JPS63251401A - Hydrophilic membrane forming composition, hydrophilic membrane formed, and its preparation - Google Patents
Hydrophilic membrane forming composition, hydrophilic membrane formed, and its preparationInfo
- Publication number
- JPS63251401A JPS63251401A JP8413587A JP8413587A JPS63251401A JP S63251401 A JPS63251401 A JP S63251401A JP 8413587 A JP8413587 A JP 8413587A JP 8413587 A JP8413587 A JP 8413587A JP S63251401 A JPS63251401 A JP S63251401A
- Authority
- JP
- Japan
- Prior art keywords
- hydrophilic
- parts
- weight
- polymer
- group
- 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.)
- Granted
Links
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- 239000012528 membrane Substances 0.000 title claims abstract description 60
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は防曇性を有する親水性膜、それを形成するため
の組成物及び親水性膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrophilic film having antifogging properties, a composition for forming the same, and a method for producing the hydrophilic film.
［従来の技術］
浴室用鏡、勺ングラス、眼鏡レンズ、腕時計のカバーガ
ラス、スキー用ゴーグル等は湿気にふれることが多いの
で曇りやすく、これらの曇りを防止するために従来種々
の試みがなされた。[Prior Art] Bathroom mirrors, glasses, eyeglass lenses, watch cover glasses, ski goggles, etc. are prone to fogging because they are often exposed to moisture, and various attempts have been made to prevent such fogging. .
特開昭５５−６９６７８号は親水性基を含有する光硬化
性エチレン性不飽和化合物と、親水性基を含有しない光
硬化性エチレン性不飽和化合物と、光硬化開始剤とから
なる防曇剤を開示している。しかしながらこの防曇剤で
は親水性基が選択的に表面に存在するわけではないので
防曇性が低い上に、光硬化開始剤を含有しているので耐
光性に劣る。JP-A-55-69678 discloses an antifogging agent comprising a photocurable ethylenically unsaturated compound containing a hydrophilic group, a photocurable ethylenically unsaturated compound not containing a hydrophilic group, and a photocuring initiator. is disclosed. However, in this antifogging agent, hydrophilic groups are not selectively present on the surface, so the antifogging property is low, and since it contains a photocuring initiator, the light resistance is poor.
特開昭５７−１６３５６８号は紫外線吸収剤を多量に含
ｎ１る紫外線じゃへい性ポリ塩化ビニル系樹脂フィルム
の少なくとも一部をカチオン重合系のエネルギー線硬化
性樹脂組成物で被覆したことを特徴とする防曇性を有す
る農業用フィルムを開示している。カチオン重合系エネ
ルギー線硬化性樹脂組成物はエネルギー線（紫外線）の
照射により高分子化又は架橋して塗膜を形成するカチオ
ーン重合性樹脂組成物で、例えばエポキシ系樹脂、環状
エーテル類、ラクトン類、ビニル化合物等である。JP-A No. 57-163568 is characterized in that at least a portion of an ultraviolet resistant polyvinyl chloride resin film containing a large amount of ultraviolet absorber is coated with a cationically polymerized energy ray curable resin composition. Discloses an agricultural film having antifogging properties. A cationic polymerizable energy ray curable resin composition is a cationic polymerizable resin composition that is polymerized or crosslinked to form a coating film by irradiation with energy rays (ultraviolet rays), and includes, for example, epoxy resins, cyclic ethers, and lactones. , vinyl compounds, etc.
しかしながら、これは表面にカチオン重合系エネルギー
線硬化性樹脂組成物の塗膜を形成することにより、ポリ
塩化ビニル系樹脂フィルム中の界面活性剤等の表面移行
及び流出飛散を防止又は抑制したものであるので、防曇
性に関しては必ずしも満足ではなかった。However, this method prevents or suppresses surface migration and outflow scattering of surfactants, etc. in polyvinyl chloride resin films by forming a coating film of a cationically polymerized energy ray-curable resin composition on the surface. Therefore, I was not necessarily satisfied with the anti-fog properties.
特開昭５８−１０３５３３に？ｉは防曇フィルムの片面
に紫外線硬化型塗料を塗布し、紫外線照射により硬化さ
せ、フィルムの防曇持続性を改良することを特徴とする
方法を開示している。この塗料の塗膜は紫外線照射によ
り架橋されるため、防曇フィルムからの防曇剤の滲出を
防止することができる。しかし塗膜自体に親水性基を有
さないために特に初期防曇性に劣る伯、紫外線硬化型で
あるために増感剤を含有しており、日光や蛍光灯の光線
中の紫外線による劣化が著しいという問題がある。In JP-A-58-103533? i discloses a method characterized by applying an ultraviolet curable coating on one side of an antifogging film and curing it by ultraviolet irradiation to improve the antifogging durability of the film. Since the coating film of this paint is crosslinked by ultraviolet irradiation, it is possible to prevent the antifogging agent from oozing out from the antifogging film. However, because the coating film itself does not have hydrophilic groups, its initial antifogging properties are particularly poor, and since it is an ultraviolet curing type, it contains a sensitizer and deteriorates due to sunlight and ultraviolet rays from fluorescent lamps. The problem is that there is a significant
その他特開昭６０−１００９１４号及び６０−１０１０
４２号は透明性の高い合成樹脂フィルムまたはシートか
らなる基材に透明アセデルセルロース系フィルムを感熱
性接着剤で接合し、しかる後表面をＮａＯト１水溶液等
で親水化処理することを特徴とする防曇性合成樹脂シー
ト状物の製造方法を開示している。Others JP-A-60-100914 and 60-1010
No. 42 is characterized by bonding a transparent acedelcellulose film to a base material made of a highly transparent synthetic resin film or sheet using a heat-sensitive adhesive, and then subjecting the surface to hydrophilic treatment with an aqueous NaO solution or the like. Discloses a method for producing an antifogging synthetic resin sheet.
しかしながらこのシート状物は架橋されていないので強
度的に不十分であり、かつ界面活性剤がフィルム内部か
ら徐々に溶出することによる防曇効果を期待することは
できない。その上この親水化処理工程自体全工程を複雑
にしているので、実用的でない。However, since this sheet-like material is not crosslinked, its strength is insufficient, and the antifogging effect due to the gradual elution of the surfactant from inside the film cannot be expected. Moreover, this hydrophilic treatment process itself complicates the entire process, making it impractical.
なお従来からある界面活性剤を樹脂に練込む方法では、
界面活性剤の滲出が著しいので、防曇性持続性が劣る。In addition, with the conventional method of kneading surfactants into resin,
Since the leaching of the surfactant is significant, the durability of the antifogging property is poor.
［弁明が解決しようとする問題点］
以上の通りいまた十分な防曇性を有するとともに耐久性
（防曇持続性）、耐劣化性、機械的強度等に優れたもの
は提案されていない。[Problems to be solved by the defense] As mentioned above, no material has been proposed that has sufficient antifogging properties and is excellent in durability (sustainability of antifogging), deterioration resistance, mechanical strength, etc.
従って本発明の目的は十分な防曇性を有するとともに耐
久性、耐劣化性、機械的強度等に優れた新規な親水性膜
を提供することである。Therefore, an object of the present invention is to provide a novel hydrophilic film that has sufficient antifogging properties and is excellent in durability, deterioration resistance, mechanical strength, etc.
本発明のもう１つの目的はかかる親水性膜を形成するた
めの組成物を提供することである。Another object of the invention is to provide a composition for forming such a hydrophilic membrane.
本発明のさらにもう１つの目的はかかる親水性膜を製造
する方法を提供することである。Yet another object of the invention is to provide a method for manufacturing such hydrophilic membranes.
［問題点を解決覆るだめの手段］
以上の目的に鑑み鋭意研究の結果、本発明者等は骨格と
なるポリマーと親水性モノマーと架橋性を向上させる架
橋性モノマーとの混合物の塗膜に電子線を照射覆ると架
橋反応により両者が結合し、かつ親水性モノマーが表面
に浮き上がることにより親水基が表面に多く存在覆る膜
が得られることを発見し、本発明に想到した。[Means to Solve and Overcome the Problems] In view of the above objectives, as a result of intensive research, the present inventors added electrons to the coating film of a mixture of a polymer skeleton, a hydrophilic monomer, and a crosslinkable monomer that improves crosslinkability. It was discovered that when irradiated with a ray, the two bond through a crosslinking reaction, and the hydrophilic monomer floats to the surface, resulting in a membrane with many hydrophilic groups present on the surface, leading to the idea of the present invention.
すなわち、本発明の電子線照射により親水性膜を形成す
る親水性膜形成組成物はポリマーと、親水性モノマーと
架橋性七ツマ−とを含有することを特徴とする。本発明
の組成物は界面活性剤を含有してもよく、さらに必要に
応じ溶剤を含有してもよい。That is, the hydrophilic film-forming composition of the present invention, which forms a hydrophilic film by electron beam irradiation, is characterized by containing a polymer, a hydrophilic monomer, and a crosslinkable monomer. The composition of the present invention may contain a surfactant and may further contain a solvent if necessary.
