JP2004082713A - Object having composite hard coat layer and process for forming composite hard coat layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To inexpensively provide an object having a hard coat, which is excellent in stain-proof, lubricity, abrasion resistance and wear resistance, and a process for forming the hard coat. <P>SOLUTION: A hard coat layer 2 in contact with the surface of an object 1 and a stain-proof layer 3 in contact with the surface of the hard coat layer 2 are formed, by applying a hard coat material composition containing an activation energy ray curable compound to form a layer of the hard coat material composition on the object 1 to be hard coat treated, film forming a surface material comprising a fluorine containing multi-functional (meth)acrylate compound and a fluorine containing mono-functional (meth)acrylate compound to form a layer of the surface material on the surface of the layer of the hard coat material composition, and irradiating the formed layers of the hard coat material composition and surface material with the activation energy ray to cure the two layers together. <P>COPYRIGHT: (C)2004,JPO

Description

【０１０４】
以上の測定結果を表１に示す。
表１から、実施例１〜５のハードコート層付き基板は、非常に高い表面硬度を有すると共に、撥水性に優れ、その耐久性も極めて良好であった。
【０１０５】
実施例１では、表面材料において単官能アクリレートに対する二官能アクリレートの使用比率がやや高く、表面平滑性は実用レベルではあるが他の実施例に比べると僅かに劣っていた。実施例２では、実施例１と同一組成の表面材料を用いたが、ハードコート層を半硬化状態とした後に表面材料層を形成したので、表面平滑性に優れていた。実施例３では、実施例１と同一の二官能アクリレート／単官能アクリレート比率であるが、表面材料中におけるフッ化アクリレート総濃度が低く、表面平滑性に優れていた。実施例４、５では、表面材料中におけるフッ化アクリレート総濃度０．５重量％とした場合に、二官能アクリレート／単官能アクリレート比率が適切であり、表面平滑性に優れていた。
【０１０６】
比較例１のハードコート層付き基板は、非常に高い表面硬度を有すると共に、初期の撥水性に優れ、表面平滑性にも優れていた。しかしながら、３０日間室温放置した後にアセトン含浸ウェスで摺動するという過酷な試験条件下では、接触角の低下が見られた。アセトン含浸ウェスでの摺動によって防汚表面層が払拭され、接触角が低下したと考えられる。
【０１０７】
比較例２においては、比較例１と同じ材料を用いたにも係わらず、初期、ウェスでの摺動後ともに撥水性に著しく劣っていた。すなわち、活性エネルギー線硬化型樹脂にフッ化アクリレートを混合し、塗布・硬化させただけではフッ化アクリレート成分が塗膜表面に露出せず、所期の目的を達成できなかった。さらに、比較例２では、調製した組成物を基材表面に塗布している段階で著しい塗布ムラを生じるのが確認された。これは、スピンコート時に希釈溶剤が揮発し、相溶性のないアクリルモノマーとフッ化アクリレートとが急激に相分離を起こしたことによるものであり、この点からも、ハードコートとしての実用に耐えるものではなかった。
【０１０８】
［実施例６］
この実施例は、複合ハードコート層が付与された光情報媒体（以下、光ディスクと略記する）の製造例である。この実施例では、相変化型の光ディスクを製造したが、本発明はこれに限らず、再生専用型の光ディスク、１回のみ記録可能な光ディスク等、記録層の種類によらず広く適用が可能である。
【０１０９】
図２は、複合ハードコート層が付与された光ディスクの一例の概略断面図である。図２において、光ディスク（１１）は、支持基体（１２）の情報ピットやプリグルーブ等の微細凹凸が形成されている側の面上に、反射層（１３）、第２誘電体層（１４）、相変化記録材料層（１５）及び第１誘電体層（１６）をこの順で有し、第１誘電体層（１６）上に光透過層（１８）を有し、光透過層（１８）上にハードコート層（１９）及び防汚表面層（２０）を有する。この例では、反射層（１３）、第２誘電体層（１４）、相変化記録材料層（１５）及び第１誘電体層（１６）が記録層（１７）を構成する。ハードコート層（１９）及び防汚表面層（２０）の両層を便宜的に複合ハードコート層という。光ディスク（１１）は、防汚表面層（２０）、ハードコート層（１９）及び光透過層（１８）を通して、記録又は再生のためのレーザー光が入射するように使用される。
【０１１０】
図２に示す層構成の光記録ディスクサンプルを以下のようにして作製した。
【０１１１】
情報記録のためにグルーブが形成されたディスク状支持基体（１２）（ポリカーボネート製、直径１２０ｍｍ、厚さ１．１ｍｍ）の表面に、Ａｌ_９８Ｐｄ_１Ｃｕ_１（原子比）からなる厚さ１００ｎｍの反射層（１３）をスパッタリング法により形成した。前記グルーブの深さは、波長λ＝４０５ｎｍにおける光路長で表してλ／６とした。グルーブ記録方式における記録トラックピッチは、０．３２μｍとした。
【０１１２】
次いで、反射層（１３）表面に、Ａｌ_２Ｏ_３ターゲットを用いてスパッタリング法により、厚さ２０ｎｍの第２誘電体層（１４）を形成した。第２誘電体層（１４）表面に、相変化材料からなる合金ターゲットを用いてスパッタリング法により、厚さ１２ｎｍの記録材料層（１５）を形成した。記録材料層（１５）の組成（原子比）は、Ｓｂ_７４Ｔｅ_１８（Ｇｅ_７Ｉｎ_１）とした。記録材料層（１５）表面に、ＺｎＳ（８０モル％）−ＳｉＯ_２（２０モル％）ターゲットを用いてスパッタリング法により、厚さ１３０ｎｍの第１誘電体層（１６）を形成した。
【０１１３】
次いで、第１誘電体層（１６）表面に、下記組成のラジカル重合性の紫外線硬化型樹脂をスピンコート法により塗布し、紫外線を照射して、硬化後の厚さが９８μｍとなるように光透過層（１８）を形成した。
【０１１４】
（光透過層：紫外線硬化型樹脂の組成）
ウレタンアクリレートオリゴマー　　　　　　　　　　　　　　５０重量部
（三菱レイヨン（株）製、ダイヤビームＵＫ６０３５）
イソシアヌル酸ＥＯ変性トリアクリレート　　　　　　　　　　１０重量部
（東亜合成（株）製、アロニックスＭ３１５）
イソシアヌル酸ＥＯ変性ジアクリレート　　　　　　　　　　　　５重量部
（東亜合成（株）製、アロニックスＭ２１５）
テトラヒドロフルフリルアクリレート　　　　　　　　　　　　２５重量部
光重合開始剤（１−ヒドロキシシクロヘキシルフェニルケトン）　３重量部
【０１１５】
次いで、光透過層（１８）上に、下記組成の紫外線／電子線硬化型ハードコート剤をスピンコート法により塗布した後、大気中６０℃で３分間加熱することにより被膜内部の希釈溶剤を除去して、未硬化のハードコート層（１９）を形成した。
【０１１６】
（ハードコート剤の組成）
反応性基修飾コロイダルシリカ（分散媒：プロピレングリコールモノメチルエー
テルアセテート、不揮発分：４０重量％）　　　　　　１００重量部
ジペンタエリスリトールヘキサアクリレート　　　　　　４８重量部
テトラヒドロフルフリルアクリレート　　　　　　　　　１２重量部
プロピレングリコールモノメチルエーテルアセテート　　４０重量部
（非反応性希釈溶剤）
イルガキュア１８４（重合開始剤）　　　　　　　　　　　５重量部
【０１１７】
次いで、フッ素系溶剤（住友スリーエム社製、フロリナートＦＣ−７７）９９．５重量部に、パーフルオロポリエーテルジアクリレート（アウジモント社製、Ｆｏｍｂｌｉｎ　Ｚ　ＤＯＬ　のアクリル変性品、分子量：約２０００）０．２５重量部と、３−パーフルオロオクチル−２−ヒドロキシプロピルアクリレート（ダイキンファインケミカル研究所社製）０．２５重量部とを加えて表面材料溶液を調製した。この溶液を上記未硬化ハードコート層（１９）上にスピンコート法によって塗布し、これを６０℃で３分間乾燥し、未硬化表面層（２０）を形成した。
【０１１８】
その後、窒素気流下で電子線を照射することによりハードコート層（１９）と表面層（２０）とを同時に硬化させた。電子線照射装置Ｍｉｎ−ＥＢ（ウシオ電機社製）を用い、電子線加速電圧を５０ｋＶ、照射線量を５Ｍｒａｄとした。照射雰囲気の酸素濃度は８０ｐｐｍであった。ハードコート層（１９）の膜厚は２．５μｍ、表面層（２０）の膜厚は約２８ｎｍであった。なお、表面層の膜厚は、パーフルオロポリエーテル（ダイキン工業社製、デムナム）を標準物質として、蛍光Ｘ線分析（ＸＲＦ）により測定した。このようにして、複合ハードコート層が付与された光記録ディスクサンプルＮｏ．１を得た。
【０１１９】
［比較例３］
実施例６と同様にして、ディスク状支持基体（１２）の表面上に、反射層（１３）、第２誘電体層（１４）、相変化記録材料層（１５）及び光透過層（１８）を順次形成した。
【０１２０】
次いで、光透過層（１８）上に、実施例６で用いたのと同じ組成の紫外線／電子線硬化型ハードコート剤をスピンコート法により塗布した後、大気中６０℃で３分間加熱することにより被膜内部の希釈溶剤を除去して、未硬化のハードコート層（１９）を形成した。
【０１２１】
次いで、２−（パーフルオロデシル）エチルアクリレート（ダイキンファインケミカル研究所社製）の０．５％（質量百分率）フロリナートＦＣ−７７（住友スリーエム社製）溶液を上記未硬化ハードコート層上にスピンコート法によって塗布し、これを６０℃で３分間乾燥し、未硬化表面層を形成した。
【０１２２】
その後、実施例６と同じ電子線照射条件で、窒素気流下で電子線を照射してハードコート層と表面層とを同時に硬化させた。硬化されたハードコート層の膜厚は２．５μｍ、硬化された表面層の膜厚は約２８ｎｍであった。このようにして、複合ハードコート層付き光記録ディスクサンプルＮｏ．２を得た。
【０１２３】
［比較例４］
実施例６と同様にして、ディスク状支持基体（１２）の表面上に、反射層（１３）、第２誘電体層（１４）、相変化記録材料層（１５）及び光透過層（１８）を順次形成した。
【０１２４】
次いで、実施例６で用いたのと同じ組成の紫外線／電子線硬化型ハードコート剤９５重量部に、２−（パーフルオロオクチル）エチルアクリレート（ダイキンファインケミカル研究所社製）５重量部を添加し、均一な組成物を調製した。上記組成物を光透過層（１８）上にスピンコート法により塗布した後、直ちに窒素気流下で電子線を照射して硬化させた。電子線照射条件は実施例６と同じにした。硬化されたハードコート層の膜厚は２．５μｍであった。このようにして、単層からなるハードコート層付き光記録ディスクサンプルＮｏ．３を得た。
【０１２５】
（評価）
実施例６及び比較例３〜４で作製した各光記録ディスクサンプルＮｏ．１〜３のハードコート表面について、ハードコート層付き基板について行ったのと同様に、（１）耐摩耗性、（２）撥水性及びその耐久性、及び（３）表面平滑性の評価を行った。実施例６の光記録ディスクサンプルＮｏ．１は、実施例４のハードコート層付き基板と同等の結果を示し、いずれの性能においても優れていた。また、比較例３の光記録ディスクサンプルＮｏ．２は、比較例１のハードコート層付き基板と同等の結果を示し、比較例４の光記録ディスクサンプルＮｏ．３は、比較例２のハードコート層付き基板と同等の結果を示した。
【０１２６】
上記実施例では、相変化型光ディスクへの複合ハードコート層の付与を示した。しかしながら、本発明は、記録層が相変化型の光ディスクのみならず、再生専用型光ディスクや、追記型光ディスクにも適用される。さらに、本発明は、光情報媒体のみならず、光学レンズ、光学フィルター、反射防止膜、及び各種表示素子にも適用される。そのため、前述の実施例はあらゆる点で単なる例示にすぎず、限定的に解釈してはならない。さらに、特許請求の範囲の均等範囲に属する変更は、すべて本発明の範囲内のものである。
