
浸されたシートを取り出し、Ａ４サイズのガラス板（厚
さ２ｍｍ）に挟み、ガラス板周囲をクリップで締め付け
た。このシートを挟み込んだガラス板を、高圧水銀ラン
プにて紫外線を５分間照射し、グラフト重合処理を行な
った。処理後、ガラス板からシートをはずし、イオン交
換水中に浸漬し、マグネティックスターラーにて攪拌し
ながら４時間水洗した。シートを取り出し、シートの上
と下をクリップで挟み、８０℃の乾燥機中にシートを吊
り下げ、２時間乾燥させて、親水化したシートを得た。Example 1 The porous sheet obtained in the sheet production example was 15 cm × 2
Cut to a size of 0 cm, and output 650 W of a low-pressure mercury lamp (manufactured by Oak Co., Ltd., VUV-65B-22-21,
(Wavelength: 185 nm, 254 nm), the sheet was supported at a distance of 10 cm from the lamp, and both sides were irradiated for 10 minutes.
The contact angle of water on the treated surface was 105 to 114 degrees. The sheet was immersed in a 5% benzophenone / acetone solution for 10 minutes, taken out, and air-dried for 15 minutes. 200 ml of a 40% by weight aqueous solution of sodium vinyl sulfonate was placed in a cylindrical glass container, the sheet was immersed therein, the cylindrical container was placed in a large bell jar, and the pressure was reduced to about 20 to 40 torr with an aspirator. When the pressure was reduced, many bubbles came out of the sheet. The sheet impregnated with the monomer solution was taken out, sandwiched between A4 size glass plates (2 mm thick), and the periphery of the glass plates was fastened with clips. The glass plate sandwiching this sheet was irradiated with ultraviolet rays for 5 minutes by a high-pressure mercury lamp to perform a graft polymerization treatment. After the treatment, the sheet was removed from the glass plate, immersed in ion-exchanged water, and washed with water for 4 hours while stirring with a magnetic stirrer. The sheet was taken out, the top and bottom of the sheet were clipped, and the sheet was suspended in a dryer at 80 ° C. and dried for 2 hours to obtain a hydrophilic sheet.
【００３５】実施例２〜４ 高圧水銀ランプによる紫外線照射時間をそれぞれ６分、
９分、１１分に変更してグラフト重合処理を行なった以
外は、実施例１と同様して親水化したシートを得た。Examples 2 to 4 The irradiation time of ultraviolet rays by a high-pressure mercury lamp was 6 minutes, respectively.
A hydrophilized sheet was obtained in the same manner as in Example 1, except that the graft polymerization treatment was performed for 9 minutes and 11 minutes.
【００３６】比較例１ 低圧水銀ランプによる紫外線照射のみを行ない、後の高
圧水銀ランプによるグラフト重合処理は行なわなかった
以外は、実施例１と同様にして親水化したシートを得
た。Comparative Example 1 A hydrophilic sheet was obtained in the same manner as in Example 1, except that only ultraviolet irradiation was performed using a low-pressure mercury lamp, and that subsequent graft polymerization was not performed using a high-pressure mercury lamp.
【００３７】比較例２ 低圧水銀ランプによる紫外線照射は行なわず、後の高圧
水銀ランプによるグラフト重合処理のみを行なった以外
は、実施例１と同様にして親水化したシートを得た。Comparative Example 2 A hydrophilic sheet was obtained in the same manner as in Example 1, except that ultraviolet irradiation was not performed by a low-pressure mercury lamp, and only graft polymerization treatment was performed by a high-pressure mercury lamp.
【００３８】実施例１〜４及び比較例１、２により得ら
れたシートのグラフト重合率と水の接触角を表１に示
す。なお、グラフト重合率及び水の接触角は、以下に示
す方法に従って求めた。Table 1 shows the graft polymerization rates and the contact angles of water of the sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2. In addition, the graft polymerization rate and the contact angle of water were determined according to the following methods.
【００３９】〔グラフト重合率の測定方法〕シートのグ
ラフト重合処理前後の重量を測定し、下記式に従って算
出する。[Measurement Method of Graft Polymerization Ratio] The weight of the sheet before and after the graft polymerization treatment is measured and calculated according to the following equation.