また本発明の親水性膜はポリマーと、親水性モノマーと
架橋性七ツマ−とを含有する混合物の膜状物に電子線を
照射してなり、前記ポリマーが前記親水性モノマー及び
前記架橋性モノマーと架橋していることを特徴とする。Further, the hydrophilic membrane of the present invention is obtained by irradiating a membrane of a mixture containing a polymer, a hydrophilic monomer, and a crosslinking monomer with an electron beam, and the polymer is formed by irradiating the membrane with an electron beam. It is characterized by being crosslinked with.
同様に本発明の親水性膜は界面活性剤を含有してもよい
。Similarly, the hydrophilic membrane of the present invention may contain a surfactant.
さらに本発明の親水性膜の製造方法はポリマーと親水性
モノマーと架橋性七ツマ−とを混合し、膜状に塗布した
上で０．５〜２０Ｍ ｒａｄの電子線を照射することを
特徴とする。本方法においても、界面活性剤を混合物に
添加してよい。Furthermore, the method for producing a hydrophilic film of the present invention is characterized by mixing a polymer, a hydrophilic monomer, and a crosslinking monomer, coating the mixture in the form of a film, and then irradiating the mixture with an electron beam of 0.5 to 20 M rad. do. Also in this method, surfactants may be added to the mixture.
本発明に使用するポリマーは親水性膜の骨格となるもの
であるので、造膜性を有する必要がある。Since the polymer used in the present invention serves as the skeleton of a hydrophilic membrane, it must have film-forming properties.
また親水性膜が十分な寿命（耐用性）を有するためには
良好な耐水性を有する必要があり、そのためにはポリマ
ーは疎水性を有づるのが望ましい。Further, in order for a hydrophilic film to have a sufficient lifespan (durability), it is necessary to have good water resistance, and for this purpose, it is desirable that the polymer has hydrophobicity.
上記ポリマーは無官能ポリマーと官能ポリマーのいずれ
でもよい。The above polymer may be either a non-functional polymer or a functional polymer.
無官能ポリマーとしては、ポリアクリル酸アルキルエス
テル、ポリメタクリル酸アルキルエステル、ポリウレタ
ン、ポリエステル、ポリアミド、ポリ酢酸ビニル、ポリ
塩化ビニル、ポリスチレン、ポリアクリロニトリル、ポ
リビニルピロリドン等を使用することができる。As the non-functional polymer, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polyurethane, polyester, polyamide, polyvinyl acetate, polyvinyl chloride, polystyrene, polyacrylonitrile, polyvinylpyrrolidone, etc. can be used.
さらに親水性モノマーとの相溶性を良好にするために無
官能ポリマーに親水性基をあらかじめ導入してもよい。Furthermore, in order to improve compatibility with hydrophilic monomers, a hydrophilic group may be introduced into the non-functional polymer in advance.
これには後述の親水性基を有するモノマー（親水性モノ
マー）との共重合体とする。For this purpose, a copolymer with a monomer having a hydrophilic group (hydrophilic monomer), which will be described later, is used.
親水性モノマーの無官能ポリマーに対する割合は５０モ
ル％以下であり、これを超えると得られる膜の耐水性が
低下する。The ratio of the hydrophilic monomer to the non-functional polymer is 50 mol% or less, and if it exceeds this, the water resistance of the resulting membrane will decrease.
さらに部分ケン化ポリビニルアルコール、ポリビニルブ
チラール、ポリビニルアセタール等のポリビニルアルコ
ールの誘導体や、ニトロセルロース、セルロースアセテ
ート、セルロースアセチートブチレート、セルロースア
セテートプロピオネート、ヒドロキシプロピルセルロー
ス等のセルロース誘導体も使用することができる。Furthermore, derivatives of polyvinyl alcohol such as partially saponified polyvinyl alcohol, polyvinyl butyral, and polyvinyl acetal, and cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and hydroxypropyl cellulose may also be used. can.
一方、官能ポリマーは電離性放射線により架橋反応を起
す官能基を有するポリマーであり、官能基の例として以
下のものがある。On the other hand, a functional polymer is a polymer having a functional group that causes a crosslinking reaction by ionizing radiation, and examples of the functional group include the following.
■
アクリロイル基 −ＱＣ−Ｃ＝ＣＨ２
ＯＨ３
メタクリロイル基 −０Ｃ−Ｃ−ＣＨ２アリル基 −Ｏ
Ｈ−ＣＨ＝ＣＨ２
の割合であるのが望ましく、分子量１００００当り１つ
未満の割合だと官能基による架橋効果はほとんどなく、
分子１４３００当り１つを超える割合だと架橋密度が高
くなりすぎる。■ Acryloyl group -QC-C=CH2 OH3 Methacryloyl group -0C-C-CH2 Allyl group -O
It is desirable that the ratio is H-CH=CH2, and if the ratio is less than 1 per 10,000 molecular weight, there will be almost no crosslinking effect due to the functional group.
If the ratio exceeds 1 per 14,300 molecules, the crosslink density becomes too high.
官能ポリマーとしてはウレタンアクリレート、ポリエス
テルアクリレート、エポキシアクリレート等や、アクリ
ル酸アルキルエステルとアクリル酸−２−とドロキシエ
チルとの共重合体の水酸基にアクリル酸クロリド又はア
クリル酸−２−ヒドロキシエチルとジイソシアナートの
１＝１付加体を付加覆ることによりアクリロイル基を導
入した共重合体や、アクリル酸アルキルエステルとアク
リル酸の共重合体のカルボキシル基にグリシジルメタク
リレートを付加した共重合体や、ポリビニルブチラール
の残存水酸基にアクリル酸クロリド又はアクリル酸−２
−ヒドロキシエチルとジイソシアナートの１＝１付加体
を付加したもの等を使用覆ることができる。Examples of functional polymers include urethane acrylate, polyester acrylate, epoxy acrylate, etc., and acrylic acid chloride or 2-hydroxyethyl acrylate and diisocyanate on the hydroxyl group of a copolymer of acrylic acid alkyl ester, acrylic acid 2-hydroxyethyl ester, and droxyethyl ester. A copolymer in which an acryloyl group is introduced by adding and covering a 1=1 adduct of Acrylic acid chloride or acrylic acid-2 on the hydroxyl group
- A 1=1 adduct of hydroxyethyl and diisocyanate can be used.
なお上記ポリマーはオリゴマー状でもよいが、造膜性の
観点から分子量は１０００〜３０万（重量平均）である
のが好ましい。The above-mentioned polymer may be in the form of an oligomer, but from the viewpoint of film-forming properties, the molecular weight is preferably from 1,000 to 300,000 (weight average).
親水性モノマーは水酸基、カルボキシル基（金属塩）、
アミド基、イミド基、スルホン基、アンモニウム塩基、
リン酸基等の親水性基を含有するモノマーであり、例え
ばアクリル酸２−ヒドロキシエチル、メタクリル酸２−
ヒドロキシエチル、アクリル酸２−ヒドロキシプロピル
、メタクリル酸２−ヒドロキシプロピル、アクリル酸、
メタクリル酸、アクリル酸金属塩、メタクリル酸金属塩
、アクリルアミド、メタクリルアミド、ジメチルアミノ
プロピルアクリルアミド、ジメチルアミノプロピルメタ
クリルアミド、Ｎ−アクリロイルモルフォリン、Ｎ−メ
タクリロイルモルフォリン、Ｎ−メチロールアクリルア
ミド、Ｎ−メチロールメタクリルアミド、ｔ−ブチルア
クリルアミド、ｔ−ブチルメタクリルアミド、Ｎ−メト
キシメチルアクリルアミド、Ｎ−エトキシメチルアクリ
ルアミド、Ｎ−ｎ−ブトキシアクリルアミド、Ｎ。Hydrophilic monomers include hydroxyl groups, carboxyl groups (metal salts),
Amide group, imide group, sulfone group, ammonium base,
A monomer containing a hydrophilic group such as a phosphoric acid group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc.
Hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid,
Methacrylic acid, metal acrylate, metal methacrylate, acrylamide, methacrylamide, dimethylaminopropylacrylamide, dimethylaminopropyl methacrylamide, N-acryloylmorpholine, N-methacryloylmorpholine, N-methylol acrylamide, N-methylol methacryl amide, t-butylacrylamide, t-butylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-n-butoxyacrylamide, N.
Ｎ−ジメチルアクリルアミド、Ｎ、Ｎ−ジメチルアミノ
プロピルアクリルアミド、Ｎ、Ｎ−ジメチルアミノプロ
ピルメタクリルアミド、ポリエチレンクリコールモノメ
タクリレ−１〜、ポリプロピレンクリコールモノメタク
リレート、グリセロールモノメタクリレート、２−アク
リルアミド２−メヂルプｒコパンスルホン酸、メタアク
リルアミドプロピルトリメチルアンモニウムクロライド
、メタクリロイルオキシエチルトリメチルアンモニウム
クロライド、モノ（２−メタクロイロキシエチル）アシ
ッドホスフェート等が挙げられる。N-dimethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, polyethylene glycol monomethacrylate-1~, polypropylene glycol monomethacrylate, glycerol monomethacrylate, 2-acrylamide 2-methacrylamide Examples include r-copanesulfonic acid, methacrylamide propyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and mono(2-methacryloyloxyethyl) acid phosphate.
