JPH11293159A - Hard coating agent for optical recording medium and optical recording medium - Google Patents
Hard coating agent for optical recording medium and optical recording mediumInfo
- Publication number
- JPH11293159A JPH11293159A JP10097315A JP9731598A JPH11293159A JP H11293159 A JPH11293159 A JP H11293159A JP 10097315 A JP10097315 A JP 10097315A JP 9731598 A JP9731598 A JP 9731598A JP H11293159 A JPH11293159 A JP H11293159A
- Authority
- JP
- Japan
- Prior art keywords
- optical recording
- recording medium
- hard coat
- fluorinated
- medium according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Paints Or Removers (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は非架橋型フッ素系界
面活性剤および架橋型フッ素系界面活性剤を含有する防
汚性ハードコート層を設けた光記録媒体に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium provided with an antifouling hard coat layer containing a non-crosslinkable fluorosurfactant and a crosslinkable fluorosurfactant.
【０００２】[0002]
【従来の技術】光ディスクは大容量で可搬性に優れてお
り、実用化が進んでいる。この光ディスクはいずれも透
明基板上に記録層などを形成した後、その上にさらに記
録層を保護するために保護樹脂層を積層した構造になっ
ており、記録層とは反対側の透明基板側からレーザー光
を入射することにより、情報の記録および／または再生
が行われる。2. Description of the Related Art Optical disks are large in capacity and excellent in portability, and are being put to practical use. Each of these optical discs has a structure in which a recording layer is formed on a transparent substrate, and a protective resin layer is further laminated on the recording layer to protect the recording layer. The transparent substrate side opposite to the recording layer Recording and / or reproduction of information is performed by injecting a laser beam from the.
【０００３】使用する基板としてはガラスやポリカーボ
ネートやポリメチルメタクリレートなどがあるが、加工
性、取り扱い性、価格などの点からポリカーボネートが
多く使用されている。しかし、このポリカーボネートは
軟らかく、また、ドライブ内での回転で生じる空気との
摩擦により静電気を帯びやすい。このため、ポリカーボ
ネート基板は空気中の汚れが付着しやすく、容易に傷が
付きやすい。付着する汚れは多種多様であるが、代表的
なものとして空気中のＳｉＯ2 、Ｆｅ2 Ｏ3 、Ａｌ2 Ｏ
3 などの無機物や人の汗や指紋などの有機物などがあ
り、その寸法も数百μｍから０．０１μｍまで分布して
いる。付着する汚れの種類や汚れ具合は使用環境によっ
て大きく異なる。これら汚れのうち、ＳｉＯ2 、Ｆｅ2
Ｏ3 、Ａｌ2 Ｏ3 などの無機物は例えば、エアーブロー
をかけることにより比較的簡単に汚れを落とすことがで
きる。一方、人の汗や指紋などの油成分（有機物）は無
機物などの汚れとは異なり、エアーブローをかけただけ
では汚れが落ちにくい。そのため、これら汚れに対して
は光ディスク専用のクリーナーを用いて汚れを落とす方
法がある。しかし、いずれにしても汚れが光記録媒体表
面に付着した状態やそれが原因で基板に傷がついた状態
で情報の記録および／または再生を行った場合、レーザ
ー光が散乱し、信号エラーとなって正確な情報の記録お
よび／または再生ができなくなる。これらを防止するた
めに通常ポリカーボネート基板の表面保護を目的として
ハードコート層を設けることが知られている。さらにゴ
ミやほこりなどを付着しにくくするためにハードコート
層自体に帯電防止性を付与することも知られている。例
えば特開昭６０−２３９９４６号公報および特開昭６１
−２７６１４５号公報では帯電防止剤としてカチオン系
のアミンを添加したり、アニオン系のアルキルベンゼン
スルホン酸塩、非イオン性のポリオール、アルキルフェ
ノールのエチレンオキサイド、両性系のイミダゾリン型
やアラニン型金属塩を添加、特開平３−４９０５３号公
報では脂肪族ジメチルエチルアンモニウムエトサルフェ
ート化合物を添加、特開平３−１７３９４９号公報では
ラウリル化合物などを添加、特開平４−８０２６７号公
報ではチオシアン酸およびアルキレングリコール鎖を有
するアニオン性界面活性剤を添加する方法がある。これ
ら界面活性剤はいずれもゴミやほこりやなどの無機物の
汚れを付着させにくくする効果がある。しかし、これら
帯電防止剤含有のハードコート剤では人の汗や指紋痕な
どの有機物の汚れに対する防汚性についてはほとんど効
果がない。それにもかかわらず、これまであまり問題と
されなかったのは書き換え型光ディスクの多くがカート
リッジに入っており、光ディスク表面に直接手で触れる
ことがあまりなかったからである。また、たとえ汚れた
場合でも光ディスク専用のクリーナー等を用いて、汚れ
を拭き取ることで解決していた。しかし、将来的には書
き換え型光ディスクもカートリッジを用いず裸のままで
の使用も考えられ、これまで以上に人の汗や指紋痕など
でディスク表面を汚染する機会が増大することが予想さ
れる。さらに高密度記録の光ディスク、例えばＤＶＤの
ような場合、レーザービームスポット径が小さいため、
より小さな汚れに対しても信号エラーとなる可能性が高
い。この場合、もちろんクリーナーを用いて汚れを拭き
取ることは可能であるが、汚れを拭き取る手間が増える
ために作業性が悪くなるばかりでなく、ハードコート層
自体に傷が生じたり、あるいはハードコート層自体が摩
耗し、すり減ることも考えられる。[0003] Substrates to be used include glass, polycarbonate, polymethyl methacrylate, and the like. However, polycarbonate is often used from the viewpoint of workability, handleability, cost, and the like. However, this polycarbonate is soft, and is easily charged with static electricity due to friction with air generated by rotation in the drive. For this reason, the polycarbonate substrate is liable to be contaminated with air and easily scratched. There are various types of stains to be attached, but typical examples are SiO 2 , Fe 2 O 3 , and Al 2 O in air.