【００４０】グラフト重合率（％）＝１００×（グラフ
ト重合後の重量−グラフト重合前の重量）／グラフト重
合前の重量Graft polymerization rate (%) = 100 × (weight after graft polymerization−weight before graft polymerization) / weight before graft polymerization
【００４１】〔水の接触角〕協和界面科学（株）製の画
像処理式接触角計ＣＡ−Ｘを用いて測定する。厚み１ｍ
ｍのスライドガラス上に１ｃｍ×５ｃｍに切り出したシ
ートサンプルを両面粘着テープにて貼り付け、測定用試
料とする。蒸留水を用いて約１．８μｌの水滴をシリン
ジ先端につくり、試料面に接触させ、得られたシート上
水滴の接触角を測定し、５点の平均値を算出し、接触角
のデータとする。[Contact angle of water] Measured using an image processing contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. 1m thick
A sheet sample cut out to 1 cm × 5 cm on a slide glass of m is attached with a double-sided adhesive tape to obtain a sample for measurement. Approximately 1.8 μl of water droplet was formed on the tip of the syringe using distilled water, brought into contact with the sample surface, the contact angle of the obtained water droplet on the sheet was measured, the average of five points was calculated, and the contact angle data and I do.
【００４２】[0042]
【表１】 [Table 1]
【００４３】表１の結果より、比較例１、２の結果と対
比して、低圧水銀ランプによる紫外線照射及び高圧水銀
ランプによる紫外線照射の両方の処理を行なった実施例
１〜４のシートは、グラフト重合率が非常に小さいにも
かかわらず、水の接触角が小さく、高い親水性が得られ
ていることがわかる。特に実施例２〜４では接触角は０
度であった。From the results shown in Table 1, in comparison with the results of Comparative Examples 1 and 2, the sheets of Examples 1 to 4 which were subjected to both the ultraviolet irradiation by the low-pressure mercury lamp and the ultraviolet irradiation by the high-pressure mercury lamp were: It can be seen that although the graft polymerization rate is very small, the contact angle of water is small and high hydrophilicity is obtained. In particular, in Examples 2 to 4, the contact angle was 0.
Degree.
【００４４】比較例３ シート製造例で得られた多孔性シートを、１５ｃｍ×２
０ｃｍの大きさに切断し、界面活性剤であるドデシルベ
ンゼンスルホン酸ナトリウム〔テイカ（株）製、テイカ
パワーＬＮ２０５０〕の５重量％水溶液中に１０分間浸
漬し、取り出して１５分間乾燥させた。得られたシート
を水中に浸漬すると、かかるシートは水に非常によく濡
れ、多孔質膜内部にまで水は容易に浸透した。Comparative Example 3 The porous sheet obtained in the sheet production example was 15 cm × 2
It was cut into a size of 0 cm, immersed in a 5% by weight aqueous solution of a surfactant, sodium dodecylbenzenesulfonate [Taika Power LN2050, manufactured by Teica Co., Ltd.] for 10 minutes, taken out and dried for 15 minutes. When the obtained sheet was immersed in water, such a sheet was very well wetted by water, and water easily penetrated into the inside of the porous membrane.
【００４５】次に、この界面活性剤により親水化したシ
ートを、実施例１と同様にして、５％ベンゾフェノン／
アセトン溶液に１０分間浸漬し、取り出した後１５分間
風乾し、４０重量％ビニルスルホン酸ナトリウム水溶液
中に浸漬し、ガラス板に挟み、クリップで締め付けた後
高圧水銀ランプにて紫外線を６分間照射してグラフト重
合処理を行なった後、水洗し、乾燥させて、親水化した
シートを得た。得られたシートの水の接触角は、紫外線
照射面、非照射面ともに１２６度であった。Next, the sheet hydrophilized with this surfactant was treated with 5% benzophenone /
It was immersed in an acetone solution for 10 minutes, taken out, air-dried for 15 minutes, immersed in a 40% by weight aqueous solution of sodium vinyl sulfonate, sandwiched between glass plates, fastened with clips, and irradiated with ultraviolet light for 6 minutes with a high-pressure mercury lamp. After the graft polymerization treatment, the sheet was washed with water and dried to obtain a hydrophilic sheet. The contact angle of water of the obtained sheet was 126 degrees on both the ultraviolet irradiation surface and the non-irradiation surface.
【００４６】比較例４ グラフト重合処理は行なわずに得られたシートの水洗を
行なった以外は、比較例３と同様にしてシートを得た。
得られたシートの水の接触角は、片面が１２８度、他の
面が１２９度であった。Comparative Example 4 A sheet was obtained in the same manner as in Comparative Example 3, except that the obtained sheet was washed with water without performing the graft polymerization treatment.
The contact angle of water of the obtained sheet was 128 degrees on one side and 129 degrees on the other side.