【０１２７】
【発明の効果】
本発明によれば、高い耐摩耗性を有するとともに、撥水性・潤滑性にも優れ、且つ、その耐久性も極めて良好なハードコートが付与された物体が安価に且つ容易に提供される。
【図面の簡単な説明】
【図１】本発明の複合ハードコート層が付与された物体の層構成例を模式的に示す断面図である。
【図２】本発明の複合ハードコート層が付与された光ディスクの一例の概略断面図である。
【符号の説明】
（１）　：対象物体
（２）　：ハードコート層
（３）　：防汚表面層
（１１）：光ディスク
（１２）：支持基体
（１３）：反射層
（１４）：第２誘電体層
（１５）：相変化記録材料層
（１６）：第１誘電体層
（１８）：光透過層
（１９）：ハードコート層
（２０）：防汚表面層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an article with a composite hard coat layer and a method for forming a composite hard coat layer. In the present invention, the composite hard coat layer is a hard coat layer provided on the surface of the object and having scratch resistance and abrasion resistance, and an antifouling surface provided on the surface of the hard coat layer and having antifouling properties and lubricity. Layers. More specifically, in the field of various objects that require antifouling properties and lubricity, and abrasion resistance and abrasion resistance, a composite hard coat layer having these properties is provided on the surface of the present invention. The present invention relates to an object and a method for forming a composite hard coat layer.
[0002]
In particular, the optical performance and recording characteristics of optical recording media, magneto-optical recording media, optical lenses, optical filters, anti-reflection coatings, and various display elements such as liquid crystal displays, CRT displays, plasma displays, and EL displays. The present invention relates to a method for forming a composite hard coat having antifouling property and lubricity, and abrasion resistance and abrasion resistance without impairing the composition, and a product on which the hard coat is formed.
[0003]
[Prior art]
Various objects requiring abrasion resistance and abrasion resistance, for example, optical recording media such as CDs (Compact Disk) and DVDs (Digital Versatile Disk), magneto-optical recording media, optical lenses, optical filters, and anti-reflection films In general, a protective layer (hard coat layer) is provided on the surface of various display elements such as a liquid crystal display, a CRT display, a plasma display, and an EL display.
[0004]
Of these various objects, stains such as fingerprints, sebum, sweat, cosmetics, etc. often adhere to the surfaces thereof by use of the user. Such dirt is not easy to remove once adhered, and in particular, in an optical recording medium and an optical lens used for recording and reproduction, the adhered dirt causes a remarkable trouble in recording and reproduction of an information signal. Therefore, it becomes a big problem.
[0005]
Further, in the magneto-optical recording medium, since the magnetic field head runs on the organic protective layer provided on the recording layer, it is required to increase the wear resistance of the protective layer and to reduce the friction coefficient.
[0006]
As means for solving the former problem, various methods have been proposed for forming a layer having a property that dirt hardly adheres and is easy to wipe off even if it adheres, that is, an antifouling layer on the surface of an optical lens or the like. Specifically, a method of providing a layer made of a fluorine-based or silicone-based compound on the surface and imparting water repellency or oil repellency to the surface to improve the antifouling property is often adopted.
[0007]
On the other hand, many measures have been proposed for the latter problem, that is, a method of reducing the friction coefficient of the surface of the protective layer (hard coat layer). Specifically, for example, a method of providing a film made of a liquid lubricant such as a fluorine-based polymer (for example, perfluoropolyether) or a silicone-based polymer (for example, polydimethylsiloxane) on the surface of the protective layer to improve lubricity Is often used.
[0008]
The former antifouling property and the latter lubricity are essentially completely different properties, but are common in that a fluorine compound or a silicone compound is often used as a means for imparting their performance. . For this reason, when imparting antifouling property or lubricity to the surface of the hard coat using a fluorine-based compound or a silicone-based compound, there are many problems common to both of them.
[0009]
Many fluorine-based or silicone-based compounds are soft, and when these compounds are used, it is extremely difficult to obtain sufficient wear resistance. In order to solve such a problem, a fluorine-based polymer or a silicone-based polymer matrix contains SiO 2.₂A method of increasing the abrasion resistance by adding an inorganic filler such as fine particles has been considered, but with some improvement, as long as a fluorine-based or silicone-based polymer is used as a matrix for dispersing the inorganic filler, it is satisfactory. High abrasion resistance cannot be obtained.
[0010]
For this reason, the protective layer has a laminated structure composed of two or more different layers, the lower layer is a layer made of a material having a high hardness, and an upper layer made of a fluorine-based or silicone-based compound is provided on the surface thereof to provide an antifouling property. Methods for imparting lubricity have been considered. In this case, the upper layer made of a fluorine-based or silicone-based compound is preferably made as thin as possible so that the uppermost layer which is the outermost surface of the laminated protective layer reflects the hardness of the lower layer. However, in this method, it is extremely difficult to obtain adhesion between the lower layer and the upper layer made of a fluorine compound or a silicone compound.