There are inorganic substances such as 3 and organic substances such as human sweat and fingerprints, and the size is distributed from several hundred μm to 0.01 μm. The type of dirt and the degree of dirt greatly differ depending on the use environment. Of these stains, SiO 2 , Fe 2
Inorganic substances such as O 3 and Al 2 O 3 can be relatively easily cleaned by air blow, for example. On the other hand, oil components (organic substances) such as human sweat and fingerprints, unlike inorganic substances, are not easily removed by air blow alone. Therefore, there is a method of removing the dirt using a cleaner dedicated to the optical disk. However, in any case, when information is recorded and / or reproduced in a state where dirt adheres to the surface of the optical recording medium or the substrate is scratched due to the dirt, the laser light is scattered and a signal error occurs. As a result, accurate information recording and / or reproduction cannot be performed. It is known that a hard coat layer is usually provided for the purpose of protecting the surface of the polycarbonate substrate in order to prevent these. It is also known that the hard coat layer itself is given an antistatic property in order to make it difficult for dust and dirt to adhere thereto. For example, JP-A-60-239946 and JP-A-61-61946
In the -276145 publication, a cationic amine is added as an antistatic agent, or an anionic alkylbenzene sulfonate, a nonionic polyol, an ethylene oxide of an alkylphenol, and an amphoteric imidazoline-type or alanine-type metal salt are added. In JP-A-3-49053, an aliphatic dimethylethylammonium ethosulfate compound is added. In JP-A-3-173949, a lauryl compound is added. In JP-A-4-80267, an anion having a thiocyanic acid and an alkylene glycol chain is added. There is a method of adding a surfactant. All of these surfactants have an effect of making it difficult to adhere inorganic dirt such as dust and dirt. However, these hard coat agents containing an antistatic agent have almost no effect on stain resistance to organic stains such as human sweat and fingerprint marks. Nevertheless, the reason why this has not been considered a problem so far is that many rewritable optical disks are contained in a cartridge, and the surface of the optical disk is rarely directly touched with a hand. In addition, even if it becomes dirty, the problem has been solved by wiping off the dirt using a cleaner or the like dedicated to an optical disk. However, in the future, rewritable optical disks may be used naked without using a cartridge, and it is expected that the chance of contaminating the disk surface with human sweat or fingerprint marks will increase more than before. . Further, in the case of an optical disk for high-density recording, for example, a DVD, since the laser beam spot diameter is small,
There is a high possibility that a smaller dirt will cause a signal error. In this case, of course, it is possible to wipe off dirt using a cleaner, but not only does the work for wiping off the dirt increase, but also the workability deteriorates, and the hard coat layer itself is damaged or the hard coat layer itself is damaged. Can be worn and worn away.
【０００４】[0004]
【発明が解決しようとする課題】本発明は光記録媒体表
面に防汚性ハードコート層を設けることにより、光記録
媒体表面の防汚性および防汚耐久性を著しく向上させた
光記録媒体を提供するものである。SUMMARY OF THE INVENTION The present invention provides an optical recording medium in which the antifouling property and the antifouling durability of the optical recording medium surface are remarkably improved by providing an antifouling hard coat layer on the surface of the optical recording medium. To provide.
【０００５】[0005]
【課題を解決するための手段】前記課題を解決するため
に、本発明は非架橋型フッ素系界面活性剤を０．０１〜
３重量％含有し、かつ架橋型フッ素系界面活性剤を０．
０１〜５重量％含有することを特徴とする光記録媒体用
ハードコート剤からなる。Means for Solving the Problems To solve the above problems, the present invention provides a non-crosslinked fluorine-based surfactant in an amount of from 0.01 to 0.01%.
3% by weight, and 0.1% of a cross-linkable fluorosurfactant.
It comprises a hard coat agent for optical recording media, characterized in that it is contained in an amount of from 0.01 to 5% by weight.
【０００６】また、本発明は表面にハードコート層を設
けた光記録媒体であって、該ハードコート層が、非架橋
型フッ素系界面活性剤を０．０１〜３重量％含有し、か
つ架橋型フッ素系界面活性剤を０．０１〜５重量％含有
することを特徴とする光記録媒体からなる。The present invention also relates to an optical recording medium having a hard coat layer on the surface, wherein the hard coat layer contains 0.01 to 3% by weight of a non-crosslinkable fluorine-based surfactant, An optical recording medium comprising 0.01 to 5% by weight of a fluorinated surfactant.
【０００７】[0007]
【発明の実施の形態】本発明では光記録媒体表面に非架
橋型フッ素系界面活性剤、および、架橋型フッ素系界面
活性剤を含有する防汚性ハードコート層を設けることに
より光記録媒体表面の防汚性および防汚耐久性が著しく
向上できることを見い出だした。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the surface of an optical recording medium is provided with a non-crosslinkable fluorine-containing surfactant and an antifouling hard coat layer containing a crosslinkable fluorine-containing surfactant. It has been found that the antifouling property and antifouling durability can be remarkably improved.