【００４７】比較例５ グラフト重合処理は行なわず、得られたシートの水洗も
行なわなかった以外は、比較例３と同様にしてシートを
得た。得られたシートの水の接触角は、両面ともに０度
であった。Comparative Example 5 A sheet was obtained in the same manner as in Comparative Example 3, except that no graft polymerization treatment was performed and the obtained sheet was not washed with water. The contact angle of water of the obtained sheet was 0 degree on both sides.
【００４８】以上の結果より、界面活性剤により親水化
した後に、グラフト重合処理を行なった比較例３のシー
トの水洗後の水の接触角と、界面活性剤のみで親水化処
理した比較例４のシートの水洗後の水の接触角に、ほと
んど変化がみられないことから、実施例１〜４の場合と
は異なり、界面活性剤処理を予め行った比較例３のシー
トはグラフト重合処理による親水化をほとんど受けてい
ないことがわかる。また、比較例４および５の結果よ
り、界面活性剤による親水化の効果は、一旦水に浸漬す
ることにより、失われてしまうことがわかる。これに対
し、実施例１〜４で得られた親水化したシートは、水洗
しても優れた親水性が保持されている。From the above results, the contact angle of water of the sheet of Comparative Example 3, which was subjected to graft polymerization treatment after being hydrophilized with a surfactant, and the comparative example 4, which was subjected to hydrophilic treatment only with a surfactant, was carried out. Unlike the cases of Examples 1 to 4, the sheet of Comparative Example 3 in which the surfactant treatment was performed in advance was not subjected to the graft polymerization treatment because the contact angle of water after the water washing of the sheet was almost unchanged. It can be seen that almost no hydrophilization has occurred. Further, from the results of Comparative Examples 4 and 5, it is understood that the effect of hydrophilization by the surfactant is lost by being immersed in water once. In contrast, the hydrophilicized sheets obtained in Examples 1 to 4 retain excellent hydrophilicity even when washed with water.
【００４９】[0049]
【発明の効果】本発明の方法により、疎水性プラスチッ
ク製基材を容易に親水化することが可能となった。本発
明の方法により得られる親水化した基材の親水性は顕著
であり、かつ水洗によっても親水性は失われることがな
いので、電池用セパレーター等として好適に用いられ
る。According to the method of the present invention, a hydrophobic plastic substrate can be easily made hydrophilic. The hydrophilicity of the substrate which has been made hydrophilic by the method of the present invention is remarkable, and the hydrophilicity is not lost even by washing with water, so that it is suitably used as a battery separator or the like.
Claims (5)
ンプにより紫外線照射した後、水素引き抜き型光重合開
始剤溶液に接触させ、乾燥させた後、水溶性ビニルモノ
マー水溶液に接触させ、酸素が実質的に存在しない条件
下で高圧水銀ランプにより紫外線照射する工程を有する
ことを特徴とする、親水化した疎水性基材の製造方法。1. A method of irradiating a hydrophobic plastic substrate with ultraviolet light from a low-pressure mercury lamp, contacting the substrate with a hydrogen-abstraction-type photopolymerization initiator solution, drying the substrate, and then contacting the substrate with an aqueous solution of a water-soluble vinyl monomer. A method for producing a hydrophilized hydrophobic substrate, comprising a step of irradiating ultraviolet light with a high-pressure mercury lamp under conditions that do not exist in a natural state.
オレフィンである請求項１記載の製造方法。2. The method according to claim 1, wherein the material of the hydrophobic plastic substrate is a polyolefin.
ェノン系光重合開始剤である請求項１又は２記載の製造
方法。3. The process according to claim 1, wherein the hydrogen abstraction type photopolymerization initiator is a benzophenone-based photopolymerization initiator.
質膜である請求項１〜３いずれか記載の製造方法。4. The method according to claim 1, wherein the shape of the hydrophobic plastic substrate is a porous film.