[0011]
As a method for solving the above-mentioned problem of adhesion, for example, the following method is known. That is, SiO₂A lower layer made of an inorganic substance such as is formed by a method such as sputtering or a sol-gel method, and an upper layer made of an alkoxysilane having a fluoroalkyl group is formed on the surface of the lower layer by a method such as vapor deposition or solution coating. Thereafter, by performing a heat treatment in the presence of a trace amount of water, silanol groups generated by the hydrolysis of the alkoxysilane, and / or SiO 2₂A dehydration condensation reaction occurs between the hydroxyl group present on the lower layer surface and the silanol group, and the upper layer is fixed to the lower layer surface through a chemical bond and / or a hydrogen bond.
[0012]
In the above method, it is desirable that the lower layer surface has an active group such as a hydroxyl group at a high density. For this reason, the material that can be used for the lower layer is an inorganic compound, in particular, SiO 2₂, Al₂O₃, TiO₂, ZnS and other metal oxides and metal chalcogenides. Moreover, the lower layer is made of SiO₂Even if it is made of a metal oxide such as that described above, in order to ensure sufficient adhesiveness with the alkoxysilane of the upper layer, prior to the formation of the upper layer, the surface of the lower layer is subjected to alkali treatment and plasma treatment in advance. It is necessary to increase the density of active groups on the surface by performing activation treatment such as corona discharge treatment.
[0013]
Attempts have been made to use an organic substance such as polyethylene, polycarbonate or polymethyl methacrylate as the lower layer, hydrophilize the lower layer surface by a method such as plasma treatment or corona discharge treatment, and provide an upper layer of the alkoxysilane on the lower layer surface. ing. However, in this case, compared with the case where the above-mentioned inorganic substance is used as the lower layer, the adhesion is significantly poor and sufficient durability is not obtained.
[0014]
When the substrate to be hard-coated is made of a resin, SiO.sub.₂In the above method using an inorganic substance such as the above, it is extremely difficult to obtain abrasion resistance as a hard coat. SiO₂When a layer made of an inorganic substance such as the above is provided on the surface of a resin base material, the film thickness that can be formed is at most several hundred nm. It is difficult to make the film thickness more than this in terms of the manufacturing method, and even if it can be formed, the self-destruction of the inorganic film is easy because the difference in elastic modulus and the coefficient of thermal expansion from the substrate is extremely large. Occurs. However, it is difficult to obtain sufficient wear resistance with an inorganic film having a thickness of several 100 nm. It is also difficult to obtain sufficient adhesion between the resin substrate and the inorganic film. Therefore, the inorganic film is easily peeled, and it is difficult to obtain sufficient wear resistance from this point as well.
[0015]
Therefore, when the substrate to be hard-coated is made of a resin, a high elastic modulus primer layer is provided on the resin substrate, and a lower layer made of the inorganic film is provided on the primer layer. It is necessary to ensure the adhesion between the film and the inorganic film and the strength of the inorganic film, further activate the lower layer surface, and provide an upper layer made of the fluorine-based alkoxysilane on the lower layer surface. Thus, it is necessary to sequentially form three layers, and the productivity is extremely low.
[0016]
JP-A-9-137117 discloses a composition containing a polymerizable compound having at least two (meth) acryloyloxy groups in a molecule and inorganic compound fine particles such as silica fine particles on a resin base material surface. It is coated, cured by photopolymerization by irradiation with active energy rays, and the surface of the cured film is subjected to corona treatment or plasma treatment. Then, at least one group capable of producing a silanol group by hydrolysis is provided on the treated surface. There is disclosed a method of forming a silane compound film having improved adhesion to a cured film by applying a silane compound having the same. Also in this case, it is necessary to perform corona treatment or plasma treatment on the surface of the cured film in order to secure the adhesion between the upper silane compound film and the lower cured film.
[0017]
On the other hand, in the above-described protective layer of the magneto-optical recording medium, when a liquid lubricant such as perfluoropolyether or polydimethylsiloxane is applied to the surface of the organic protective layer to form a lubricant film, the lubricant may be a viscous liquid. Therefore, the adhesion between the organic protective layer and the liquid lubricant film does not need to be considered so much. However, in the long term, the lubricant may decrease due to repeated sliding of the magnetic field modulation head, or the lubricant may evaporate little by little during long-term storage. Therefore, also in this method, it is desirable that the lubricant is firmly fixed to the surface of the organic protective layer.
[0018]
By the way, as described above, in order to obtain antifouling properties, it is necessary to impart water repellency and oil repellency to the surface of the protective layer, but this is not always sufficient. Since the operation of wiping off the adhered dirt is generally performed by the hand of the user, when the user performs the wiping operation of the dirt, the friction coefficient of the surface of the protective layer is reduced so that the wiping is easily felt. It is necessary to plan. The relationship between the antifouling property and the coefficient of friction has hardly been pointed out so far, but in practice, in imparting the antifouling property, lowering the friction coefficient is an essential property together with water repellency and oil repellency. It can be said.
[0019]
In addition, by setting the surface to have a low coefficient of friction, the impact at the time when the hard projection comes into contact can be slid and released, so that the occurrence of abrasion can be suppressed. Therefore, from the viewpoint of further improving the scratch-preventing property of the hard coat, a lower friction coefficient on the surface is required.
[0020]
JP-A-6-219945 and JP-A-2000-301053 disclose a composition in which a fluoroalkyl acrylate and an acrylic monomer having no compatibility with the fluoroalkyl acrylate are dissolved in a solvent capable of dissolving both at a predetermined ratio. It is disclosed that a hard coat layer is formed by applying the composition on a material and irradiating the composition with an electron beam immediately after application to cure the composition. According to these publications, by applying the composition to a thickness of 1 to 15 μm, and immediately thereafter irradiating with an electron beam, the solvent is instantaneously evaporated, and the fluoroalkyl acrylate component and the acrylic monomer component are It is localized and cures in a state where the fluoroalkyl acrylate is unevenly distributed on the coating film surface.
[0021]
However, according to the above publications, since a composition containing an incompatible component is used, it is necessary to apply an electron beam and then immediately cure the composition before localization due to solvent volatilization occurs after the composition is applied. There is. For this reason, the timing of electron beam irradiation from application is difficult, and the application method is also extremely limited. For example, it is not possible to use a coating method such as a spin coating method in which the evaporation rate of the solvent is high.
[0022]
Further, as the biggest problem, in the methods described in the two publications, since the solvent is evaporated at the same time as the electron beam irradiation, there is a high possibility that the solvent in the cured film cannot be completely removed. The publication does not verify at all whether the solvent was completely removed from the cured film. If a small amount of solvent remains inside, even if there is no problem immediately after the formation of the hard coat, there is a possibility that cracks or peeling may occur in the film in long-term use. Further, the hardness becomes insufficient, and the warp of the substrate on which the hard coat is formed is apt to gradually increase.
[0023]
Further, in the method of evaporating the solvent at the same time as the electron beam irradiation, the cured film tends to have a porous structure, so that not only the hardness is insufficient but also the optical characteristics may be deteriorated. Therefore, even if there is no problem in application to general-purpose products, it is difficult to apply to applications requiring extremely high optical characteristics, such as optical lenses and optical recording media.
[0024]
That is, there has been no hard coat which simultaneously realizes antifouling property, lubricity and abrasion resistance at a high level.
[0025]
[Patent Document 1]
JP-A-9-137117
[Patent Document 2]
JP-A-6-212945
[Patent Document 3]
JP 2000-301053 A
[0026]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and provide an inexpensive object provided with a hard coat having excellent antifouling properties and lubricity, and excellent scratch resistance and abrasion resistance. It is in. Another object of the present invention is to provide a method for easily and inexpensively forming a hard coat having excellent antifouling properties and lubricity, and excellent scratch resistance and abrasion resistance.
[0027]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and found that a hard coat layer that is responsible for scratch resistance and abrasion resistance is on the surface of the target object, and an antifouling surface layer that is responsible for antifouling properties and lubricity is on the surface of the hard coat layer. It has been found that a composite hard coat layer in which the antifouling surface layer and the hard coat layer are firmly adhered to each other by being simultaneously cured by irradiation with active energy rays is formed, and the present invention has been achieved.
[0028]
The present invention is an object provided with a composite hard coat layer including a hard coat layer provided on the object surface and an antifouling surface layer provided on the hard coat layer surface,
The hard coat layer is made of a cured product of a hard coat agent composition containing an active energy ray-curable compound, and the antifouling surface layer is made of a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) ) A cured product of a surface material containing an acrylate compound, and the antifouling surface layer is an object provided with a composite hard coat layer, which is fixed to the hard coat layer.
[0029]
The present invention is the object provided with the composite hard coat layer, wherein the antifouling surface layer has a thickness of 1 nm or more and 100 nm or less.