【０００８】本発明において、対象とした汚れは主に人
間の汗や指紋痕であって、防汚とはこれらの汚れが付着
しないこと、または付着しにくいこと、または容易に拭
き取りが可能であることを意味する。[0008] In the present invention, the target dirt is mainly human sweat or fingerprint marks, and the antifouling means that these dirt does not adhere, is difficult to adhere, or can be easily wiped off. Means that.
【０００９】本発明は非架橋型フッ素系界面活性剤を含
有する防汚性ハードコート剤および防汚性ハードコート
層を有する光記録媒体に関するものである。本発明にお
ける光記録媒体とは光の照射により、情報の記録、消
去、再生が可能である光ディスク、光カード、光テープ
などを示す。これら光記録媒体には再生専用（ＲＯＭ）
光記録媒体、光磁気記録媒体や相変化光記録媒体などの
書換型（ＲＡＭ）光記録媒体、部分再生専用型（ＰＲＯ
Ｍ）光記録媒体、追記型（ＷＯ）光記録媒体などがある
が、特にカートリッジを用いず、裸のままで使用される
光ディスク、例えばＣＤ−ＲＯＭのようなものや従来の
光記録媒体に比べて高記録密度化により、レーザービー
ムスポット径がかなり小さくなり、より小さな汚れに対
しても信号エラーとなりやすいような光記録媒体、例え
ばＤＶＤのようなものに対して特に効果がある。The present invention relates to an antifouling hard coat agent containing a non-crosslinking type fluorine-containing surfactant and an optical recording medium having an antifouling hard coat layer. The optical recording medium in the present invention refers to an optical disk, an optical card, an optical tape, etc., on which information can be recorded, erased, and reproduced by irradiating light. These optical recording media are read-only (ROM)
Rewritable (RAM) optical recording media, such as optical recording media, magneto-optical recording media, and phase-change optical recording media;
M) There are optical recording media, write-once (WO) optical recording media, etc., but compared to optical discs that are used in a naked state without using a cartridge, such as a CD-ROM, and conventional optical recording media. As the recording density is increased, the spot diameter of the laser beam is considerably reduced, and this is particularly effective for an optical recording medium, such as a DVD, which is liable to cause a signal error even with smaller contamination.
【００１０】本発明において、防汚性ハードコート層を
設ける方法は、特に限定されないが、例えば、非架橋型
フッ素系界面活性剤および架橋型フッ素系界面活性剤を
ベースとなる硬化樹脂に溶解または練り込み、塗布し硬
化する方法などが用いられる。また、非架橋型フッ素系
界面活性剤および架橋型フッ素系界面活性剤を含まない
ハードコート層を塗布した上に、さらに前記の防汚性ハ
ードコート層を設けてもかまわない。塗布方法は、スピ
ンコート法、ディップコート法、スプレーコート法、ロ
ールコート法などを用いることができる。In the present invention, the method of providing the antifouling hard coat layer is not particularly limited. For example, a non-crosslinkable fluorine-based surfactant and a crosslinkable fluorine-based surfactant dissolved or dissolved in a base cured resin are used. A method of kneading, coating and curing is used. Further, a hard coat layer not containing a non-crosslinking type fluorine-containing surfactant and a cross-linking type fluorine-containing surfactant may be applied, and the antifouling hard coat layer may be further provided. As a coating method, a spin coating method, a dip coating method, a spray coating method, a roll coating method, or the like can be used.
【００１１】ベースとなる硬化樹脂としては１分子中に
少なくとも１個以上の架橋性二重結合を有する化合物が
挙げられる。例えば、一般によく用いられる光硬化型樹
脂、熱硬化型樹脂、嫌気硬化型樹脂、あるいはこれら併
用硬化型樹脂などが使用できる。Examples of the base cured resin include compounds having at least one crosslinkable double bond in one molecule. For example, a photo-curable resin, a thermo-curable resin, an anaerobic-curable resin, a commonly used curable resin, or the like can be used.
【００１２】光硬化型樹脂としては、ポリウレタンアク
リレート、エポキシアクリレート、ポリオールアクリレ
ートなどのアクリル系樹脂が好ましい。具体的には、架
橋性オリゴマー、単官能または多官能モノマー、光重合
開始剤、光開始助剤などを含むものである。As the photocurable resin, an acrylic resin such as polyurethane acrylate, epoxy acrylate, or polyol acrylate is preferable. Specifically, it contains a crosslinkable oligomer, a monofunctional or polyfunctional monomer, a photopolymerization initiator, a photoinitiator, and the like.
【００１３】架橋性オリゴマーとしては、ポリエステル
（メタ）アクリレート、ポリエーテル（メタ）アクリレ
ート、ポリウレタン（メタ）アクリレート、エポキシ
（メタ）アクリレート、シリコーン（メタ）アクリレー
ト等のアクリルオリゴマーが好ましい。具体的にはポリ
エチレングリコールジ（メタ）アクリレート、ポリプロ
ピレングリコールジ（メタ）アクリレート、ビスフェノ
ールＡ型エポキシアクリレート、ポリウレタンのジアク
リレート、クレゾールノボラック型エポキシ（メタ）ア
クリレート等がある。As the crosslinkable oligomer, acrylic oligomers such as polyester (meth) acrylate, polyether (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate and silicone (meth) acrylate are preferred. Specific examples include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A type epoxy acrylate, polyurethane diacrylate, and cresol novolak type epoxy (meth) acrylate.