架橋性七ツマ−はアクリルロイル基、メタクリロイル基
、アリル基、エポキシ基等電子線照射によって容易にラ
ジカルどなる基を２つ以上有する七ツマ−であり、骨格
ポリマーと親水性モノマーのいずれとも架橋結合するの
で、膜全体の架橋密度を向上させ、膜強度を高めるとと
もに未反応の親水性七ツマ−が残存しないＪ：うにする
。このような架橋性七ツマ−として、エチレングリコー
ルジメタクリレート、ジエチレンクリコールジメタクリ
レート、１，６−ヘキザンジオールジメタクリレート、
クリシジルメタクリレート、ネオペンチルグリコールジ
メタクリレート、テトラエチレングリコールジメタクリ
レート、２，２−ビス（４−（アクリロキシジェトキシ
）フェニル）プロパン、２．２−ビス〔４−（メタクリ
ロキシジェトキシ）フェニル〕プロパン、２，２−ビス
〔４−（アクリロキシポリエトキシ）フェニル）プロパ
ン、２，２−ビス（４−（メタクリロキシポリエトキシ
）フェニル〕プロパン等の２官能七ツマ−、トリメチロ
ールプロパントリメタクリレート等の３官能七ツマ−１
その他テトラメヂロールメタンテ１〜ラアクリレート、
ジペンタエリスリトールへキサアクリレ−１〜等の多官
能七ツマー等が挙げられる。Crosslinkable heptamers are heptamers that have two or more groups that easily become radicals when irradiated with electron beams, such as acryloyl groups, methacryloyl groups, allyl groups, and epoxy groups, and can be crosslinked with either the backbone polymer or the hydrophilic monomer. Therefore, the crosslinking density of the entire membrane is improved, the strength of the membrane is increased, and unreacted hydrophilic hexamers do not remain. Examples of such crosslinking seven polymers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate,
Chrycidyl methacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2,2-bis(4-(acryloxyjethoxy)phenyl)propane, 2,2-bis[4-(methacryloxyjethoxy)phenyl] Propane, 2-functional septamers such as 2,2-bis[4-(acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-(methacryloxypolyethoxy)phenyl]propane, trimethylolpropane trimethacrylate etc. 3-functional 7-summer-1
Others tetramedilol methante 1-la acrylate,
Examples include polyfunctional heptamers such as dipentaerythritol hexaacrylate-1 and the like.
本発明の親水性膜形成組成物はまた界面活性剤を含有す
ることができる。界面活性剤は親水性膜から徐々に表面
に滲出することにより防曇性を付与する作用を有Ｊる。The hydrophilic film-forming composition of the present invention can also contain a surfactant. The surfactant has the effect of imparting antifogging properties by gradually exuding from the hydrophilic film to the surface.
親水性膜形成組成物との相溶性が良ければ敗イオン性、
非イオン性及び陽イオン性のいずれの界面活性剤も使用
することができる。If the compatibility with the hydrophilic film-forming composition is good, it will have anti-ionic properties;
Both nonionic and cationic surfactants can be used.
陰イオン性界面活性剤としては脂肪酸塩、アルキル硫酸
エステル塩、アルキルベンゼンスルホン酸塩、アルキル
ナフタレンスルホン酸塩、ジアルキルスルホコハク酸エ
ステル塩、アルギルリン酸エステル塩、ナフタレンスル
ホン酸−ホルマリン縮合物、ポリオキシエチレンアルキ
ル硫酸エステル塩等があり、非イオン性界面活性剤とし
てはポリオキシエチレンアルキルエーテル、ポリオギル
エチレンアルキルフェノールエーテル、ポリオキシエチ
レン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリ
オキシエチレンソルビタン脂肪酸エステル、ポリオキシ
エチレンアルキルアミン、グリセリン脂肪酸エステル、
オキシエヂレンーオキシプロピレンブロツクポリマー等
があり、陽イオン性界面活性剤としてはアルキルアミン
、４級アンモニウム塩等がある。Examples of anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinate ester salts, argyl phosphate ester salts, naphthalene sulfonic acid-formalin condensates, polyoxyethylene alkyl There are sulfate ester salts, etc. Nonionic surfactants include polyoxyethylene alkyl ether, polyogylethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerin fatty acid ester,
Examples include oxyethylene-oxypropylene block polymers, and cationic surfactants include alkyl amines and quaternary ammonium salts.
本発明の組成物は必要に応じ溶剤を含有してもよい。溶
剤は単に組成物の流動性を調節づるだけでなく、塗膜の
表面に親水性モノマーを浮き上がらせる作用も荷重るの
で、本発明の親水膜を形成するのに好ましい。使用し得
る溶剤としては、メタノール、エタノール、イソプロパ
ツール、メチルセルソルブ、エチルセルソルブ等のアル
コール類、テトラヒドロフラン等のエーテル類、メチル
エチルケトン、アセトン、メチルイソブチルケトン等の
ケトン類、酢酸エチル、酢酸ブチル等のエステル類、ト
ルエン、キシレン等の芳香族炭化水素類等、又はこれら
の混合溶剤がある。The composition of the present invention may contain a solvent if necessary. A solvent is preferable for forming the hydrophilic film of the present invention because it not only controls the fluidity of the composition but also has the effect of lifting the hydrophilic monomer onto the surface of the coating film. Usable solvents include alcohols such as methanol, ethanol, isopropanol, methyl cellosolve, and ethyl cellosolve, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ethyl acetate, and butyl acetate. and aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.
本発明の親水性膜形成組成物においては、ポリマー１０
０重量部当り、親水性モノマーは５〜２００重量部であ
る。５重量部未満だと十分な親水性が付与されず、逆に
２００重吊都合超えると膜の耐水性が低下覆る。好まし
い親水性モノマーの含有量は２０〜１５０重恒部である
。In the hydrophilic film-forming composition of the present invention, polymer 10
0 parts by weight, the hydrophilic monomer is 5 to 200 parts by weight. If it is less than 5 parts by weight, sufficient hydrophilicity will not be imparted, and if it exceeds 200 parts by weight, the water resistance of the membrane will deteriorate. The preferred content of hydrophilic monomer is 20 to 150 parts by weight.
架橋性モノマーはポリマー１００重量部当り１〜３００
Ｉｆｆｉ部である。１重量部未満だと未反応の親水性モ
ノマーの架橋化が不十分であり、逆に３００重量部を超
えると膜全体の架橋密度が高くなりすき゛る。特にポリ
マーか官能基を有しない場合、架橋性モノマーの含有量
は５〜３００重量部とするのが好ましく、５〜２００重
量部と小母のがより好ましい。またポリマーが官能基を
有する場合、架橋性モノマーの含有量は１〜２００重量
部と都合のが好ましく、５〜１００重量部とするのがよ
り好ましい。The amount of crosslinking monomer is 1 to 300 per 100 parts by weight of polymer.
This is the Iffi department. If it is less than 1 part by weight, crosslinking of the unreacted hydrophilic monomer will be insufficient, and if it exceeds 300 parts by weight, the crosslinking density of the entire membrane will be too high. In particular, when the polymer has no functional group, the content of the crosslinkable monomer is preferably 5 to 300 parts by weight, more preferably 5 to 200 parts by weight. Further, when the polymer has a functional group, the content of the crosslinking monomer is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight.
界面活性剤を添加づる場合、ポリマー１００重量部当り
１００重量部以下である。１００重量部を超えると界面
活性剤の滲出が多過ぎるようになる。好ましい含有量は
１〜５０重量部小母る。When a surfactant is added, the amount is 100 parts by weight or less per 100 parts by weight of the polymer. If it exceeds 100 parts by weight, too much surfactant leaches out. The preferred content is 1 to 50 parts by weight.
溶剤の添加量は膜の形成方法により異るが、塗布により
塗膜を形成する場合、組成物中の固形分が５〜５０重量
％、好ましくは５〜３０重量％となるようにする。一般
的には溶剤添加量はポリマー１００重量部当り６０００
重量部以下とする。The amount of solvent added varies depending on the film formation method, but when forming a coating film by coating, the solid content in the composition is 5 to 50% by weight, preferably 5 to 30% by weight. Generally, the amount of solvent added is 6000 parts per 100 parts by weight of polymer.
Part by weight or less.
上記本発明の組成物を用い、以下の方法により親水性膜
を形成することができる。A hydrophilic film can be formed by the following method using the composition of the present invention.