[0030]
In the present invention, the active energy ray-curable compound contained in the hard coat agent composition has at least one reactive group selected from a (meth) acryloyl group, a vinyl group and a mercapto group. Is an object to which the composite hard coat layer is applied.
[0031]
The present invention is the object provided with the composite hard coat layer, wherein the hard coat agent composition contains a photopolymerization initiator and, if necessary, an inorganic filler.
[0032]
The present invention forms a hard coat agent composition layer by applying a hard coat agent composition containing an active energy ray-curable compound on the surface of a target object to be subjected to hard coat treatment,
Forming a surface material containing a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) acrylate compound on the surface of the hard coat agent composition layer to form a surface material layer,
Irradiating the formed hard coat agent composition layer and the surface material layer with active energy rays, simultaneously curing the two layers, a hard coat layer in contact with the target object surface and an antifouling surface layer in contact with the hard coat layer surface Wherein a composite hard coat layer including a hard coat layer and an antifouling surface layer is formed on the surface of a target object.
[0033]
The present invention is the method for forming a composite hard coat layer described above, wherein the antifouling surface layer is formed to a thickness of 1 nm or more and 100 nm or less.
[0034]
The present invention is to apply the hard coat agent composition on the surface of the target object, and then dry the solvent to remove the solvent contained in the hard coat agent composition from the hard coat agent composition layer. This is a method for forming the composite hard coat layer described above.
[0035]
The present invention, after applying the hard coating composition on the surface of the target object, if necessary, dried, irradiated with active energy rays to make the hard coating composition layer a semi-cured state, and then the surface material This is a method for forming the composite hard coat layer described above.
[0036]
The present invention is the above-described method for forming a composite hard coat layer, wherein a surface material is formed by coating or vapor-depositing a surface material.
[0037]
The present invention forms a surface material layer by coating a surface material to form a surface material layer, in which case the active energy ray-curable compound in the already formed hard coat agent composition layer is substantially dissolved as a solvent. This is a method for forming the above-mentioned composite hard coat layer using a solvent that is not used.
[0038]
In the present invention, the active energy ray-curable compound contained in the hard coat agent composition has at least one reactive group selected from a (meth) acryloyl group, a vinyl group and a mercapto group. This is a method for forming a composite hard coat layer.
[0039]
The present invention is the above-described method for forming a composite hard coat layer, wherein an electron beam or an ultraviolet ray is used as an active energy ray.
[0040]
The present invention is the above-described method for forming a composite hard coat layer, wherein the irradiation with active energy rays is performed in an atmosphere having an oxygen concentration of 500 ppm or less.
[0041]
The present invention forms a hard coat agent composition layer by applying a hard coat agent composition containing an active energy ray-curable compound on the surface of a target object to be subjected to hard coat treatment,
Forming a surface material containing a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) acrylate compound on the surface of the hard coat agent composition layer to form a surface material layer,
Irradiating the formed hard coat agent composition layer and the surface material layer with active energy rays, simultaneously curing the two layers, a hard coat layer in contact with the target object surface and an antifouling surface layer in contact with the hard coat layer surface Is an object provided with a composite hard coat layer including a hard coat layer provided on the surface of the object and an antifouling surface layer provided on the surface of the hard coat layer.
[0042]
In the present invention, examples of the object include an optical recording medium, a magneto-optical recording medium, an optical lens, an optical filter, an antireflection film, and various display elements. Examples of the display element include a liquid crystal display, a CRT display, a plasma display, an EL display, and the like.
[0043]
In this specification, the “hard coat agent composition layer” means a hard coat layer in an uncured or semi-cured (partially cured) state. The “surface material layer” means a surface layer in an uncured state, that is, an antifouling surface layer.
[0044]
BEST MODE FOR CARRYING OUT THE INVENTION
An embodiment of the present invention will be described in detail with reference to FIG.
FIG. 1 is a cross-sectional view schematically showing a layer configuration example of an object provided with a composite hard coat layer of the present invention. In FIG. 1, a target object (1) to be subjected to a hard coat treatment (a hard coat layer (2)) is formed on a surface, and a hard coat layer (2) (an antifouling surface layer (3)) is formed in contact with the surface. Both the hard coat layer (2) and the antifouling surface layer (3) are conveniently referred to as a composite hard coat layer.
[0045]
The target object (1) includes various objects requiring a hard coat treatment. Examples include, but are not limited to, sheets and substrates made of thermoplastic resins such as polyethylene terephthalate (PET), polymethyl methacrylate, polyethylene, polypropylene, and polycarbonate. More specific products include an optical recording medium, a magneto-optical recording medium, an optical lens, an optical filter, an antireflection film, and various display elements such as a liquid crystal display, a CRT display, a plasma display, and an EL display.
[0046]
First, a hard coat agent composition containing an active energy ray-curable compound is applied to the surface of the target object (1) to form a hard coat agent composition layer, and then, on the surface of the hard coat agent composition layer, Forming a surface material (material having antifouling and lubricating functions) containing a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) acrylate compound to form a surface material layer . Each component of the hard coat agent composition and the surface material will be described.
[0047]
The structure of the active energy ray-curable compound contained in the hard coat agent composition is particularly limited as long as it has at least one active group selected from a (meth) acryloyl group, a vinyl group and a mercapto group. Not done. The active energy ray-curable compound preferably contains a polyfunctional monomer or oligomer containing two or more, preferably three or more polymerizable groups in one molecule in order to obtain sufficient hardness as a hard coat. . It may contain a monofunctional monomer.
[0048]
Among such active energy ray polymerizable compounds, examples of the compound having a (meth) acryloyl group include 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and ethylene oxide-modified bisphenol. A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include 3- (meth) acryloyloxyglycerin mono (meth) acrylate, urethane acrylate, epoxy acrylate, and ester acrylate, but are not necessarily limited thereto. Not intended to be.
[0049]
Examples of the compound having a vinyl group include ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, and ethylene oxide-modified bisphenol A divinyl ether. Examples include vinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane polyvinyl ether, but are not necessarily limited thereto.
[0050]
Examples of the compound having a mercapto group include, for example, ethylene glycol bis (thioglycolate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (thioglycolate), and trimethylolpropane tris (3-glycolate). Mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptopropionate) and the like, but are not necessarily limited thereto.
[0051]
As the active energy ray-curable compound contained in the hard coat agent composition, only one kind may be used, or two or more kinds may be used in combination.
[0052]
The hard coat agent composition may contain a known photopolymerization initiator. The photopolymerization initiator is not particularly required when an electron beam is used as an active energy ray, but is required when an ultraviolet ray is used. Among the photopolymerization initiators, examples of the photoradical initiator include Darocure 1173, Irgacure 651 #, Irgacure 184 #, Irgacure 907 # (all manufactured by Ciba Specialty Chemicals). The content of the photopolymerization initiator is, for example, about 0.5 to 5% by weight in the hard coat agent composition (as solid content).
[0053]
The hard coat agent composition may contain an inorganic filler as needed to improve abrasion resistance. Examples of the inorganic filler include silica, alumina, zirconia, titania and the like. The particle size of the inorganic filler is, for example, about 5 to 50 nm. Among the inorganic fillers, reactive silica particles described in, for example, JP-A-9-100111 as those in which the filler surface is modified with a compound having an active energy ray-polymerizable group and fixed in a polymer matrix after the reaction. And can be preferably used in the present invention. By adding such an inorganic filler to the hard coat agent composition, the wear resistance of the hard coat layer can be further increased. The content of the inorganic filler is, for example, about 5 to 80% by weight in the hard coat agent composition (as solid content). When the content of the inorganic filler is more than 80% by weight, the film strength of the hard coat layer tends to be weak.
[0054]
In addition, the hard coat agent composition may further contain a non-polymerizable diluent solvent, a photopolymerization initiator, an organic filler, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, , A leveling agent, a pigment, a silicon compound and the like.
[0055]
As a surface material, a polyfunctional (meth) acrylate compound containing fluorine and a monofunctional (meth) acrylate compound containing fluorine are used. These are active energy ray polymerizable, and these cured products have antifouling and lubricating functions, that is, they can impart water repellency and / or lubricity to the surface of the object. When a fluorine-containing polyfunctional (meth) acrylate compound is used as the surface material, the adhesion to the hard coat layer is improved, and a composite hard coat layer having extremely excellent durability can be obtained. When a fluorine-containing monofunctional (meth) acrylate compound is used as a surface material, a composite hard coat layer having extremely excellent surface smoothness can be obtained.
[0056]
Examples of the fluorine-containing polyfunctional (meth) acrylate compound include linear perfluoroalkylene di (meth) acrylate, perfluoropolyether di (meth) acrylate, perfluoropolyether tri (meth) acrylate, and perfluoropolyether Tetra (meth) acrylate is exemplified.