【００１４】単官能または多官能モノマーとしては、
（メタ）アクリル酸エステル等のアクリルモノマーが好
ましい。具体的には２官能の（メタ）アクリル酸エステ
ルとしてはトリプロピレングリコールジ（メタ）アクリ
レート、１，６−ヘキサンジオールジアクリレート、テ
トラエチレングリコールジ（メタ）アクリレート等があ
る。３官能の（メタ）アクリル酸エステルとしてはトリ
メチロールプロパントリ（メタ）アクリレート、ペンタ
エリスリトールトリ（メタ）アクリレート等がある。４
官能の（メタ）アクリル酸エステルとしてはテトラメチ
ロールメタンテトラ（メタ）アクリレート、ペンタエリ
スリトールテトラ（メタ）アクリレート等がある。６官
能の（メタ）アクリル酸エステルとしてはジペンタエリ
スリトールヘキサアクリレート等がある。The monofunctional or polyfunctional monomers include:
Acrylic monomers such as (meth) acrylates are preferred. Specifically, examples of the bifunctional (meth) acrylate include tripropylene glycol di (meth) acrylate, 1,6-hexanediol diacrylate, and tetraethylene glycol di (meth) acrylate. Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. 4
Examples of the functional (meth) acrylate include tetramethylolmethanetetra (meth) acrylate and pentaerythritoltetra (meth) acrylate. Hexafunctional (meth) acrylates include dipentaerythritol hexaacrylate.
【００１５】光重合開始剤としては、ケトン系、ベンゾ
イン系、チオキサン系等の光重合開始剤が好ましい。具
体的にはケトン系としてはアセトフェノン、ベンゾフェ
ノン等がある。ベンゾイン系としてはベンゾイン、ベン
ゾインメチルエーテル等がある。チオキサン系としては
チオキサン、２−メチルチオキサン等がある。As the photopolymerization initiator, ketone-based, benzoin-based, thioxane-based photopolymerization initiators and the like are preferable. Specifically, ketones include acetophenone and benzophenone. Benzoin includes benzoin, benzoin methyl ether and the like. Examples of the thioxane include thioxane and 2-methylthioxane.
【００１６】光開始助剤としては、ｎ−ブチルアミン、
トリエチルアミン、アリルチオ尿素等の光開始助剤が好
ましい。As the photoinitiator, n-butylamine,
Photoinitiating aids such as triethylamine and allylthiourea are preferred.
【００１７】また、塗工時の作業性や塗工膜厚の制御の
ため有機溶剤を配合することができる。有機溶剤として
はアルコール系溶剤が好ましい。Further, an organic solvent can be blended for controlling the workability during coating and the coating film thickness. As the organic solvent, an alcohol solvent is preferable.
【００１８】光硬化型樹脂は、アクリルオリゴマー２０
〜８０重量％およびアクリルモノマー８０〜２０重量％
を含むものが好ましく、特に好ましくはウレタンアクリ
レートおよび／またはエポキシアクリレート２０〜８０
重量％、単官能および／または多官能アクリレート８０
〜２０重量％の混合系が挙げられる。The photocurable resin is an acrylic oligomer 20
80% by weight and 80-20% by weight of acrylic monomer
Is preferable, and particularly preferably, urethane acrylate and / or epoxy acrylate 20 to 80
% By weight, monofunctional and / or polyfunctional acrylate 80
-20% by weight of a mixed system.
【００１９】これら光硬化型樹脂を硬化させるのに用い
る光は紫外線、電子線、あるいはガンマ線などであり、
電子線あるいはガンマ線の場合、必ずしも光重合開始剤
や光開始助剤を含有する必要はない。これらの線源とし
ては高圧水銀灯、キセノンランプ、メタルハライドラン
プや加速電子などが使用できる。Light used for curing these photo-curable resins is ultraviolet light, electron beam, gamma ray, or the like.
In the case of an electron beam or a gamma ray, it is not always necessary to contain a photopolymerization initiator or a photoinitiator. As these radiation sources, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an accelerating electron, and the like can be used.
【００２０】フッ素系界面活性剤には重合性二重結合を
持たずベースとなる樹脂とは架橋しない、いわゆる非架
橋型と重合性二重結合を有しベースとなる樹脂と架橋す
る架橋型とがある。非架橋型フッ素系界面活性剤として
はフッ素化アルキルエステル、パーフルオロアルキルア
ルコキシレート、パーフルオロアルキルスルホン酸塩、
パーフルオロアルキルカルボン酸塩、パーフルオロアル
キルアンモニウム塩などがある。架橋型フッ素系界面活
性剤としてはアクリレートあるいはメタアクリレートの
水素原子をフッ素原子に置換した、いわゆるフッ素化ア
クリレートあるいはフッ素化メタアクリレートやフッ素
化エポキシアクリレートなどがある。The fluorine-based surfactant has no polymerizable double bond and does not crosslink with the base resin, that is, a non-crosslinking type and a crosslinkable type which has a polymerizable double bond and crosslinks with the base resin. There is. Non-crosslinkable fluorine surfactants such as fluorinated alkyl esters, perfluoroalkyl alkoxylates, perfluoroalkyl sulfonates,
Perfluoroalkyl carboxylate, perfluoroalkyl ammonium salt and the like. Examples of the crosslinkable fluorine-based surfactant include a so-called fluorinated acrylate, a fluorinated methacrylate, and a fluorinated epoxy acrylate in which a hydrogen atom of acrylate or methacrylate is replaced with a fluorine atom.