まず適当な粘度に調整した組成物を、グラビアリバ、−
ス法、三本リバース法、グラビアダイレクト法、四本リ
バース法等のロールコート方式により、塗布する。用途
に応じ、塗布をベースフィルム等の支持体上に行うのが
好ましい。ベースフィルムとしては一般に透明なプラス
チックを使用するが、装飾等の目的で着色フィルムや不
透明フィルムを使用することもできる。また塗膜との接
着性を向上させるため、易接着処理をしたフィルムを用
いることもできる。ベースフィルムの材質としてはポリ
エステル、ポリエチレン、ポリプロピレン、ポリカーボ
ネート、ポリアクリレート、ポリスチレン、ポリアミド
、ポリイミド、ポリ塩化ビニル等を使用することができ
る。First, the composition adjusted to an appropriate viscosity was mixed with Gravure Liva, -
Coating is performed using a roll coating method such as the 3-line reverse method, the gravure direct method, or the 4-line reverse method. Depending on the application, the coating is preferably carried out on a support such as a base film. Transparent plastic is generally used as the base film, but colored or opaque films can also be used for decorative purposes. Furthermore, in order to improve the adhesion to the coating film, a film that has been treated to facilitate adhesion can also be used. As the material of the base film, polyester, polyethylene, polypropylene, polycarbonate, polyacrylate, polystyrene, polyamide, polyimide, polyvinyl chloride, etc. can be used.
ベースフィルム等の上に形成した組成物の塗膜は溶剤を
蒸発除去するため、ドライヤー等で加熱しながら乾燥す
る。加熱温度が高すぎると七ツマー類も蒸発してしまう
ので、最高１４０℃程度とする。The coating film of the composition formed on the base film etc. is dried while being heated with a dryer etc. in order to remove the solvent by evaporation. If the heating temperature is too high, the 7mers will also evaporate, so the maximum temperature should be around 140°C.
以上のようにして形成した本発明の組成物の塗膜におい
ては、モノマーが表面に浮ぎ上がり、モノマー・リッチ
相とポリマー・リッチ相とからなる傾向があることがわ
かった。これは本発明の重要な特徴である。すなわち、
このような「配向」のため親水性基が表面に相対的に多
く存在し、耐水性、ぼ械的強度等を有するポリマー骨格
部分に支持された親水性膜構造が得られる。It has been found that in the coating film of the composition of the present invention formed as described above, the monomer tends to float to the surface and consists of a monomer-rich phase and a polymer-rich phase. This is an important feature of the invention. That is,
Due to such "orientation", a relatively large number of hydrophilic groups are present on the surface, resulting in a hydrophilic membrane structure supported by a polymer skeleton having water resistance, mechanical strength, and the like.
次に、この塗膜に電子線の照射を行う。照射方法として
はエレクトロンカーテン方式、ビームスキャニング方式
等任意の方法を用いることができる。電子線の照射によ
り、ポリマーは官能基の有無にかかわらず架橋可能とな
り、モノマーがグラフト重合又はブロック重合の形式で
ポリマーに架橋する。この点が紫外線照射による架橋と
著しい相違点である。Next, this coating film is irradiated with an electron beam. As the irradiation method, any method such as an electron curtain method or a beam scanning method can be used. By irradiation with electron beams, polymers with or without functional groups can be crosslinked, and the monomers crosslink to the polymer in the form of graft or block polymerization. This point is markedly different from crosslinking by ultraviolet irradiation.
照射する電子線のエネルギーは１５０〜２００ｋｅＶ程
度であり、照射量は組成物の組成及び所望する架橋密度
の程度等により異なる。ポリマーに官能基がある程、ま
た架橋性モノマーが多い程照射量は少なくてすみ、また
架橋密度を高くする程照射吊を多くする必要がある。特
に界面活性剤を含有する場合、架橋密度が高すぎるとそ
の滲出が不十分となり、防曇作用が低下するので、照射
量の制御は重要である。以上のことから一般に照射量は
０．５〜２０Ｍｒａｄであり、０．５Ｍ ｒａｄ未満で
あると未反応モノマーが残留することがあり、２０Ｍ
ｒａｄを超えると架橋密度が高くなりすぎる。The energy of the irradiated electron beam is about 150 to 200 keV, and the irradiation amount varies depending on the composition of the composition, the desired degree of crosslinking density, etc. The more functional groups there are in the polymer and the more crosslinking monomers there are, the lower the amount of irradiation will be required, and the higher the crosslinking density, the more it will be necessary to increase the amount of irradiation. In particular, when a surfactant is contained, if the crosslinking density is too high, its exudation will be insufficient and the antifogging effect will be reduced, so controlling the irradiation amount is important. From the above, the irradiation amount is generally 0.5 to 20 Mrad, and if it is less than 0.5 Mrad, unreacted monomer may remain,
If it exceeds rad, the crosslinking density becomes too high.
特に個々の組成のものについて言えば、（ａ）前官能ポ
リマー十親水性モノマー十栗橋性モノマーの場合０．５
〜１５Ｍ ｒａｄが好ましく、（ｂ）官能ポリマー十親
水性モノマー十架橋性モノマーの場合０．５−１５Ｍｒ
ａｄが好ましく、（ｃ）前官能ポリマー→−親水性モツ
マー十架橋性モノマー÷界面活性剤の場合０，５〜１０
Ｍ１・ａｄが好ましく、（ｄ）官能ポリマー十親水性モ
ノマー十架橋性モノマー十界面活性剤の場合０．５〜Ｉ
ＯＭ ｒａｄが好ましい。Particularly regarding individual compositions, (a) 0.5 in the case of prefunctional polymer + hydrophilic monomer + Kurihashi monomer
~15M rad is preferred, and (b) functional polymer ten hydrophilic monomer ten crosslinkable monomers 0.5-15 Mr
ad is preferred, and (c) prefunctional polymer→-hydrophilic motumer crosslinking monomer÷surfactant: 0.5 to 10
M1.ad is preferable, and in the case of (d) a functional polymer, a hydrophilic monomer, a crosslinking monomer, and a surfactant, 0.5 to I
OM rad is preferred.
このようにして作成した親水性膜は、ポリマー骨格に親
水性モノマーが架橋しているとともに、膜表面に親水性
モノマーの親木基が集中しているという独特の構造を有
する。このため良好な防曇性を有する。その上膜全体は
架橋しているので、十分な硬度及び強度を有する。The hydrophilic membrane thus prepared has a unique structure in which the polymer skeleton is crosslinked with hydrophilic monomers and the parent groups of the hydrophilic monomers are concentrated on the membrane surface. Therefore, it has good antifogging properties. Since the entire upper film is crosslinked, it has sufficient hardness and strength.
このように表面に存在する親水性基のために、特に水蒸
気が短期間当たるような用途において優れた防暑性を荷
重る。従って、そのような用途に使用するものには界面
活性剤を含有する必要は特にない。Due to the hydrophilic groups present on the surface, it has excellent heat resistance, especially in applications where it is exposed to water vapor for a short period of time. Therefore, it is not particularly necessary to contain a surfactant in those used for such purposes.
これに対して、長期間水蒸気に曝される用途に使用する
ものについては、界面活性剤を含有する必要がある。こ
の場合、表面の親水性基が初期防曇性を発揮し、膜中に
存在する界面活性剤は膜表面に付着した水分により表面
に滲出してぎて長期防曇性を発揮する。ここで本発明の
親水性膜は架橋しているので、界面活性剤の滲出は徐々
であり、非常に長期間にわたって防曇性を維持すること
ができる。また電子線の照射条件を変えることにより架
橋密度を調節して、界面活性剤の滲出速度をコン］−ロ
ールすることができる。On the other hand, for those used in applications that are exposed to water vapor for a long period of time, it is necessary to contain a surfactant. In this case, the hydrophilic groups on the surface exhibit initial antifogging properties, and the surfactant present in the film oozes out to the surface due to moisture adhering to the membrane surface, thereby exhibiting long-term antifogging properties. Here, since the hydrophilic film of the present invention is crosslinked, the surfactant leaches out gradually, and the antifogging property can be maintained for a very long period of time. Furthermore, by changing the electron beam irradiation conditions, the crosslinking density can be adjusted to control the leaching rate of the surfactant.
なお、組成物に装飾や遮光のために着色剤を添加できる
。着色剤は、顔料、染料等で、耐候性の良いものが好ま
しい。In addition, a coloring agent can be added to the composition for decoration or light shielding. The colorant is preferably a pigment, dye, or the like, and has good weather resistance.
本発明の親水性膜はベースフィルム上に塗膜として形成
することができるので、ベースフィルムに接看剤を塗布
することにより、鏡や窓等所望の所に貼着することがで
きる。また可撓性とすることもできるので、メガネやｊ
−グル等の曲面状のものにも貼着できる。Since the hydrophilic film of the present invention can be formed as a coating film on a base film, it can be attached to a desired location such as a mirror or window by applying a viewing agent to the base film. It can also be made flexible, so it can be used for glasses and
- Can be attached to curved objects such as glue.
なお本発明の親水性膜はベースフィルム上の塗膜として
形成する場合、０．１〜３０μｍの厚さを有するように
する。０．１μｍ未満だと膜強度が弱いのみならず防曇
性が長続きせず、また３０μｍを超える厚さとしても効
果の一層の向上はほとんど期待できない。なお、ベース
フィルム上の他にガラス板、プラスチック板、金属板等
の上に塗膜として形成しても特性自体は同じである。In addition, when the hydrophilic film of the present invention is formed as a coating film on a base film, it has a thickness of 0.1 to 30 μm. If the thickness is less than 0.1 μm, not only will the film strength be weak, but the antifogging property will not last long, and even if the thickness exceeds 30 μm, further improvement in effectiveness cannot be expected. Note that the properties are the same even if the film is formed as a coating film on a glass plate, plastic plate, metal plate, etc. in addition to the base film.