[0057]
Examples of the linear perfluoroalkylene di (meth) acrylate include a di (meth) acrylate represented by the following general formula having a perfluoroalkylene group having 12 or less, preferably 8 or more and 12 or less carbon atoms.
[0058]
CH₂= C (R¹) COO-R³− (CF₂) N-R⁴-OCOC (R²) = CH₂
Where R¹And R²May be the same or different and each represents H or a methyl group;³And R⁴May be the same or different and each represents a lower alkylene group, and n represents an integer of 1 to 12. R³And R⁴Examples of the lower alkylene group include -CH₂-, -CH₂CH₂−, (((CF₂) N group side) -CH₂OCH₂-CH (OH) CH₂-(Acryl group side) and the like.
[0059]
As the linear perfluoroalkylene di (meth) acrylate, specifically, for example, 1H, 1H, 6H, 6H -perfluoro-1,6 -hexanediol di (meth) acrylate, 1H, 1H, 10H, 10H -per Fluoro-1,10-decanediol di (meth) acrylate, 1H, 1H, 10H, 10H-perfluoro-1,10-decanediol diepoxy (meth) acrylate, but not necessarily limited to these. Absent.
[0060]
Examples of the perfluoropolyether di (meth) acrylate include di (meth) acrylate and diepoxy (meth) acrylate obtained from a diol-modified perfluoropolyether. Specifically, for example, di (meth) acrylate or diepoxy (meth) acrylate synthesized using the following diol-modified perfluoropolyether as a diol component is exemplified.
[0061]
HOCH₂CF₂O- (CF₂CF₂O) m − / − (CF₂O) n-CF₂CH₂OH
(Fomblin Z ZDOL, manufactured by Ausimont, molecular weight: about 2000)
HO (CH₂CH₂O) l-CH₂CF₂O- (CF₂CF₂O) m − / − (CF₂O) n-CF₂CH₂− (OCH₂CH₂) OH
(Fomblin Z DOL TX 2000, manufactured by Ausimont, molecular weight: about 2200)
1, m and n each represent a degree of polymerization.
[0062]
Examples of the perfluoropolyether tetra (meth) acrylate include tetra (meth) acrylate and tetraepoxy (meth) acrylate obtained from tetraol-modified perfluoropolyether. Specifically, for example, tetra (meth) acrylate or tetraepoxy (meth) acrylate synthesized using the following tetraol-modified perfluoropolyether as a tetraol component is exemplified.
[0063]
HOCH₂CH (OH) CH₂O-CH₂CF₂O- (CF₂CF₂O) m − / − (CF₂O) n-CF₂CH₂OCH₂CH (OH) CH₂OH
(Fomblin Z Tetraol, manufactured by Ausimont)
m and n each represent a degree of polymerization.
[0064]
As the fluorine-containing polyfunctional (meth) acrylate compound, only one kind may be used, or two or more kinds may be used in combination.
[0065]
Examples of the fluorine-containing monofunctional (meth) acrylate compound include linear perfluoroalkyl mono (meth) acrylate and perfluoropolyether mono (meth) acrylate.
[0066]
Examples of the linear perfluoroalkyl mono (meth) acrylate include those having a perfluoroalkyl group having 12 or less carbon atoms. Specifically, for example, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,2-trifluoroethyl (Meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H} -perfluoro-n-octyl (meth) acrylate, 1H, 1H} -perfluoro-n-decyl (meth) acrylate, 3 -(Perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (Perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-9) Methyl (octyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-7) -Methyloctyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, and the like. It is not necessarily limited to these.
[0067]
As the linear perfluoroalkyl mono (meth) acrylate, those having a perfluoroalkyl group having 8 to 12 carbon atoms are preferable, and among the above, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, (Perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate and the like preferable.
[0068]
Examples of the perfluoropolyether mono (meth) acrylate include (meth) acrylate and epoxy (meth) acrylate obtained from alcohol-modified perfluoropolyether. Specifically, for example, (meth) acrylate or epoxy (meth) acrylate synthesized using the following alcohol-modified perfluoropolyether as an alcohol component is exemplified.
F- (CF₂CF₂CF₂O) -CF₂CF₂CF₂OH (Demkin SA, Demnum SA)
F- [CF (CF₃) CF₂O] -CF (CF₃) CF₂OH (Krytox-OH, manufactured by DuPont)
[0069]
As the fluorine-containing monofunctional (meth) acrylate compound, only one kind may be used, or two or more kinds may be used in combination.
[0070]
The ratio between the fluorine-containing polyfunctional (meth) acrylate compound (P) and the fluorine-containing monofunctional (meth) acrylate compound (M) as the surface material is not particularly limited because it depends on the type thereof. In consideration of the improvement in adhesion and surface smoothness, P / M = 0.05 / 1.0 to 10 / 1.0, preferably P / M = 0.1 / 1. It is good to be 0-5.0 / 1.0. When the ratio P / M is larger than 10 / 1.0, the surface smoothness tends to decrease slightly. When the ratio P / M is smaller than 0.05 / 1.0, the fluorine-containing polyfunctional (meth) It is difficult to obtain the effect of improving the adhesion to the hard coat layer by the acrylate compound (P).
[0071]
Further, even when the P / M is relatively large, the total concentration of the polyfunctional and monofunctional fluorine-containing (meth) acrylate (P + M) in the surface material solution is, for example, 1.0% by weight or less, preferably 0.1 to 10% by weight. By adjusting the content to about 0.5% by weight, the surface smoothness can be improved.
[0072]
Also, in the surface material, as in the hard coat agent composition, if necessary, a non-polymerizable diluent solvent, a photopolymerization initiator, a photopolymerization initiation aid, an organic filler, an inorganic filler, and a polymerization inhibition Agents, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, leveling agents, pigments, silicon compounds, and the like. However, it is necessary to select a material that can form an ultrathin antifouling surface layer having a thickness of 1 nm to 100 nm.
[0073]
In the present invention, first, the hard coat agent composition is applied to the surface of the target object (1) （to form a hard coat agent composition layer. The application method is not limited, and various application methods such as spin coating, dip coating, and gravure coating may be used.
[0074]
After applying the hard coat agent composition to the surface of the target object (1) 塗布, it is preferable to eliminate the fluidity of the hard coat agent composition layer before forming the surface material. By eliminating the fluidity of the hard coat agent composition layer, it is possible to prevent a change in the thickness of the hard coat agent composition layer and deterioration of the surface property when a surface material is formed thereon. In addition, it is easy to uniformly form a surface material.
[0075]
In order to eliminate the fluidity of the hard coat agent composition layer, for example, it is preferable to remove the solvent contained in the hard coat agent composition layer from the hard coat agent composition layer by drying after application. Further, after the application, if necessary, the layer may be dried and irradiated with an active energy ray such as an ultraviolet ray so that the hard coat agent composition layer is in a semi-cured state. Here, semi-cured means that a part of the hard coat agent composition is not reacted. Accordingly, the degree of physical curing of the hard coat agent composition layer is not particularly limited, and the surface tackiness (tack) may be lost. In order to achieve such a semi-cured state, for example, the irradiation amount of active energy rays such as ultraviolet rays may be reduced. By doing so, the unreacted hard coat agent composition is present at least in the vicinity of the surface of the hard coat agent composition layer.
[0076]
Next, the surface material is formed on the uncured or partially cured (semi-cured) hard coat agent composition layer surface to form a surface material layer. The surface material layer may be formed so that the finally obtained antifouling surface layer has a thickness of 1 nm to 100 nm, preferably 5 nm to 50 nm. If the thickness is less than 1 nm, the effects of antifouling property and lubricity are not sufficiently obtained. .
[0077]
The film can be formed by applying a surface material or by vapor deposition. Hereinafter, the case of coating will be described as an example. The coating may be performed by diluting the above surface material with an appropriate solvent and applying the coating solution by various coating methods such as spin coating, dip coating, gravure coating, and spray coating without any limitation.
[0078]
As the solvent at this time, it is preferable to select and use a solvent that does not substantially dissolve the active energy ray-curable compound in the uncured or partially cured (semi-cured) hard coat agent composition layer. Whether or not the hard coat agent composition layer is substantially dissolved depends not only on the type of solvent but also on the application method. For example, when using a spin coating method as a coating method of the surface material layer, in many cases, most of the diluting solvent contained in the coating solution during the spin coating is volatilized, so that a solvent that dissolves the hard coating agent composition layer to some extent Even if is used as a diluting solvent, there is no practical problem. On the other hand, for example, when the dip coating method is used as a coating method of the surface material layer, the contact time between the uncured hard coat agent composition layer surface and the surface material layer coating liquid is long, so that the hard coat agent composition It is necessary to use a solvent which does not dissolve the material at all or hardly dissolves it.