【００２１】非架橋型フッ素系界面活性剤はベースとな
る樹脂とは架橋しないために、硬化時にコーティング層
の表面に凝集する傾向がある。そのため、少量加えるだ
けで防汚効果が発揮される。しかしながら、非架橋型フ
ッ素系界面活性剤は、拭き取り耐久性が低く、ディスク
表面に付着した汚れを拭き取る際に表面に凝集している
非架橋型の活性剤が拭き取られてしまい、防汚効果が損
なわれやすい。Since the non-crosslinkable fluorosurfactant does not crosslink with the base resin, it tends to aggregate on the surface of the coating layer during curing. Therefore, the antifouling effect is exhibited only by adding a small amount. However, the non-crosslinking type fluorine-based surfactant has low wiping durability, and the non-crosslinking type surfactant which is agglomerated on the surface is wiped off when the dirt attached to the disk surface is wiped off, and the antifouling effect is obtained. Is easily damaged.
【００２２】一方、架橋型フッ素系界面活性剤の場合、
ベースとなる樹脂と架橋し固定される。そのため、拭き
取り耐久性は高いが、防汚効果が十分ではない。On the other hand, in the case of a cross-linkable fluorine-based surfactant,
Crosslinked with the base resin and fixed. Therefore, the wiping durability is high, but the antifouling effect is not sufficient.
【００２３】非架橋型フッ素系界面活性剤と架橋型フッ
素系界面活性剤を併用すると、最表面の非架橋型フッ素
系界面活性剤が消失しても、新たな非架橋型フッ素系界
面活性剤が、コーティング層内部からしみ出してくる間
の防汚性を架橋型フッ素系界面活性剤保つため、高い防
汚効果を持ち、かつ、防汚耐久性を上げるために効果的
である。When a non-crosslinked fluorine-based surfactant and a crosslinked fluorine-based surfactant are used in combination, a new non-crosslinked fluorine-based surfactant can be used even if the topmost non-crosslinked fluorine-based surfactant disappears. However, since the antifouling property during the exudation from the inside of the coating layer is maintained by the cross-linking type fluorine-based surfactant, it has a high antifouling effect and is effective for increasing the antifouling durability.
【００２４】非架橋型フッ素系界面活性剤のなかでは、
フッ素化アルキルエステルが特に防汚効果に優れてい
る。例えば、次のような構造式をもつものが挙げられ
る。[0024] Among the non-crosslinked fluorine surfactants,
Fluorinated alkyl esters are particularly excellent in antifouling effects. For example, those having the following structural formula can be mentioned.
【００２５】[0025]
【化１】 ここでａは０〜１５の整数、ｂ、ｃおよびｄは０〜１５
の整数である。Ｒは水素、または、メチル基、エチル基
などのアルキル基である。Embedded image Here, a is an integer of 0 to 15, b, c and d are 0 to 15
Is an integer. R is hydrogen or an alkyl group such as a methyl group and an ethyl group.
【００２６】このようなフッ素化アルキルエステルとし
ては例えば、住友スリーエム（株）の“フロラードＦＣ
−４３０”などがある。Examples of such a fluorinated alkyl ester include, for example, "Fluorad FC" manufactured by Sumitomo 3M Limited.
-430 ".
【００２７】架橋型フッ素系界面活性剤としては、フッ
素化アクリレート、フッ素化メタアクリレート、フッ素
化エポキシアクリレートが防汚性に優れ、かつ、ベース
樹脂に対する相溶性にも優れている点で好ましい。例え
ば、パーフロロオクチルエチルアクリレート、パーフロ
ロオクチルエチルメタアクリレート、ヘキサフルオロプ
ロピルアクリレート、ヘキサフルオロプロピルメタアク
リレート、オクタフルオロペンチルアクリレート、オク
タフルオロペンチルメタアクリレート等が挙げられる。As the cross-linkable fluorine-based surfactant, fluorinated acrylate, fluorinated methacrylate, and fluorinated epoxy acrylate are preferable because they have excellent antifouling properties and excellent compatibility with the base resin. For example, perfluorooctylethyl acrylate, perfluorooctylethyl methacrylate, hexafluoropropyl acrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate and the like can be mentioned.
【００２８】本発明で使用する非架橋型フッ素系界面活
性剤はベース硬化樹脂に対して０．０１〜３重量％であ
ることが好ましく、より好ましくは０．１〜１重量％含
有される。架橋型フッ素系界面活性剤は０．０１〜５重
量％であることが好ましく、より好ましくは０．１〜３
重量％含有される。非架橋型フッ素系界面活性剤、架橋
型フッ素系界面活性剤のいずれかが０．０１重量％未満
では本発明の効果が十分発現せず、非架橋型フッ素系界
面活性剤が３重量％を越えると、あるいは架橋型フッ素
系界面活性剤が５重量％を越えると粘度変化が生じ、膜
厚制御が困難になるばかりでなく、硬化物の表面硬度が
低下し、傷が付きやすくなったり、表面に曇りを生じた
りして好ましくない。The non-crosslinked fluorine-based surfactant used in the present invention is preferably contained in an amount of 0.01 to 3% by weight, more preferably 0.1 to 1% by weight, based on the weight of the base cured resin. The cross-linking type fluorine-containing surfactant is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight.