［実 施 例］ 本発明を以下の実施例によりさらに詳細に説明する。[Example] The present invention will be explained in further detail by the following examples.
実施例 １
アクリルポリマー溶液３００重量部と、親水性七ツマ−
として２−ヒドロキシエチルメタクリレ−ｈ１００重量
部と、架橋性七ツマ−としてジエチレンクリコールジメ
タクリレート１０重量部と、界面活性剤としてエマルゲ
ン１０６（花王（株）製）５重置部と、溶剤としてメチ
ルセルソルブ３００ 千ｍ部とを均一に混合し、本発明
の組成物を調製した。Example 1 300 parts by weight of acrylic polymer solution and hydrophilic nitrate
As a solvent, 100 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of diethylene glycol dimethacrylate as a cross-linkable hexamer, 5 parts of Emulgen 106 (manufactured by Kao Corporation) as a surfactant, and A composition of the present invention was prepared by uniformly mixing 300,000 m parts of methylcellosolve.
なおアクリルポリマー溶液の調製は以下の手順で行った
。すなわち、メチルメタクリレート７００重量部と、２
−ヒドロキシエチルメタクリレート３つｏＩＩ部と、ア
ゾビスイソブチロニトリル１゜５重量部とメチ小母ルソ
ルブ２２１０重量部とを、還流管及び撹拌器を具備し、
窒素置換したセパラブルフラスコに入れ、Ｎ２気流中で
８５°Ｃで５時間反応させた。その後さらにアゾビスイ
ソブチロニトリルを１．５重量部添加し、３時間反応さ
せた。生成したアクリルポリマー溶液は３３重量％の濃
度であり、ゲル透過クロマトグラフィー（ＧＰＣ）によ
り測定したところ、重量平均分子ｆＪ （Ｍｗ ）は７
．５ｘ１０４であった。またモノマーのピークは認めら
れなかった。Note that the acrylic polymer solution was prepared according to the following procedure. That is, 700 parts by weight of methyl methacrylate and 2
- 3 oII parts of hydroxyethyl methacrylate, 1.5 parts by weight of azobisisobutyronitrile, and 2210 parts by weight of methyl methacrylate, equipped with a reflux tube and a stirrer,
The mixture was placed in a separable flask purged with nitrogen, and reacted at 85°C for 5 hours in a N2 stream. Thereafter, 1.5 parts by weight of azobisisobutyronitrile was further added, and the mixture was reacted for 3 hours. The resulting acrylic polymer solution has a concentration of 33% by weight and has a weight average molecular fJ (Mw) of 7 as determined by gel permeation chromatography (GPC).
．． It was 5x104. Moreover, no monomer peak was observed.
上記組成物をロールコータ−により厚さ５０μ班のポリ
エステルフィルム（ルミラーＴタイプ）に５μ班の厚み
で均一に塗布し、ドライヤーで乾燥後、エレクトロンカ
ーテン型ＥＢ装置（ＥＳ Ｉ社製）により１１５ｋｅＶ
の電子線を５Ｍｒａｄ照射し、塗膜を硬化させた。 得
られた親水性フィルムの防曇性は下記テストにより行っ
た。The above composition was uniformly applied to a polyester film (Lumirror T type) with a thickness of 50 μm using a roll coater, and after drying with a dryer, the composition was applied at 115 keV using an electron curtain type EB device (manufactured by ES I).
The coating film was cured by irradiation with an electron beam of 5 Mrad. The antifogging property of the obtained hydrophilic film was tested by the following test.
（１）水の接触角テスト。(1) Water contact angle test.
（２）呼気テス１〜（呼気により曇りが発生するか否か
を調べる）。(2) Exhalation test 1~ (investigating whether or not cloudiness occurs due to exhalation).
（３）氷水呼気テスト（氷水入りのビーカーにフィルム
を貼り、１分後に呼気をかけて曇りが発生するか否かを
調べる）。(3) Ice water breath test (apply a film to a beaker containing ice water, exhale after 1 minute and check whether cloudiness occurs).
［４） ６０°Ｃ渇気テスト＜６０’Ｃの湯気にフィ
ルムを当てて曇りが発生するか否かを調べる）。[4) 60°C thirst test (examine whether clouding occurs by exposing the film to steam at 60°C).
上記（２）〜（４）のテストにおいて、結果を下記の第
１表に示す。In the tests (2) to (4) above, the results are shown in Table 1 below.
実施例 ２〜８
第１表に示す各組成の組成物を用いて、実施例１と同様
の方法で親水性フィルムを作成し、同じテストを行った
。結果を同じく第１表に示す。Examples 2 to 8 Hydrophilic films were prepared in the same manner as in Example 1 using the compositions shown in Table 1, and the same tests were conducted. The results are also shown in Table 1.
実施例９
官能ポリマーとしてウレタンアクリレート １００重量
部と、親水性七ツマ−としてＮ、Ｎ−ジメチルアクリル
アミド５０重量部と、架橋性モノマーとしてテト５エチ
レングリコールジアクリレート１０重量部と、界面活性
剤として「エキセル３００ｊ（花工（株）製）３重量部
と、溶剤としてメチルエチルケトン５００重量部とを混
合し、本発明の親水性膜形成用組成物を調製した。Example 9 100 parts by weight of urethane acrylate as a functional polymer, 50 parts by weight of N,N-dimethylacrylamide as a hydrophilic monomer, 10 parts by weight of tetraethylene glycol diacrylate as a crosslinking monomer, and A composition for forming a hydrophilic film of the present invention was prepared by mixing 3 parts by weight of Excel 300j (manufactured by Hanako Co., Ltd.) and 500 parts by weight of methyl ethyl ketone as a solvent.
なおウレタンアクリレートの調製は以下の通り行った。The urethane acrylate was prepared as follows.
すなわち、実施例１と同じ装置を用い、その中にブチレ
ンアジペート（「ニラポランＮ−４５フ０Ｊ日本ポリウ
レタン（株）製）６５０ｇと、メチルエチルケトン３０
０ｑと、イソホロンジイソシアネート４４４ｑとを入れ
、６０℃で攪拌しながら、ジブチル錫ジラウレート１ｇ
をメチルエチルケトン１０ｇに溶かしたものを滴下した
。That is, using the same apparatus as in Example 1, 650 g of butylene adipate (Niraporan N-45F0J manufactured by Nippon Polyurethane Co., Ltd.) and 30 g of methyl ethyl ketone were placed in it.
Add 0q and 444q of isophorone diisocyanate, and while stirring at 60°C, add 1g of dibutyltin dilaurate.
was dissolved in 10 g of methyl ethyl ketone and added dropwise.
５時間窒素気流中で攪拌しながら２−ヒドロキシエチル
アクリレート２３２９を滴下し、滴下終了後さらに７０
℃で３時間攪拌を継続した。赤外線吸収スペクトルによ
り−ＮＧＯ基のピークが消失したのを確認して、反応を
終了した。2-Hydroxyethyl acrylate 2329 was added dropwise while stirring in a nitrogen stream for 5 hours, and after the completion of the addition, an additional 70
Stirring was continued for 3 hours at °C. The reaction was terminated when it was confirmed by infrared absorption spectrum that the peak of the -NGO group had disappeared.
上記組成物を実施例１と同様の方法で塗布、乾燥し、同
じ電子線照射条件で硬化させた。得られた親水性塗膜の
防暑性について、実施例１と同じテストを行った。結果
を第２表に示す。The above composition was applied and dried in the same manner as in Example 1, and cured under the same electron beam irradiation conditions. The same test as in Example 1 was conducted regarding the heat resistance of the obtained hydrophilic coating film. The results are shown in Table 2.
実施例１０〜１４
実施例９と同様にして、第２表に示す組成の組成物から
親水性塗膜のフィルムを形成し、各親水性フィルムにつ
いて同じ防曇性のテストを行った。Examples 10 to 14 Hydrophilic coating films were formed from the compositions shown in Table 2 in the same manner as in Example 9, and the same antifogging test was conducted for each hydrophilic film.
結果を第２表に示す。The results are shown in Table 2.
実施例１５
実施例１において調製した組成物において、界面活性剤
の吊を０〜３０重量部の間で種々に変化させた。得られ
た各組成物について、実施例１と同じテストを行うとと
もに、長期防曇性を評価するために耐水浸漬のテストを
行った。なお耐水浸漬７ストは２５°Ｃの水にフィルム
を２４時間浸漬し、水から敢り出した後で６０°Ｃ渇気
テストを行い、防曇性を維持しているか否か調べるるこ
とからなり、６０°Ｃの湯気にさらして１分間曇らなけ
れば（防曇性を維持していれば）Ｏｌそうでなければ×
とした。結果を第３表に示す。Example 15 In the composition prepared in Example 1, the amount of surfactant was varied from 0 to 30 parts by weight. Each of the obtained compositions was subjected to the same test as in Example 1, and also to a water immersion test to evaluate long-term antifogging properties. Water-resistant immersion 7 strokes involves soaking the film in 25°C water for 24 hours, then taking it out of the water and conducting a 60°C thirst test to see if it maintains its anti-fogging properties. If it doesn't fog up for 1 minute after being exposed to steam at 60°C (if it maintains its anti-fog properties), then it's OK.