[0079]
In this way, an uncured or partially cured (semi-cured) hard coat agent composition layer and an uncured surface material layer are formed on the surface thereof.
[0080]
Next, the formed hard coat agent composition layer and the surface material layer are irradiated with active energy rays to simultaneously cure the two layers. At this time, an active energy ray having an energy amount sufficient to completely cure the two layers is irradiated to complete the curing reaction of both layers. By simultaneously curing the uncured or partially cured (semi-cured) hard coat agent composition layer and the uncured surface material layer provided in contact with the surface, these two layers are firmly bonded at the interface. That is, the cured hard coat layer (2) {cured antifouling surface layer (3)} is obtained with good adhesion.
[0081]
By using such a process of the present invention, an antifouling surface having a high water repellency and lubricity on a hard coat layer (2) having a high hardness is thin enough to reflect the hardness on the outermost surface. In addition to providing the layer (3), good adhesion between the hard coat layer (2) and the antifouling surface layer (3) can be obtained.
[0082]
As a means for simultaneously curing the hard coat agent composition layer and the surface material layer, an appropriate one may be selected from active energy rays such as ultraviolet rays, electron beams, and visible lights. However, in the present invention, the thickness of the antifouling surface layer is extremely thin, 1 nm or more and 100 nm or less, preferably 5 nm or more and 50 nm or less. It is necessary to use a curing means capable of obtaining good reactivity.
[0083]
Specifically, regardless of whether an electron beam or an ultraviolet ray is used as the active energy ray, nitrogen is used so that the oxygen concentration in the active energy ray irradiation atmosphere is 500 ppm or less, preferably 200 ppm or less, more preferably 10 ppm or less. It is preferable to perform purging with an inert gas such as. This is to suppress surface hardening inhibition caused by oxygen radicals present in the irradiation atmosphere. Alternatively, instead of controlling the oxygen concentration in the irradiation atmosphere, conventionally known various oxygen inhibition inhibitors may be added to the hard coat agent composition and / or the surface material. As such an oxygen inhibition inhibitor, for example, the oxygen inhibition inhibitors described in JP-A-2000-109828, JP-A-2000-109828 and JP-A-2000-1440011 can be used. Needless to say, the oxygen inhibition inhibitor may be used in combination with the control of the oxygen concentration in the irradiation atmosphere.
[0084]
By using such a material, and a film forming and curing method, a composite hard coat layer having excellent wear resistance, water repellency and lubricity and excellent durability can be formed.
[0085]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
[0086]
[Example 1]
On a polycarbonate substrate (diameter 12 cm) having a thickness of 0.6 mm, an ultraviolet / electron beam-curable hard coating agent (Desolite Z7503, manufactured by JSR) is applied by spin coating, and then heated at 60 ° C. for 3 minutes in the atmosphere. Then, the diluting solvent inside the coating was removed to form an uncured hard coat layer. The hard coat agent was a composition containing a reactive inorganic filler disclosed in JP-A-9-100111.
[0087]
Next, perfluoropolyether diacrylate (acrylic modified product of Fomblin Z ZDOL, molecular weight: about 2000) 0.39 in 99.5 parts by weight of a fluorine-based solvent (Fluorinert FC-77, manufactured by Sumitomo 3M Limited), 0.33 A surface material solution was prepared by adding 0.17 parts by weight of 3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.). This solution was applied on the uncured hard coat layer by spin coating, and dried at 60 ° C. for 3 minutes to form an uncured surface layer.
[0088]
Thereafter, the hard coat layer and the surface layer were simultaneously cured by irradiating an electron beam under a nitrogen stream. Using an electron beam irradiation apparatus Curetron (manufactured by Nissin High Voltage Co., Ltd.), the electron beam acceleration voltage was 200 kV, and the irradiation dose was 5 Mrad. The oxygen concentration in the irradiation atmosphere was 80 ppm. The thickness of the cured hard coat layer was 3.4 μm, and the thickness of the cured surface layer was about 30 nm. In addition, the film thickness of the surface layer was measured by X-ray fluorescence analysis (XRF) using perfluoropolyether (manufactured by Daikin Industries, Ltd., Demnum) as a standard substance. Thus, a substrate with a composite hard coat layer was obtained.
[0089]
[Example 2]
On a polycarbonate substrate (diameter 12 cm) having a thickness of 0.6 mm, an ultraviolet / electron beam-curable hard coating agent (Desolite Z7503, manufactured by JSR) is applied by spin coating, and then heated at 60 ° C. for 3 minutes in the atmosphere. Thus, the diluting solvent inside the coating was removed. Then, weak ultraviolet light (high pressure mercury lamp, 80 mJ / cm²) To form a semi-cured hard coat layer.
[0090]
Next, perfluoropolyether diacrylate (acrylic modified product of Fomblin Z ZDOL, molecular weight: about 2000) 0.39 in 99.5 parts by weight of a fluorine-based solvent (Fluorinert FC-77, manufactured by Sumitomo 3M Limited), 0.33 A surface material solution was prepared by adding 0.17 parts by weight of 3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.). This solution was applied on the semi-cured hard coat layer by a spin coating method, and dried at 60 ° C. for 3 minutes to form an uncured surface layer.
[0091]
Thereafter, under the same electron beam irradiation conditions as in Example 1, the hard coat layer and the surface layer were simultaneously cured by irradiating an electron beam under a nitrogen stream to obtain a substrate with a composite hard coat layer. The thickness of the cured hard coat layer was 3.4 μm, and the thickness of the cured surface layer was about 32 nm.
[0092]
[Example 3]
To 99.75 parts by weight of a fluorine-based solvent (Fluorinert FC-77, manufactured by Sumitomo 3M Limited) and 0.17 parts by weight of perfluoropolyether diacrylate (acrylic modified product of Fomblin Z ZDOL, manufactured by Ausimont, molecular weight: about 2000) And 0.08 parts by weight of 3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory) to prepare a surface material solution. A substrate with a composite hard coat layer was obtained in the same manner as in Example 1 except that this solution was used as a surface material solution. The thickness of the cured hard coat layer was 3.4 μm, and the thickness of the cured surface layer was about 19 nm.
[0093]
[Example 4]
99.5 parts by weight of a fluorinated solvent (Fluorinert FC-77, manufactured by Sumitomo 3M Limited) and 0.25 parts by weight of perfluoropolyether diacrylate (acrylic modified product of Fomblin Z ZDOL, manufactured by Ausimont, molecular weight: about 2000) And 0.25 parts by weight of 3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory) to prepare a surface material solution. A substrate with a composite hard coat layer was obtained in the same manner as in Example 1 except that this solution was used as a surface material solution. The thickness of the cured hard coat layer was 3.4 μm, and the thickness of the cured surface layer was about 32 nm.
[0094]
[Example 5]
0.13 parts by weight of a perfluoropolyether diacrylate (acrylic modified product of Fomblin Z ZDOL, molecular weight: about 2000) per 99.5 parts by weight of a fluorinated solvent (Fluorinert FC-77, manufactured by Sumitomo 3M Limited) And 0.38 parts by weight of 3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory) were added to prepare a surface material solution. A substrate with a composite hard coat layer was obtained in the same manner as in Example 1 except that this solution was used as a surface material solution. The thickness of the cured hard coat layer was 3.4 μm, and the thickness of the cured surface layer was about 35 nm.
[0095]
[Comparative Example 1]
On a polycarbonate substrate (diameter 12 cm) having a thickness of 0.6 mm, an ultraviolet / electron beam-curable hard coating agent (Desolite Z7503, manufactured by JSR) is applied by spin coating, and then heated at 60 ° C. for 3 minutes in the atmosphere. Then, the diluting solvent inside the coating was removed to form an uncured hard coat layer.
[0096]
Next, a 0.5% (mass percentage) Fluorinert FC-77 (manufactured by Sumitomo 3M) solution of 2- (perfluorodecyl) ethyl acrylate (manufactured by Daikin Fine Chemical Laboratory) is spin-coated on the uncured hard coat layer. This was applied by a method and dried at 60 ° C. for 3 minutes to form an uncured surface layer.
[0097]
Thereafter, under the same electron beam irradiation conditions as in Example 1, the hard coat layer and the surface layer were simultaneously cured by irradiating an electron beam under a nitrogen stream to obtain a substrate with a composite hard coat layer. The thickness of the cured hard coat layer was 3.4 μm, and the thickness of the cured surface layer was about 36 nm.