酸、ビニルスルホン酸塩、スチレンスルホン酸又はスチ
レンスルホン酸塩である請求項１〜４いずれか記載の製
造方法。5. The method according to claim 1, wherein the water-soluble vinyl monomer is vinylsulfonic acid, vinylsulfonic acid salt, styrenesulfonic acid or styrenesulfonic acid salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11082515A JP2000273229A (en) | 1999-03-25 | 1999-03-25 | Production of hydrophilized hydrophobic substrate |
Applications Claiming Priority (1)
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| JP11082515A JP2000273229A (en) | 1999-03-25 | 1999-03-25 | Production of hydrophilized hydrophobic substrate |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005023921A1 (en) * | 2003-09-03 | 2005-03-17 | Toagosei Co., Ltd. | Method for continuous production of functional film |
| JP2008094923A (en) * | 2006-10-11 | 2008-04-24 | Kanto Gakuin Univ Surface Engineering Research Institute | Surface modification method of cycloolefin polymer material, surface-modified cycloolefin polymer material obtained using the same, method for forming metallic film on surface-modified cycloolefin polymer material, and cycloolefin polymer material with metallic film |
| JP2009001791A (en) * | 2007-05-24 | 2009-01-08 | Nitto Denko Corp | Method for producing porous film, porous film, separator for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using the separator |
| US9738744B2 (en) | 2013-06-11 | 2017-08-22 | Sumitomo Rubber Industries, Ltd. | Surface modification method for three-dimensional object and syringe gasket |
| US9752003B2 (en) | 2012-11-30 | 2017-09-05 | Sumitomo Rubber Industries, Ltd. | Surface-modified elastic body |
| US9758605B2 (en) | 2012-11-20 | 2017-09-12 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US9963565B2 (en) | 2014-10-02 | 2018-05-08 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US10189944B2 (en) | 2013-04-25 | 2019-01-29 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US10214608B2 (en) | 2015-08-03 | 2019-02-26 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified body |
| US10280274B2 (en) | 2014-01-06 | 2019-05-07 | Sumitomo Rubber Industries, Ltd. | Method for modifying surface and surface modified elastic body |
| US10344109B2 (en) | 2012-09-10 | 2019-07-09 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US10759918B2 (en) | 2015-08-03 | 2020-09-01 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| JP2022551617A (en) * | 2019-11-08 | 2022-12-12 | エルジー エナジー ソリューション リミテッド | Crosslinked separation membrane for lithium secondary battery containing crosslinked polyolefin and method for producing the same |
-
1999
- 1999-03-25 JP JP11082515A patent/JP2000273229A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005023921A1 (en) * | 2003-09-03 | 2005-03-17 | Toagosei Co., Ltd. | Method for continuous production of functional film |
| US7674349B2 (en) | 2003-09-03 | 2010-03-09 | Toagosei Co., Ltd. | Method for continuous production of a functional film |
| JP2008094923A (en) * | 2006-10-11 | 2008-04-24 | Kanto Gakuin Univ Surface Engineering Research Institute | Surface modification method of cycloolefin polymer material, surface-modified cycloolefin polymer material obtained using the same, method for forming metallic film on surface-modified cycloolefin polymer material, and cycloolefin polymer material with metallic film |
| JP4738308B2 (en) * | 2006-10-11 | 2011-08-03 | 株式会社関東学院大学表面工学研究所 | Method for producing cycloolefin polymer material with metal film and cycloolefin polymer material with metal film obtained by using the method |
| JP2009001791A (en) * | 2007-05-24 | 2009-01-08 | Nitto Denko Corp | Method for producing porous film, porous film, separator for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using the separator |
| US10344109B2 (en) | 2012-09-10 | 2019-07-09 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US9758605B2 (en) | 2012-11-20 | 2017-09-12 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US9752003B2 (en) | 2012-11-30 | 2017-09-05 | Sumitomo Rubber Industries, Ltd. | Surface-modified elastic body |
| US10189944B2 (en) | 2013-04-25 | 2019-01-29 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US9738744B2 (en) | 2013-06-11 | 2017-08-22 | Sumitomo Rubber Industries, Ltd. | Surface modification method for three-dimensional object and syringe gasket |
| US10280274B2 (en) | 2014-01-06 | 2019-05-07 | Sumitomo Rubber Industries, Ltd. | Method for modifying surface and surface modified elastic body |
| US9963565B2 (en) | 2014-10-02 | 2018-05-08 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| US10214608B2 (en) | 2015-08-03 | 2019-02-26 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified body |
| US10759918B2 (en) | 2015-08-03 | 2020-09-01 | Sumitomo Rubber Industries, Ltd. | Surface modification method and surface-modified elastic body |
| JP2022551617A (en) * | 2019-11-08 | 2022-12-12 | エルジー エナジー ソリューション リミテッド | Crosslinked separation membrane for lithium secondary battery containing crosslinked polyolefin and method for producing the same |
| JP7391201B2 (en) | 2019-11-08 | 2023-12-04 | エルジー エナジー ソリューション リミテッド | Crosslinked separation membrane for lithium secondary batteries containing crosslinked polyolefin and method for producing the same |
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