And so. The results are shown in Table 3.
実施例１６
実施例１におけるのと同じ組成物を用いて、同様の方法
で５μｍの厚さに塗布を行い、ドライＶ−で乾燥させた
。得られた塗膜に種々の照射量で１１５ｋｅＶの電子線
を照射し、種々の架橋密度の親水性塗膜を得た。得られ
た親水性塗膜の防曇性を測定した。結果を電子線照射量
とともに第４表に示す。Example 16 Using the same composition as in Example 1, coating was carried out in a similar manner to a thickness of 5 μm and dried in Dry V-. The obtained coating films were irradiated with a 115 keV electron beam at various doses to obtain hydrophilic coating films with various crosslinking densities. The antifogging property of the obtained hydrophilic coating film was measured. The results are shown in Table 4 along with the electron beam irradiation amount.
４１ 一
実施例１７
実施例２に示す組成の組成物に対して実施例１６と同じ
実験を行った。結果を第５表に示す。41 Example 17 The same experiment as in Example 16 was conducted on the composition shown in Example 2. The results are shown in Table 5.
比較例１
実施例３において親水性モノマーとしてのクリセＤ−ル
モノメタクリレ−１〜を使用しない以外全く同じように
して、塗膜を形成し、得られた塗膜の防曇性を評価した
。結果は以下の通りであった。Comparative Example 1 A coating film was formed in exactly the same manner as in Example 3, except that Chrysel D-L monomethacrylate 1~ was not used as the hydrophilic monomer, and the antifogging properties of the resulting coating film were evaluated. The results were as follows.
水の接触角 ６０゜
呼気テスｉへ ×
氷水呼気テスト ×
６０°Ｃ潟気テスト ×
以上の結果から明らかなように、親水性モノマーを添加
せずに作成した塗膜は初期防曇性を有さない。Water contact angle 60° breath test i × Ice water breath test × 60°C lagoon air test I don't.
比較例２
実施例１に示づ一絹成の組成物を塗布後、Ｆｕ−ｓｉｏ
ｎ ＤＲ８−１２０ＵＶ装置＜’）マール製ｒを用い
て紫外線の照射を１０秒間行った。しかしながら硬化反
応は起きなかった。このことから、本発明の組成物は電
子線によりはじめて架ａ（硬化）Ｊ゛ることがわかる。Comparative Example 2 After applying the composition shown in Example 1, Fu-sio
n DR8-120UV device<') Ultraviolet rays were irradiated for 10 seconds using a Marl r. However, no curing reaction occurred. This shows that the composition of the present invention can be cured (cured) only by electron beams.
［発明の効果］
以上の通り本発明の親水性膜形成組成物は親水性モノマ
ーを表面に析出させて硬化する性質を有でるため、初！
υ］防テ性を有する親水性膜を提供することができる。[Effects of the Invention] As described above, the hydrophilic film-forming composition of the present invention has the property of curing by precipitating hydrophilic monomers on the surface.
[υ] A hydrophilic film having anti-tetanus properties can be provided.
、また電子線により架橋するものであるので、熱硬化と
比較して架橋密度を自由に調整Ｊ〜ることかてきる。そ
のため界面活性剤（長期防曇性付与剤）の滲出を制御す
ることかできる。Moreover, since crosslinking is performed by electron beam, the crosslinking density can be adjusted more freely than in thermosetting. Therefore, the leaching of the surfactant (long-term antifogging agent) can be controlled.
また加熱せずに硬化（架橋）できるので、熱に弱い素材
にも防曇性を付与できる。さらに紫外線による架橋のよ
うに増感剤を用いないので、耐候性が良好であり、長期
の使用によっても劣化が少ない。Furthermore, since it can be cured (crosslinked) without heating, anti-fog properties can be imparted to heat-sensitive materials. Furthermore, since no sensitizer is used as in crosslinking with ultraviolet rays, weather resistance is good and there is little deterioration even after long-term use.
またこのような組成物から形成される本発明の親水性膜
は表面の親水基により初期防曇性を有し、かつ界面活性
剤を含有する場合には、架橋した構造を通して徐々に滲
出覆ることにより長期にわたり防＠性を維持することか
できる。また架橋しているので十分な機械的強度及び硬
度を有する。In addition, the hydrophilic film of the present invention formed from such a composition has initial antifogging properties due to the hydrophilic groups on the surface, and when it contains a surfactant, it gradually oozes out through the crosslinked structure. It is possible to maintain @ resistance for a long period of time. Furthermore, since it is crosslinked, it has sufficient mechanical strength and hardness.
さらに本発明の製造方法は組成物の塗膜に所望量の電子
線を照射づるので、親水性膜の硬化度（架橋密度）を適
当に調節することができ、それによりとくに長期防曇性
をコントロールすることができる。Furthermore, since the production method of the present invention irradiates the coating film of the composition with a desired amount of electron beams, the degree of curing (crosslinking density) of the hydrophilic film can be appropriately adjusted, thereby improving long-term antifogging properties. can be controlled.
Claims (55)
いて、ポリマーと、親水性モノマーと、架橋性モノマー
とを含有することを特徴とする親水性膜形成組成物。(1) A composition for forming a hydrophilic film by electron beam irradiation, characterized by containing a polymer, a hydrophilic monomer, and a crosslinkable monomer.
物において、前記ポリマーが官能基を実質的に有さない
ことを特徴とする親水性膜形成組成物。(2) The hydrophilic film-forming composition according to claim 1, wherein the polymer has substantially no functional group.
物において、前記ポリマーが官能基を有することを特徴
とする親水性膜形成組成物。(3) The hydrophilic film-forming composition according to claim 1, wherein the polymer has a functional group.
物において、前記ポリマーの官能基がアクリロイル基、
メタクリロイル基、アリル基及びエポキシ基のいずれか
１種又は２種以上であることを特徴とする親水性膜形成
組成物。(4) In the hydrophilic film-forming composition according to claim 3, the functional group of the polymer is an acryloyl group,
A hydrophilic film-forming composition comprising one or more of methacryloyl groups, allyl groups, and epoxy groups.
載の親水性膜形成組成物において、前記親水性モノマー
は水酸基、カルボキシル基及びその金属塩、アミド基、
イミド基、スルホン酸基及びその金属塩、アンモニウム
塩基及びリン酸基のいずれか１種又は２種以上を含有す
ることを特徴とする親水性膜形成組成物。(5) In the hydrophilic film-forming composition according to any one of claims 1 to 4, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group,
A hydrophilic film-forming composition characterized by containing one or more of an imide group, a sulfonic acid group and its metal salt, an ammonium base, and a phosphoric acid group.
載の親水性膜形成組成物において、前記架橋性モノマー
はアクリロイル基、メタクリロイル基、アリル基及びエ
ポキシ基のいずれか１種又は２種以上を含有することを
特徴とする親水性膜形成組成物。(6) In the hydrophilic film-forming composition according to any one of claims 1 to 5, the crosslinkable monomer is any one of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group, or A hydrophilic film-forming composition characterized by containing two or more kinds.
載の親水性膜形成組成物において、前記ポリマー１００
重量部に対して前記親水性モノマーは５〜２００重量部
であり、前記架橋性モノマーは１〜３００重量部である
ことを特徴とする親水性膜形成組成物。(7) In the hydrophilic film-forming composition according to any one of claims 1 to 6, the polymer 100
A hydrophilic film-forming composition characterized in that the amount of the hydrophilic monomer is 5 to 200 parts by weight, and the amount of the crosslinkable monomer is 1 to 300 parts by weight.
物において、前記ポリマーが官能基を有し、かつ前記ポ
リマー１００重量部に対して前記親水性モノマーは５〜
２００重量部であり、前記架橋性モノマーは１〜２００
量部であることを特徴とする親水性膜形成組成物。(8) In the hydrophilic film-forming composition according to claim 7, the polymer has a functional group, and the hydrophilic monomer is 5 to 5 parts by weight based on 100 parts by weight of the polymer.
200 parts by weight, and the crosslinking monomer is 1 to 200 parts by weight.
1. A hydrophilic film-forming composition characterized in that:
物において、前記ポリマーが官能基を有さず、かつ前記
ポリマー１００重量部に対して前記親水性モノマーは５
〜２００重量部であり、前記架橋性モノマーは５〜３０
０重量部であることを特徴とする親水性膜形成組成物。(9) In the hydrophilic film-forming composition according to claim 7, the polymer has no functional group, and the hydrophilic monomer is 5 parts by weight based on 100 parts by weight of the polymer.