% By weight. If the content of either the non-crosslinked fluorine-based surfactant or the crosslinked fluorine-based surfactant is less than 0.01% by weight, the effect of the present invention is not sufficiently exhibited, and the amount of the non-crosslinked fluorine-based surfactant is 3% by weight. If the amount exceeds the above range, or if the amount of the cross-linking fluorine-containing surfactant exceeds 5% by weight, a change in viscosity occurs, which makes not only difficult to control the film thickness, but also lowers the surface hardness of the cured product and makes the cured product easily scratched. It is not preferable because the surface is clouded.
【００２９】ハードコート層の防汚性はハードコート層
に対する汚れ物質の接触角を測定することにより評価が
可能であり、この接触角が大きければ防汚性に優れてい
ることを示す。汚れ物質は、主に人間の汗や指紋痕であ
るが、測定の際には、それらの代用となる測定液として
人工汗を用いることができる。また、汗や指紋痕の主成
分である有機物のオレイン酸を用いることも好ましい。
より好ましくは、人工汗の接触角が９０°以上、オレイ
ン酸の接触角が７０°以上であると良好な防汚性を得る
ことができる。The antifouling property of the hard coat layer can be evaluated by measuring the contact angle of a contaminant with the hard coat layer. A large contact angle indicates that the antifouling property is excellent. The contaminants are mainly human sweat and fingerprint marks, and at the time of measurement, artificial sweat can be used as a measurement liquid as a substitute for them. It is also preferable to use organic oleic acid, which is a main component of sweat and fingerprint marks.
More preferably, when the contact angle of artificial sweat is 90 ° or more and the contact angle of oleic acid is 70 ° or more, good antifouling properties can be obtained.
【００３０】[0030]
【実施例】以下に本発明について、実施例により説明す
る。ただし、本発明は以下の実施例により限定されるも
のではない。EXAMPLES The present invention will be described below with reference to examples. However, the present invention is not limited by the following examples.
【００３１】防汚性の評価は（１）接触角の測定、
（２）疑似指紋を用いて人工指紋液を圧着させ、拭き取
り後の払拭性の２種類について行った。さらに、クリー
ナーでの防汚耐久性試験後に再び前記の測定を行い、防
汚耐久性評価を行った。接触角の測定は協和界面科学
（株）の接触角計”ＦＡＣＥ ＣＯＮＴＡＣＴ−ＡＮＧ
ＬＥＭＥＴＥＲ”を用い、静止接触角（以下、単に接触
角と略す）でおこなった。対象とした測定液は人工汗、
人工指紋液、および汗や指紋痕の主成分のうち、有機物
のオレイン酸、スクアレン、トリオレインとした。人工
指紋液の拭き取り後の目視評価は疑似指紋（シリコン
製）に人工指紋液をつけ、２ｋｇ／ｃｍ2 の荷重で付着
させた後、”キムワイプ ワイパーＳ−２０００”（十
条キンバリー（株））で３回拭き取り、人工指紋液の払
拭性を評価した。以下にその評価を示す。The antifouling property was evaluated by (1) measurement of contact angle,
(2) The artificial fingerprint liquid was press-bonded using a pseudo fingerprint, and two types of wiping properties after wiping were performed. Further, after the antifouling durability test with a cleaner, the above measurement was performed again to evaluate the antifouling durability. Contact angle measurement is Kyowa Interface Science
FACE CONTACT-ANG
LEMETER "at a static contact angle (hereinafter simply abbreviated as" contact angle ").
Among the main components of the artificial fingerprint liquid and sweat and fingerprint marks, organic oleic acid, squalene and triolein were used. Visual evaluation after wiping of the artificial fingerprint liquid was performed by applying an artificial fingerprint liquid to a pseudo fingerprint (made of silicon) and attaching the artificial fingerprint liquid with a load of 2 kg / cm 2 , and then using “Kimwipe Wiper S-2000” (Jujo Kimberly Co., Ltd.). It was wiped three times, and the wiping property of the artificial fingerprint liquid was evaluated. The evaluation is shown below.
【００３２】 ○：人工指紋痕が見えない △：人工指紋痕が一部残っている ×：人工指紋痕がほとんど残っている 用いた人工汗および人工指紋液の成分は、下記のとおり
である。：: Artificial fingerprint mark is not visible Δ: Part of the artificial fingerprint mark remains ×: Artificial fingerprint mark almost remains The components of the artificial sweat and the artificial fingerprint liquid used are as follows.
【００３３】人工汗の成分（水１リットルあたり） Ｌ−ヒスチジンＨＣｌ・Ｈ2 Ｏ ０．５ｇ ＮａＣｌ ５．０ｇ リン酸二ナトリウム１２Ｈ2 Ｏ ５．０ｇ １／１０Ｎ ＮａＯＨ ２５．０ｍｌ 人工指紋液の成分（水：エタノール＝１：１（体積比）
混合溶媒１リットルあたり） ＮａＣｌ ７．０ｇ 尿素 １．０ｇ 乳酸（８５％） ４．０ｇ 防汚耐久性試験には光ディスク専用クリーナーＬＦ−Ｋ
１０６（松下電器産業（株））を用いた。専用クリーニ
ング液１滴を専用クリーニングクロスにしみこませディ
スク表面を５０回拭き取り、乾燥後に上記（１）、
（２）の測定を行った。Components of artificial sweat (per liter of water) L-histidine HCl.H 2 O 0.5 g NaCl 5.0 g Disodium phosphate 12H 2 O 5.0 g 1 / 10N NaOH 25.0 ml Components of artificial fingerprint liquid (Water: ethanol = 1: 1 (volume ratio)
NaCl 7.0 g Urea 1.0 g Lactic acid (85%) 4.0 g Cleaner for optical disc LF-K for antifouling durability test
106 (Matsushita Electric Industrial Co., Ltd.) was used. Dip one drop of the special cleaning liquid into the special cleaning cloth and wipe the disk surface 50 times.