[0098]
[Comparative Example 2]
5 parts by weight of 2- (perfluorooctyl) ethyl acrylate (manufactured by Daikin Fine Chemical Laboratories) are added to 95 parts by weight of an ultraviolet / electron beam-curable hard coat agent (manufactured by JSR Corporation, Desolite Z7503) to obtain a uniform composition. Was prepared. The composition was applied on a polycarbonate substrate (diameter: 12 cm) having a thickness of 0.6 mm by a spin coating method, and then immediately irradiated with an electron beam under a nitrogen stream to be cured, thereby producing a substrate with a hard coat layer. The electron beam irradiation conditions were the same as in Example 1. The thickness of the cured hard coat layer was 4.0 μm.
[0099]
(Evaluation)
The following performance tests were performed on the samples prepared in Examples 1 to 5 and Comparative Examples 1 and 2.
[0100]
(1) Wear resistance
Using steel wool # 0000, the surface of the hard coat of the sample was set to a load of 4.9 N / cm.²The degree of scratches caused by sliding 20 times back and forth was visually determined. The criteria are as follows.
○: no scratch
△: slightly scratched
×: Scratches occurred
[0101]
(2) Water repellency and its durability
The contact angle of water on the hard coat surface of the sample was measured. The measurement was carried out for a sample left at room temperature for 1 day from the preparation (initial sample), a sample after leaving the hard coat surface of the sample left at room temperature for 1 day from the preparation and sliding with a cloth containing a solvent, and 30 days after the preparation. The test was performed on each of the samples after sliding the hard coat surface of the sample left at room temperature with a waste cloth containing a solvent. The sliding conditions were as follows. That is, a nonwoven fabric (manufactured by Asahi Kasei Kogyo Co., Ltd., Bencott Lint Free CT-8) is impregnated with acetone, and the load is 4.9 N / cm.²Slid 50 times. The measurement of the contact angle was performed using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. in an environment at a temperature of 20 ° C. and a relative humidity of 60%.
[0102]
(3) Surface smoothness
The smoothness of the hard coat surface of the sample was visually confirmed. The surface of the sample is held up by electric light and observed from an oblique direction of 20 to 30 degrees, and unevenness or undulation considered to be caused by the uniformity of the surface layer (the presence or absence of microscopic aggregation) and the surface property of the hard coat layer is observed. Was checked. The criteria are as follows.
：: The surface layer was uniform without microscopic aggregation, and no unevenness or undulation was observed in the hard coat layer.
＋+: Microscopic aggregation was observed in the surface layer but extremely slight, and no unevenness or undulation was observed in the hard coat layer.
−-: Microscopic aggregation was observed on the surface layer, but no unevenness or undulation was observed on the hard coat layer.
Δ: Microscopic aggregation is remarkably observed on the surface layer, and irregularities and undulations are also observed on the hard coat layer.
X: The unevenness and undulation of the hard coat layer are remarkable, and cloudiness is generated.
[0103]
[Table 1]

[0104]
Table 1 shows the above measurement results.
As shown in Table 1, the substrates with the hard coat layers of Examples 1 to 5 had extremely high surface hardness, excellent water repellency, and extremely good durability.
[0105]
In Example 1, the use ratio of the bifunctional acrylate to the monofunctional acrylate in the surface material was slightly high, and the surface smoothness was at a practical level, but was slightly inferior to the other examples. In Example 2, although the surface material having the same composition as in Example 1 was used, the surface material layer was formed after the hard coat layer was in a semi-cured state, so that the surface smoothness was excellent. In Example 3, the same bifunctional acrylate / monofunctional acrylate ratio as in Example 1 was used, but the total concentration of fluorinated acrylate in the surface material was low, and the surface smoothness was excellent. In Examples 4 and 5, when the total concentration of the fluorinated acrylate in the surface material was 0.5% by weight, the bifunctional acrylate / monofunctional acrylate ratio was appropriate, and the surface smoothness was excellent.
[0106]
The substrate with the hard coat layer of Comparative Example 1 had an extremely high surface hardness, was excellent in initial water repellency, and was also excellent in surface smoothness. However, under severe test conditions of sliding with an acetone-impregnated waste after being left at room temperature for 30 days, a decrease in the contact angle was observed. It is considered that the antifouling surface layer was wiped off by sliding with the acetone-impregnated waste, and the contact angle was reduced.
[0107]
In Comparative Example 2, although the same material as in Comparative Example 1 was used, the water repellency was remarkably poor both in the initial stage and after the sliding with the rag. That is, the fluorinated acrylate component was not exposed to the coating film surface only by mixing the active energy ray-curable resin with the fluorinated acrylate, followed by coating and curing, and the intended purpose could not be achieved. Furthermore, in Comparative Example 2, it was confirmed that significant application unevenness occurred during the stage of applying the prepared composition to the substrate surface. This is due to the fact that the diluting solvent volatilized during spin coating, and the incompatible acrylic monomer and fluorinated acrylate rapidly separated into phases. Was not.
[0108]
[Example 6]
This embodiment is an example of manufacturing an optical information medium (hereinafter abbreviated as an optical disk) provided with a composite hard coat layer. In this embodiment, a phase change type optical disk is manufactured. However, the present invention is not limited to this, and can be widely applied regardless of the type of the recording layer, such as a read-only optical disk and an optical disk which can record only once. is there.
[0109]
FIG. 2 is a schematic cross-sectional view of an example of an optical disk provided with a composite hard coat layer. In FIG. 2, an optical disk (11) has a reflective layer (13) and a second dielectric layer (14) on a surface of a support base (12) on which fine irregularities such as information pits and pregrooves are formed. , A phase change recording material layer (15) and a first dielectric layer (16) in this order, a light transmitting layer (18) on the first dielectric layer (16), and a light transmitting layer (18). ) Has a hard coat layer (19) and an antifouling surface layer (20). In this example, the reflective layer (13), the second dielectric layer (14), the phase change recording material layer (15), and the first dielectric layer (16) constitute a recording layer (17). Both layers of the hard coat layer (19) and the antifouling surface layer (20) are conveniently referred to as a composite hard coat layer. The optical disc (11) is used so that a laser beam for recording or reproduction is incident through an antifouling surface layer (20), a hard coat layer (19) and a light transmitting layer (18).
[0110]
An optical recording disk sample having the layer configuration shown in FIG. 2 was produced as follows.
[0111]
On the surface of a disk-shaped support substrate (12) (groove formed for information recording, made of polycarbonate, diameter 120 mm, thickness 1.1 mm), Al₉₈Pd₁Cu₁A reflection layer (13) having a thickness of 100 nm (atomic ratio) was formed by a sputtering method. The depth of the groove was represented by λ / 6 as an optical path length at a wavelength λ = 405 nm. The recording track pitch in the groove recording method was 0.32 μm.
[0112]
Next, on the surface of the reflective layer (13), Al was added.₂O₃A 20-nm-thick second dielectric layer (14) was formed by sputtering using a target. A 12-nm thick recording material layer (15) was formed on the surface of the second dielectric layer (14) by a sputtering method using an alloy target made of a phase change material. The composition (atomic ratio) of the recording material layer (15) is Sb₇₄Te₁₈(Ge₇In₁). On the surface of the recording material layer (15), ZnS (80 mol%)-SiO₂(20 mol%) A first dielectric layer (16) having a thickness of 130 nm was formed by a sputtering method using a target.
[0113]
Next, the surface of the first dielectric layer (16) is coated with a radical polymerizable ultraviolet-curable resin having the following composition by spin coating, and is irradiated with ultraviolet light so that the cured film has a thickness of 98 μm. A transmission layer (18) was formed.
[0114]
(Light transmitting layer: composition of ultraviolet curable resin)
Urethane acrylate oligomer 50 parts by weight
(Diabeam UK6035 manufactured by Mitsubishi Rayon Co., Ltd.)
Isocyanuric acid EO modified triacrylate @ 10 parts by weight
(Aronix M315, manufactured by Toa Gosei Co., Ltd.)
Isocyanuric acid EO-modified diacrylate 5 parts by weight
(Aronix M215, manufactured by Toa Gosei Co., Ltd.)
Tetrahydrofurfuryl acrylate 25 parts by weight
Photopolymerization initiator (1-hydroxycyclohexylphenyl ketone) 3 parts by weight
[0115]
Next, an ultraviolet / electron beam-curable hard coat agent having the following composition is applied on the light transmitting layer (18) by spin coating, and then heated at 60 ° C. for 3 minutes in the air to remove the diluting solvent inside the coat. Thus, an uncured hard coat layer (19) was formed.