~200 parts by weight, and the crosslinking monomer is 5 to 30 parts by weight.
A hydrophilic film-forming composition characterized in that the amount is 0 parts by weight.
記載の親水性膜形成組成物において、さらに溶剤を含有
することを特徴とする親水性膜形成組成物。(10) The hydrophilic film-forming composition according to any one of claims 1 to 9, further comprising a solvent.
物において、前記溶剤は前記ポリマー１００重量部に対
して６０００重量部以下であることを特徴とする親水性
膜形成組成物。(11) The hydrophilic film-forming composition according to claim 10, wherein the amount of the solvent is 6000 parts by weight or less based on 100 parts by weight of the polymer.
おいて、ポリマーと、親水性モノマーと、架橋性モノマ
ーと、界面活性剤とを含有することを特徴とする親水性
膜形成組成物。(12) A composition for forming a hydrophilic film by electron beam irradiation, which contains a polymer, a hydrophilic monomer, a crosslinking monomer, and a surfactant.
組成物において、前記ポリマーが官能基を実質的に有さ
ないことを特徴とする親水性膜形成組成物。(13) The hydrophilic film-forming composition according to claim 12, wherein the polymer has substantially no functional group.
組成物において、前記ポリマーが官能基を有することを
特徴とする親水性膜形成組成物。(14) The hydrophilic film-forming composition according to claim 12, wherein the polymer has a functional group.
組成物において、前記ポリマーの官能基がアクリロイル
基、メタクリロイル基、アリル基及びエポキシ基のいず
れか１種又は２種以上であることを特徴とする親水性膜
形成組成物。(15) In the hydrophilic film-forming composition according to claim 14, the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic film-forming composition characterized by:
かに記載の親水性膜形成組成物において、前記親水性モ
ノマーは水酸基、カルボキシル基及びその金属塩、アミ
ド基、イミド基、スルホン酸基及びその金属塩、アンモ
ニウム塩基及びリン酸基のいずれか１種又は２種以上を
含有することを特徴とする親水性膜形成組成物。(16) In the hydrophilic film-forming composition according to any one of claims 12 to 15, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfonic acid group. A hydrophilic film-forming composition characterized by containing one or more of a group and a metal salt thereof, an ammonium base, and a phosphoric acid group.
かに記載の親水性膜形成組成物において、前記架橋性モ
ノマーはアクリロイル基、メタクリロイル基、アリル基
及びエポキシ基のいずれか１種又は２種以上を含有する
ことを特徴とする親水性膜形成組成物。(17) In the hydrophilic film-forming composition according to any one of claims 12 to 16, the crosslinkable monomer is any one of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group, or A hydrophilic film-forming composition characterized by containing two or more kinds.
かに記載の親水性膜形成組成物において、前記ポリマー
１００重量部に対して前記親水性モノマーは５〜２００
重量部であり、前記架橋性モノマーは１〜３００重量部
であることを特徴とする親水性膜形成組成物。(18) In the hydrophilic film-forming composition according to any one of claims 12 to 17, the hydrophilic monomer is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer.
1 to 300 parts by weight of the crosslinkable monomer.
組成物において、前記ポリマーが官能基を有し、かつ前
記ポリマー１００重量部に対して前記親水性モノマーは
５〜２００重量部であり、前記架橋性モノマーは１〜２
００重量部であることを特徴とする親水性膜形成組成物
。(19) In the hydrophilic film-forming composition according to claim 18, the polymer has a functional group, and the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer. Yes, the crosslinking monomer is 1 to 2
00 parts by weight of a hydrophilic film-forming composition.
組成物において、前記ポリマーが官能基を有さず、かつ
前記ポリマー１００重量部に対して前記親水性モノマー
は５〜２００重量部であり、前記架橋性モノマーは５〜
３００重量部であることを特徴とする親水性膜形成組成
物。(20) The hydrophilic film-forming composition according to claim 18, wherein the polymer has no functional group, and the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer. and the crosslinking monomer is 5-
300 parts by weight of a hydrophilic film-forming composition.
親水性膜形成組成物において、前記界面活性剤は前記ポ
リマー１００重量部に対して１００重量部以下であるこ
とを特徴とする親水性膜形成組成物。(21) The hydrophilic film-forming composition according to claims 12 to 20, wherein the surfactant is present in an amount of 100 parts by weight or less based on 100 parts by weight of the polymer. Film-forming composition.
組成物において、前記界面活性剤は１〜５０重量部であ
ることを特徴とする親水性膜形成組成物。(22) The hydrophilic film-forming composition according to claim 21, wherein the surfactant is contained in an amount of 1 to 50 parts by weight.
かに記載の親水性膜形成組成物において、さらに溶剤を
含有することを特徴とする親水性膜形成組成物。(23) The hydrophilic film-forming composition according to any one of claims 12 to 22, further comprising a solvent.
組成物において、前記溶剤は前記ポリマー１００重量部
に対して６０００重量部以下であることを特徴とする親
水性膜形成組成物。(24) The hydrophilic film-forming composition according to claim 23, wherein the amount of the solvent is 6000 parts by weight or less based on 100 parts by weight of the polymer.
ーとを含有する混合物の膜状物に電子線を照射してなり
、前記ポリマーが前記親水性モノマー及び前記架橋性モ
ノマーと架橋していることを特徴とする親水性膜。(25) A film-like material of a mixture containing a polymer, a hydrophilic monomer, and a crosslinkable monomer is irradiated with an electron beam, and the polymer is crosslinked with the hydrophilic monomer and the crosslinkable monomer. A hydrophilic membrane characterized by
いて、前記ポリマーが官能基を実質的に有さないことを
特徴とする親水性膜。(26) The hydrophilic membrane according to claim 25, wherein the polymer has substantially no functional groups.
いて、前記ポリマーが官能基を有することを特徴とする
親水性膜。(27) The hydrophilic membrane according to claim 25, wherein the polymer has a functional group.
いて、前記ポリマーの官能基がアクリロイル基、メタク
リロイル基、アリル基及びエポキシ基のいずれか１種又
は２種以上であることを特徴とする親水性膜。(28) The hydrophilic membrane according to claim 27, wherein the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. hydrophilic membrane.
かに記載の親水性膜において、前記親水性モノマーは水
酸基、カルボキシル基及びその金属塩アミド基、イミド
基、スルホン酸基及びその金属塩、アンモニウム塩基及
びリン酸基のいずれか１種又は２種以上を含有すること
を特徴とする親水性膜。(29) In the hydrophilic membrane according to any one of claims 25 to 28, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, a sulfonic acid group, and a metal salt thereof. A hydrophilic membrane characterized by containing one or more of a salt, an ammonium base, and a phosphoric acid group.
かに記載の親水性膜において、前記架橋性モノマーはア
クリロイル基、メタクリロイル基、アリル基及びエポキ
シ基のいずれか１種又は２種以上を含有することを特徴
とする親水性膜。(30) In the hydrophilic membrane according to any one of claims 25 to 29, the crosslinking monomer is any one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic membrane characterized by containing.
かに記載の親水性膜において、前記ポリマー１００重量
部に対して前記親水性モノマーは５〜２００重量部であ
り、前記架橋性モノマーは１〜３００重量部であること
を特徴とする親水性膜。(31) In the hydrophilic membrane according to any one of claims 25 to 30, the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer, and the crosslinkable monomer is is 1 to 300 parts by weight.
いて、前記ポリマーが官能基を有し、かつ前記ポリマー
１００重量部に対して前記親水性モノマーは５〜２００
重量部であり、前記架橋性モノマーは１〜２００重量部
であることを特徴とする親水性膜。(32) In the hydrophilic membrane according to claim 31, the polymer has a functional group, and the hydrophilic monomer is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer.
1 to 200 parts by weight of the crosslinkable monomer.
いて、前記ポリマーが官能基を有さず、かつ前記ポリマ
ー１００重量部に対して前記親水性モノマーは５〜２０
０重量部であり、前記架橋性モノマーは５〜３００重量
部であることを特徴とする親水性膜。(33) In the hydrophilic membrane according to claim 31, the polymer has no functional group, and the hydrophilic monomer is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the polymer.
0 parts by weight, and the crosslinking monomer is 5 to 300 parts by weight.
かに記載の親水性膜において、前記混合物がさらに溶剤
を含有することを特徴とする親水性膜。(34) The hydrophilic membrane according to any one of claims 25 to 33, wherein the mixture further contains a solvent.
いて、前記溶剤は前記ポリマー１００重量部に対して６
０００重量部以下であることを特徴とする親水性膜。(35) In the hydrophilic membrane according to claim 34, the solvent is 6 parts by weight based on 100 parts by weight of the polymer.
1,000 parts by weight or less.
かに記載の親水性膜において、前記親水性基が表面に多
く存在することを特徴とする親水性膜。(36) The hydrophilic membrane according to any one of claims 25 to 35, characterized in that many of the hydrophilic groups are present on the surface.
かに記載の親水性膜において、前記膜状物が支持体上に
塗布された塗膜であることを特徴とする親水性膜。(37) The hydrophilic membrane according to any one of claims 25 to 36, wherein the membrane-like material is a coating film applied on a support.