The measurement of (2) was performed.
【００３４】ハードコート層の表面硬度の測定は表面性
測定機”トライボギア ＴＹＰＥ：ＨＥＩＤＯＮ−１４
ＤＲ”（新東科学（株））を用いて行った。測定条件は
ＪＩＳ Ｋ５４００−１９９０に準じて行った。以下に
その条件を示す。The surface hardness of the hard coat layer is measured by a surface property measuring device “Tribogear TYPE: HEIDON-14”.
DR "(Shinto Kagaku Co., Ltd.). The measurement conditions were based on JIS K5400-1990. The conditions are shown below.
【００３５】 移動速度：０．５ｍｍ／秒（３０ｍｍ／分） 測定回数：５ 荷重 ：１．００±０．０５kg 鉛筆 ：”三菱ユニ”Moving speed: 0.5 mm / sec (30 mm / min) Number of measurements: 5 Load: 1.00 ± 0.05 kg Pencil: “Mitsubishi Uni”
【００３６】（実施例１）紫外線硬化型ハードコート剤
（”ウレタンアクリレート”５０重量％、多官能アクリ
レート４８重量％、光重合開始剤”Ｉｒｇａｃｕｒｅ１
８４” ２重量％）に非架橋型フッ素系界面活性剤とし
て住友スリーエム（株）の“フロラードＦＣ−４３０”
を０．６重量％、架橋型フッ素系界面活性剤として大阪
有機化学工業（株）の“ビスコート ８Ｆ”を２重量％
添加し、充分に撹拌した。これを光ディスク用ポリカー
ボネート基板（直径１２０ｍｍ、厚さ０．６ｍｍ）の記
録層形成面と反対側にスピンコート法により膜厚６μｍ
に塗布した。その後、７００ｍＪ／ｃｍ2 の紫外線を照
射し、ハードコート層の硬化をおこない、防汚耐久性試
験前後の表面の接触角を測定した。各溶媒の接触角は以
下のようであった。Example 1 UV-curable hard coat agent ("urethane acrylate" 50% by weight, polyfunctional acrylate 48% by weight, photopolymerization initiator "Irgacure 1")
84 "(2% by weight) as a non-crosslinkable fluorosurfactant" FLORARD FC-430 "manufactured by Sumitomo 3M Limited.
0.6% by weight, and 2% by weight of "Biscoat 8F" of Osaka Organic Chemical Industry Co., Ltd. as a crosslinkable fluorine-based surfactant
Add and stir well. This was coated on a polycarbonate substrate for optical discs (diameter 120 mm, thickness 0.6 mm) on the side opposite to the recording layer forming surface by spin coating to a thickness of 6 μm.
Was applied. Thereafter, the hard coat layer was cured by irradiating 700 mJ / cm 2 ultraviolet rays, and the contact angles of the surfaces before and after the antifouling durability test were measured. The contact angle of each solvent was as follows.
【００３７】 [0037]
【００３８】（比較例１）非架橋型フッ素系界面活性剤
と架橋型フッ素系界面活性剤を添加しなかった以外は、
実施例１と同様にハードコート剤をスピンコートし、硬
化させた後、接触角を測定した。(Comparative Example 1) Except that the non-crosslinkable fluorine-based surfactant and the crosslinkable fluorine-based surfactant were not added,
After the hard coat agent was spin-coated and cured as in Example 1, the contact angle was measured.
【００３９】 人工指紋液の払拭性、鉛筆硬度は以下のようになった。[0039] The wiping property and pencil hardness of the artificial fingerprint liquid were as follows.
【００４０】 人工指紋液の払拭性 × 鉛筆硬度 ＨＢWipeability of artificial fingerprint liquid × Pencil hardness HB
【００４１】（比較例２）架橋型フッ素系界面活性剤を
添加しなかった以外は、実施例１と同様にし、防汚耐久
性試験前後の表面の接触角を測定した。(Comparative Example 2) The contact angle of the surface before and after the antifouling durability test was measured in the same manner as in Example 1 except that the cross-linkable fluorine-based surfactant was not added.
【００４２】 [0042]
【００４３】[0043]
【発明の効果】光記録媒体の表面に非架橋型フッ素系界
面活性剤および架橋型フッ素系界面活性剤を含有する防
汚性ハードコート層を設けることにより人の汗や指紋痕
などに対する高い防汚性を持つと共に、防汚耐久性が向
上した。By providing an antifouling hard coat layer containing a non-crosslinkable fluorine-based surfactant and a crosslinkable fluorine-based surfactant on the surface of an optical recording medium, high protection against human sweat and fingerprint marks can be obtained. It has soiling properties and has improved antifouling durability.