[0116]
(Composition of hard coat agent)
Reactive group-modified colloidal silica (dispersion medium: propylene glycol monomethyl acrylate)
Tel acetate, non-volatile content: 40% by weight) 100 parts by weight
Dipentaerythritol hexaacrylate 48 parts by weight
Tetrahydrofurfuryl acrylate @ 12 parts by weight
Propylene glycol monomethyl ether acetate @ 40 parts by weight
(Non-reactive diluting solvent)
Irgacure 184 (polymerization initiator) 5 parts by weight
[0117]
Next, 99.5 parts by weight of a fluorine-based solvent (Fluorinert FC-77, manufactured by Sumitomo 3M Ltd.) was added to 0.25 of perfluoropolyether diacrylate (acrylic modified product of Fomblin Z ZDOL, manufactured by Audimont, molecular weight: about 2000). A surface material solution was prepared by adding 0.25 parts by weight of 3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.). This solution was applied on the uncured hard coat layer (19) by a spin coating method, and dried at 60 ° C. for 3 minutes to form an uncured surface layer (20).
[0118]
Thereafter, the hard coat layer (19) and the surface layer (20) were simultaneously cured by irradiating an electron beam under a nitrogen stream. Using an electron beam irradiation device Min-EB (manufactured by Ushio Inc.), the electron beam acceleration voltage was 50 kV, and the irradiation dose was 5 Mrad. The oxygen concentration in the irradiation atmosphere was 80 ppm. The thickness of the hard coat layer (19) was 2.5 μm, and the thickness of the surface layer (20) was about 28 nm. In addition, the film thickness of the surface layer was measured by X-ray fluorescence analysis (XRF) using perfluoropolyether (made by Daikin Industries, Demnum) as a standard substance. Thus, the optical recording disk sample No. 1 was obtained.
[0119]
[Comparative Example 3]
In the same manner as in Example 6, a reflective layer (13), a second dielectric layer (14), a phase change recording material layer (15), and a light transmitting layer (18) are formed on the surface of the disk-shaped support base (12). Were sequentially formed.
[0120]
Next, an ultraviolet / electron beam curable hard coat agent having the same composition as that used in Example 6 is applied on the light transmitting layer (18) by spin coating, and then heated at 60 ° C. in the atmosphere for 3 minutes. The diluting solvent inside the coating was removed by the above to form an uncured hard coat layer (19).
[0121]
Next, a 0.5% (mass percentage) Fluorinert FC-77 (manufactured by Sumitomo 3M) solution of 2- (perfluorodecyl) ethyl acrylate (manufactured by Daikin Fine Chemical Laboratory) is spin-coated on the uncured hard coat layer. This was applied by a method and dried at 60 ° C. for 3 minutes to form an uncured surface layer.
[0122]
Thereafter, under the same electron beam irradiation conditions as in Example 6, the hard coat layer and the surface layer were simultaneously cured by irradiating an electron beam under a nitrogen stream. The thickness of the cured hard coat layer was 2.5 μm, and the thickness of the cured surface layer was about 28 nm. Thus, the optical recording disk sample No. 2 was obtained.
[0123]
[Comparative Example 4]
In the same manner as in Example 6, a reflective layer (13), a second dielectric layer (14), a phase change recording material layer (15), and a light transmitting layer (18) are formed on the surface of the disk-shaped support base (12). Were sequentially formed.
[0124]
Next, 5 parts by weight of 2- (perfluorooctyl) ethyl acrylate (manufactured by Daikin Fine Chemical Laboratory) were added to 95 parts by weight of the ultraviolet / electron beam curable hard coat agent having the same composition as that used in Example 6. A homogeneous composition was prepared. The composition was applied onto the light transmitting layer (18) by spin coating, and then immediately cured by irradiating with an electron beam under a nitrogen stream. The electron beam irradiation conditions were the same as in Example 6. The thickness of the cured hard coat layer was 2.5 μm. In this way, the optical recording disk sample No. 3 was obtained.
[0125]
(Evaluation)
Each optical recording disk sample No. produced in Example 6 and Comparative Examples 3-4. Evaluations of (1) abrasion resistance, (2) water repellency and its durability, and (3) surface smoothness were performed on hard coat surfaces 1 to 3 in the same manner as performed on the substrate with a hard coat layer. Was. The optical recording disk sample No. No. 1 showed the same result as the substrate with a hard coat layer of Example 4, and was excellent in any performance. In addition, the optical recording disk sample No. 2 shows the same results as the substrate with the hard coat layer of Comparative Example 1, and the optical recording disk sample No. No. 3 showed a result equivalent to that of the substrate with a hard coat layer of Comparative Example 2.
[0126]
In the above embodiment, the application of the composite hard coat layer to the phase-change optical disc was described. However, the present invention is applied not only to an optical disk having a recording layer of a phase change type, but also to a read-only optical disk and a write-once optical disk. Further, the present invention is applied not only to an optical information medium but also to an optical lens, an optical filter, an antireflection film, and various display elements. Therefore, the above-described embodiment is merely an example in every aspect, and should not be construed as limiting. Furthermore, all modifications belonging to the equivalent scope of the claims are within the scope of the present invention.
[0127]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, while having high abrasion resistance, being excellent in water repellency and lubricity, and having extremely good durability, an object provided with a hard coat is inexpensively and easily provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing a layer configuration example of an object provided with a composite hard coat layer of the present invention.
FIG. 2 is a schematic sectional view of an example of an optical disk provided with a composite hard coat layer according to the present invention.
[Explanation of symbols]
(1): Target object
(2): Hard coat layer
(3): Antifouling surface layer
(11): Optical disk
(12): Support base
(13): reflective layer
(14): Second dielectric layer
(15): phase change recording material layer
(16): First dielectric layer
(18): Light transmission layer
(19): Hard coat layer
(20): Antifouling surface layer

Claims (10)

An object provided with a composite hard coat layer including a hard coat layer provided on the object surface and an antifouling surface layer provided on the hard coat layer surface,
The hard coat layer is made of a cured product of a hard coat agent composition containing an active energy ray-curable compound, and the antifouling surface layer is made of a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) An object provided with a composite hard coat layer, comprising a cured product of a surface material containing an acrylate compound, wherein the antifouling surface layer is fixed to the hard coat layer. The active energy ray-curable compound contained in the hard coat agent composition has at least one reactive group selected from a (meth) acryloyl group, a vinyl group, and a mercapto group. An object provided with a composite hard coat layer of The article provided with the composite hard coat layer according to claim 1 or 2, wherein the hard coat agent composition contains a photopolymerization initiator and, if necessary, an inorganic filler. On the surface of the object to be hard-coated, a hard coat agent composition containing an active energy ray-curable compound is applied to form a hard coat agent composition layer,
Forming a surface material containing a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) acrylate compound on the surface of the hard coat agent composition layer to form a surface material layer,
Irradiating the formed hard coat agent composition layer and the surface material layer with active energy rays, simultaneously curing the two layers, a hard coat layer in contact with the target object surface and an antifouling surface layer in contact with the hard coat layer surface Forming a composite hard coat layer including a hard coat layer and an antifouling surface layer on the surface of a target object. After applying the hard coat agent composition to the surface of the target object, drying, remove the solvent contained in the hard coat agent composition from the hard coat agent composition layer, and then form a surface material layer, A method for forming a composite hard coat layer according to claim 4. After applying the hard coat agent composition to the surface of the target object, drying as necessary, irradiating active energy rays to make the hard coat agent composition layer in a semi-cured state, and then forming a surface material layer The method for forming a composite hard coat layer according to claim 4. The surface material layer is formed by coating the surface material to form a surface material layer, and in this case, a solvent that does not substantially dissolve the active energy ray-curable compound in the already formed hard coat agent composition layer is used. The method for forming a composite hard coat layer according to any one of claims 4 to 6. The active energy ray-curable compound contained in the hard coat agent composition has at least one reactive group selected from a (meth) acryloyl group, a vinyl group and a mercapto group. The method for forming a composite hard coat layer according to any one of the above. On the surface of the object to be hard-coated, a hard coat agent composition containing an active energy ray-curable compound is applied to form a hard coat agent composition layer,
Forming a surface material containing a fluorine-containing polyfunctional (meth) acrylate compound and a fluorine-containing monofunctional (meth) acrylate compound on the surface of the hard coat agent composition layer to form a surface material layer,
Irradiating the formed hard coat agent composition layer and the surface material layer with active energy rays, simultaneously curing the two layers, a hard coat layer in contact with the target object surface and an antifouling surface layer in contact with the hard coat layer surface An object provided with a composite hard coat layer comprising a hard coat layer provided on the object surface and an antifouling surface layer provided on the hard coat layer surface, obtained by forming The composite hard coat layer according to any one of claims 1 to 3, wherein the object is an optical recording medium, a magneto-optical recording medium, an optical lens, an optical filter, an antireflection film, or various display elements. An object with.

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