いて、膜厚が０．１〜３０μｍであることを特徴とする
親水性膜。(38) The hydrophilic membrane according to claim 37, wherein the hydrophilic membrane has a thickness of 0.1 to 30 μm.
ーと、界面活性剤とを含有する混合物の膜状物に電子線
を照射してなり、前記ポリマーが前記親水性モノマー及
び前記架橋性モノマーと架橋していることを特徴とする
親水性膜。(39) A film of a mixture containing a polymer, a hydrophilic monomer, a crosslinkable monomer, and a surfactant is irradiated with an electron beam, and the polymer is combined with the hydrophilic monomer and the crosslinkable monomer. A hydrophilic membrane characterized by being crosslinked.
いて、前記ポリマーが官能基を実質的に有さないことを
特徴とする親水性膜。(40) The hydrophilic membrane according to claim 39, wherein the polymer has substantially no functional groups.
いて、前記ポリマーが官能基を有することを特徴とする
親水性膜。(41) The hydrophilic membrane according to claim 39, wherein the polymer has a functional group.
いて、前記ポリマーの官能基がアクリロイル基、メタク
リロイル基、アリル基及びエポキシ基のいずれか１種又
は２種以上であることを特徴とする親水性膜。(42) The hydrophilic membrane according to claim 41, wherein the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. hydrophilic membrane.
かに記載の親水性膜において、前記親水性モノマーは水
酸基、カルボキシル基及びその金属塩、アミド基、イミ
ド基、スルホン酸基及びその金属塩、アンモニウム塩基
及びリン酸基のいずれか１種又は２種以上を含有するこ
とを特徴とする親水性膜。(43) In the hydrophilic membrane according to any one of claims 39 to 42, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, a sulfonic acid group, and a sulfonic acid group. A hydrophilic membrane characterized by containing one or more of a metal salt, an ammonium base, and a phosphoric acid group.
かに記載の親水性膜において、前記架橋性モノマーはア
クリロイル基、メタクリロイル基、アリル基及びエポキ
シ基のいずれか１種又は２種以上を含有することを特徴
とする親水性膜。(44) In the hydrophilic membrane according to any one of claims 39 to 43, the crosslinkable monomer is any one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic membrane characterized by containing.
かに記載の親水性膜において、前記ポリマー１００重量
部に対して前記親水性モノマーは５〜２００重量部であ
り、前記架橋性モノマーは１〜３００重量部であること
を特徴とする親水性膜。(45) In the hydrophilic membrane according to any one of claims 39 to 44, the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer, and the crosslinkable monomer is is 1 to 300 parts by weight.
いて、前記ポリマーが官能基を有し、かつ前記ポリマー
１００重量部に対して前記親水性モノマーは５〜２００
重量部であり、前記架橋性モノマーは１〜２００重量部
であることを特徴とする親水性膜。(46) In the hydrophilic membrane according to claim 45, the polymer has a functional group, and the hydrophilic monomer is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer.
1 to 200 parts by weight of the crosslinkable monomer.
いて、前記ポリマーが官能基を有さず、かつ前記ポリマ
ー１００重量部に対して前記親水性モノマーは５〜２０
０重量部であり、前記架橋性モノマーは５〜３００重量
部であることを特徴とする親水性膜。(47) In the hydrophilic membrane according to claim 45, the polymer has no functional group, and the hydrophilic monomer is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the polymer.
0 parts by weight, and the crosslinking monomer is 5 to 300 parts by weight.
親水性膜において、前記界面活性剤は前記ポリマー１０
０重量部に対して１００重量部以下であることを特徴と
する親水性膜。(48) In the hydrophilic membrane according to claims 39 to 47, the surfactant is
A hydrophilic membrane characterized in that the amount is 100 parts by weight or less relative to 0 parts by weight.
いて、前記界面活性剤は１〜５０重量部であることを特
徴とする親水性膜。(49) The hydrophilic membrane according to claim 48, wherein the surfactant is contained in an amount of 1 to 50 parts by weight.
かに記載の親水性膜において、前記親水性基が表面に多
く存在することを特徴とする親水性膜。(50) The hydrophilic membrane according to any one of claims 39 to 49, characterized in that many of the hydrophilic groups are present on the surface.
かに記載の親水性膜において、表面に存在する前記親水
性基が初期防曇性を発揮し、膜中から滲出する前記界面
活性剤が長期防曇性を発揮することを特徴とする親水性
膜。(51) In the hydrophilic film according to any one of claims 39 to 50, the hydrophilic group present on the surface exhibits initial antifogging properties, and the surfactant exudes from within the film. A hydrophilic film characterized by a long-term antifogging agent.
かに記載の親水性膜において、前記膜状物が支持体上に
塗布された塗膜であることを特徴とする親水性膜。(52) The hydrophilic membrane according to any one of claims 39 to 51, wherein the membrane-like material is a coating film applied on a support.
かに記載の親水性膜において、膜厚が０．１〜３０μｍ
であることを特徴とする親水性膜。(53) The hydrophilic film according to any one of claims 40 to 54, wherein the film thickness is 0.1 to 30 μm.
A hydrophilic membrane characterized by:
を混合し、膜状に塗布した上で０．５〜２０Ｍｒａｄの
電子線を照射することを特徴とする親水性膜の製造方法
。(54) A method for producing a hydrophilic film, which comprises mixing a polymer, a hydrophilic monomer, and a crosslinking monomer, coating the mixture in the form of a film, and then irradiating it with an electron beam of 0.5 to 20 Mrad.
界面活性剤とを混合し、膜状に塗布した上で０．５〜２
０Ｍｒａｄの電子線を照射することを特徴とする親水性
膜の製造方法。(55) Mix a polymer, a hydrophilic monomer, a crosslinking monomer, and a surfactant, apply it in a film, and
A method for producing a hydrophilic membrane, which comprises irradiating an electron beam of 0 Mrad.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8413587A JP2649799B2 (en) | 1987-04-06 | 1987-04-06 | Hydrophilic film-forming composition, hydrophilic film thereof and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8413587A JP2649799B2 (en) | 1987-04-06 | 1987-04-06 | Hydrophilic film-forming composition, hydrophilic film thereof and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63251401A true JPS63251401A (en) | 1988-10-18 |
| JP2649799B2 JP2649799B2 (en) | 1997-09-03 |
Family
ID=13822053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8413587A Expired - Lifetime JP2649799B2 (en) | 1987-04-06 | 1987-04-06 | Hydrophilic film-forming composition, hydrophilic film thereof and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2649799B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058900A1 (en) * | 2002-12-26 | 2004-07-15 | Mitsui Chemicals, Inc. | Antifouling material using hydroxyl group-containing acrylamide derivative and use thereof |
| CN100345917C (en) * | 2002-12-26 | 2007-10-31 | 东赛璐株式会社 | Antifouling material using hydroxyl group-containing acrylamide derivative and use thereof |
| JP2015128134A (en) * | 2013-08-30 | 2015-07-09 | キヤノン株式会社 | Curable composition, film, manufacturing method of the same |
| JP2018090685A (en) * | 2016-12-01 | 2018-06-14 | Dic株式会社 | Active energy ray curable antifogging composition and cured article using the same |
| JP2019210396A (en) * | 2018-06-06 | 2019-12-12 | Dic株式会社 | Active energy ray-curable antifogging composition and cured product |
| CN111529988A (en) * | 2020-04-16 | 2020-08-14 | 江苏斯迪克新材料科技股份有限公司 | Medical antifogging protective mask |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7375144B2 (en) | 2005-06-16 | 2008-05-20 | Eastman Chemical Company | Abrasion resistant coatings |
-
1987
- 1987-04-06 JP JP8413587A patent/JP2649799B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058900A1 (en) * | 2002-12-26 | 2004-07-15 | Mitsui Chemicals, Inc. | Antifouling material using hydroxyl group-containing acrylamide derivative and use thereof |
| CN100345917C (en) * | 2002-12-26 | 2007-10-31 | 东赛璐株式会社 | Antifouling material using hydroxyl group-containing acrylamide derivative and use thereof |
| JP2015128134A (en) * | 2013-08-30 | 2015-07-09 | キヤノン株式会社 | Curable composition, film, manufacturing method of the same |
| US10208183B2 (en) | 2013-08-30 | 2019-02-19 | Canon Kabushiki Kaisha | Curable composition, film, and method of producing film |
| JP2018090685A (en) * | 2016-12-01 | 2018-06-14 | Dic株式会社 | Active energy ray curable antifogging composition and cured article using the same |
| JP2019210396A (en) * | 2018-06-06 | 2019-12-12 | Dic株式会社 | Active energy ray-curable antifogging composition and cured product |
| CN111529988A (en) * | 2020-04-16 | 2020-08-14 | 江苏斯迪克新材料科技股份有限公司 | Medical antifogging protective mask |
| CN111529988B (en) * | 2020-04-16 | 2021-12-03 | 江苏斯迪克新材料科技股份有限公司 | Medical antifogging protective mask |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2649799B2 (en) | 1997-09-03 |
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