Claims (15)
〜３重量％含有し、かつ架橋型フッ素系界面活性剤を
０．０１〜５重量％含有することを特徴とする光記録媒
体用ハードコート剤。1. The method according to claim 1, wherein the non-crosslinking type fluorine-containing surfactant is 0.01%.
1 to 3% by weight and 0.01 to 5% by weight of a cross-linkable fluorinated surfactant.
アルキルエステル、パーフルオロアルキルアルコキシレ
ート、パーフルオロアルキルスルホン酸塩、パーフルオ
ロアルキルカルボン酸塩、パーフルオロアルキルアンモ
ニウム塩から選ばれる１種類以上からなる請求項１記載
の光記録媒体用ハードコート剤。2. The at least one non-crosslinked fluorine surfactant selected from fluorinated alkyl esters, perfluoroalkyl alkoxylates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylate salts, and perfluoroalkyl ammonium salts. The hard coat agent for an optical recording medium according to claim 1, comprising:
アルキルエステルである請求項２記載の光記録媒体用ハ
ードコート剤。3. The hard coat agent for an optical recording medium according to claim 2, wherein the non-crosslinkable fluorine-based surfactant is a fluorinated alkyl ester.
クリレート、フッ素化メタアクリレート、フッ素化エポ
キシアクリレートから選ばれる１種類以上からなる請求
項１記載の光記録媒体用ハードコート剤。4. The hard coat agent for an optical recording medium according to claim 1, wherein the cross-linkable fluorinated surfactant comprises at least one selected from fluorinated acrylates, fluorinated methacrylates, and fluorinated epoxy acrylates.
の光記録媒体用ハードコート剤。5. The hard coating agent for an optical recording medium according to claim 1, further comprising a photocurable resin.
〜８０重量％およびアクリルモノマー８０〜２０重量％
を含む請求項５記載の光記録媒体用ハードコート剤。6. The photo-curable resin is an acrylic oligomer 20.
80% by weight and 80-20% by weight of acrylic monomer
The hard coat agent for an optical recording medium according to claim 5, comprising:
ートおよび／またはエポキシアクリレートであり、か
つ、アクリルモノマーが単官能および／または多官能ア
クリレートである請求項６記載の光記録媒体用ハードコ
ート剤。7. The hard coat agent for an optical recording medium according to claim 6, wherein the acrylic oligomer is urethane acrylate and / or epoxy acrylate, and the acrylic monomer is monofunctional and / or polyfunctional acrylate.
体であって、該ハードコート層が、非架橋型フッ素系界
面活性剤を０．０１〜３重量％含有し、かつ架橋型フッ
素系界面活性剤を０．０１〜５重量％含有することを特
徴とする光記録媒体。8. An optical recording medium provided with a hard coat layer on the surface, wherein the hard coat layer contains 0.01 to 3% by weight of a non-crosslinkable fluorine-based surfactant, and is a crosslinkable fluorine-based surfactant. An optical recording medium comprising 0.01 to 5% by weight of a surfactant.
アルキルエステル、パーフルオロアルキルアルコキシレ
ート、パーフルオロアルキルスルホン酸塩、パーフルオ
ロアルキルカルボン酸塩、パーフルオロアルキルアンモ
ニウム塩から選ばれる１種類以上からなる請求項８記載
の光記録媒体。9. The non-crosslinkable fluorosurfactant is at least one selected from fluorinated alkyl esters, perfluoroalkylalkoxylates, perfluoroalkylsulfonates, perfluoroalkylcarboxylates, and perfluoroalkylammonium salts. 9. The optical recording medium according to claim 8, comprising:
化アルキルエステルである請求項９記載の光記録媒体。10. The optical recording medium according to claim 9, wherein the non-crosslinkable fluorinated surfactant is a fluorinated alkyl ester.
アクリレート、フッ素化メタアクリレート、フッ素化エ
ポキシアクリレートから選ばれる１種類以上からなる請
求項８記載の光記録媒体。11. The optical recording medium according to claim 8, wherein the cross-linkable fluorinated surfactant comprises at least one selected from fluorinated acrylates, fluorinated methacrylates, and fluorinated epoxy acrylates.
む請求項８記載の光記録媒体。12. The optical recording medium according to claim 8, wherein the hard coat layer contains an acrylic resin.
角が９０°以上である請求項８記載の光記録媒体。13. The optical recording medium according to claim 8, wherein the contact angle of artificial sweat on the hard coat layer is 90 ° or more.
接触角が７０°以上である請求項８記載の光記録媒体。14. The optical recording medium according to claim 8, wherein the contact angle of oleic acid to the hard coat layer is 70 ° or more.
角が９０°以上でかつオレイン酸の接触角が７０°以上
である請求項８記載の光記録媒体。15. The optical recording medium according to claim 8, wherein the contact angle of artificial sweat to the hard coat layer is 90 ° or more and the contact angle of oleic acid is 70 ° or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10097315A JPH11293159A (en) | 1998-04-09 | 1998-04-09 | Hard coating agent for optical recording medium and optical recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10097315A JPH11293159A (en) | 1998-04-09 | 1998-04-09 | Hard coating agent for optical recording medium and optical recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11293159A true JPH11293159A (en) | 1999-10-26 |
Family
ID=14189063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10097315A Pending JPH11293159A (en) | 1998-04-09 | 1998-04-09 | Hard coating agent for optical recording medium and optical recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11293159A (en) |
Cited By (33)
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-
1998
- 1998-04-09 JP JP10097315A patent/JPH11293159A/en active Pending
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