JP4337164B2 - Optical product and manufacturing method thereof - Google Patents

Description

【００９３】
実施例１で得られたプラスチックレンズの分光特性を図３（ａ）に示す。
【００９４】
＜実施例２＞
密着性改善層の材料をＣｒ₂Ｏ₃にした以外は、実施例１と同様に、同じ真空成膜装置を用いて、同じ基板に密着性改善層、屈折率調整層、ハードコート層、反射防止層を形成した。
【００９５】
実施例２で得られたプラスチックレンズの分光特性は、実施例１とほぼ同じであった。
【００９６】
＜実施例３＞
密着性改善層の材料をＡｌ₂Ｏ₃にした以外は、実施例１と同様に、同じ真空成膜装置を用いて、同じ基板に密着性改善層、屈折率調整層、ハードコート層、反射防止層を形成した。
【００９７】
実施例２で得られたプラスチックレンズの分光特性は、実施例１とほぼ同じであった。
【００９８】
＜実施例４＞
反射防止層を表２に示すように変更した以外は、実施例１と同様に、同じ真空成膜装置を用いて、同じ基板に密着性改善層、屈折率調整層、ハードコート層、反射防止層を形成した。
【００９９】
【表２】

【０１００】
実施例４で得られたプラスチックレンズの分光特性を図３（ｂ）に示す。
【０１０１】
＜比較例１＞
実施例１で密着性改善層を形成しない以外は、すべて実施例１と同様に、同じ真空成膜装置１０を用いて、同じ基板に屈折率調整層、ハードコート層、反射防止層を形成した。
【０１０２】
＜比較例２＞
（１）コーティング組成物の調製
攪拌装置を備えたフラスコ中に、エチルセロソルブ４１．１５ｇ、γ−グリシドキシプロピルトリメトキシシラン３８．４４ｇ、テトラメトキシシラン４．１３ｇを攪拌しつつ順に加え、その後０．０５規定塩酸水１２．９０ｇを加え３０分間攪拌した。続いてシリコン系界面活性剤（日本ユニカー（株）製、商品名“Ｌ−７６０４”）を０．０４ｇさらにメチルセロソルブ分散二酸化チタン−二酸化ジルコニウム−二酸化ケイ素複合微粒子ゾル（ＴｉＯ₂／ＺｒＯ₂／ＳｉＯ₂＝６８／１７／１５（重量比）、固形分濃度２０．５重量％、ＴｉＯ₂とＺｒＯ₂の固溶体を核としてＳｉＯ₂で被覆された微粒子構造をもつ複合微粒子）１０３．３９ｇを添加し充分攪拌した後、０℃で２４時間放置し熟成を行いコーティング組成物を得た。
【０１０３】
（２）プラスチックレンズ基板の作製
４-メルカプトメチル-３,６-ジチオ-１,８- オクタンジチオール８７ｇ、ｍ-キシリレンジイソシアネート９４ｇ、ジブチルスズジラウレート０．０２ｇ、内部離型剤０．１５ｇ、２-（５-メチル-２-ヒドロキシフェニル）ベンゾトリアゾール０．０９ｇを混合し、充分に攪拌した後、５ｍｍＨｇの真空下で６０分脱気を行った。その後、ガラス型とガスケットよりなるモールド型中に注入し、４０℃で７時間保持し、その後４０℃から１２０℃まで１０時間かけて昇温する加熱炉中で重合を行い、冷却後、ガラス型とガスケットを除去し、含硫ウレタン系樹脂レンズを得た。
【０１０４】
得られたレンズは屈折率１．６６、アッベ数３３であった。
【０１０５】
（３）硬化被膜の形成
上記方法で作製した含硫ウレタン系樹脂レンズを５重量％濃度の水酸化ナトリウム水溶液中に５分間浸漬し、洗浄・乾燥した後、（１）で調整したコーティング液を用い、スピンコート法による塗布を行った。スピンコートの条件は、低回転中にハードコート液を塗布した後、回転数：２５００ｒｐｍ、回転時間：１秒で振り切りを行った。塗布後、１２０℃で３０分仮焼成し冷却後、残りの面に同様の条件で塗布し、１２０℃で３時間加熱・硬化を行い、硬化被膜を設けた。得られた被膜の膜厚は２．３μｍであった。
【０１０６】
尚、市販のプラスチックレンズ用染色剤（セイコープラックス用アンバーＤ）を用いて９０℃の染色浴で３分間生地染色を行ったものについて同様の被膜を設けた。被膜形成前後の透過率を分光光度計（大塚電子（株）製、ＭＣＰＤ−１０００）を用いて測定し色差を求めたところΔＥabは０．５であり見た目でも大きな色調変化は感じられなかった。
【０１０７】
（４）反射防止膜の形成
上記の方法で、形成した硬化膜を有するレンズを真空中２００Ｗの出力のアルゴンガスプラズマ中に３０秒間暴露させた後、真空蒸着法により、レンズ側から大気側へ向かってＳｉＯ₂、ＺｒＯ₂、ＳｉＯ₂、ＺｒＯ₂、ＳｉＯ₂の５層の薄膜を形成した。形成された反射防止膜の光学的膜厚は、順にＳｉＯ₂が、約λ／４、次のＺｒＯ₂とＳｉＯ₂の合計膜厚が、約λ／４、次のＺｒＯ₂が、約λ／４、そして最上層のＳｉＯ₂が約λ／４である（設計波長λは５１０ｎｍ）。
【０１０８】
以上の実施例１〜４、比較例１、２により得られた合成樹脂製レンズについて次の性能評価試験を行った。
【０１０９】
（ａ）耐擦傷性：#００００スチールウールにより荷重１kg／cm²で１０往復させた後の被膜の状態を次のように評価した。
【０１１０】
◎：ほとんど傷がつかない、 ○：少し傷がつく、×：多く傷がつく。
【０１１１】
（ｂ）密着性：ＪＩＳＤ−０２０２に準じてクロスカットテープ試験によって評価した。すなわち、ナイフを用いて基材表面に縦横に１ｍｍ間隔に切れ目を入れ、１平方ｍｍのマス目を１００個形成する。次に、その上へセロファン粘着テープ（ニチバン（株）製、商品名「セロテープ」）を強く押しつけ、表面から９０度方向に急に強く引張って剥離した後に、基材に残っているマス目の数を見た。
【０１１２】
（ｃ）耐温水性：６０℃の温水に１．５時間浸漬した後も表面状態の変化のないものを良とした。
【０１１３】
（ｄ）耐久性：耐久性は本質的に密着性の持続であるとの考えから、（ｃ）、（ｅ）、（ｆ）の試験を行った後に、（ｂ）の試験を行い、評価結果に変化のないものを良とした。
【０１１４】
（ｅ）耐候性：キセノンロングライフフェードメーター（スガ試験機（株）製）を用い、１５０時間暴露した後、以下の評価を行った。 ｉ）外観：染色を施さないレンズ（白レンズ）の着色の有無を肉眼で評価した。ii）透過率：試験後、分光光度計で染色を施さないレンズ（白レンズ）の可視光の平均透過率を測定した。 iii）密着性：試験後のレンズについて、前記と同様のクロスカット・テープ試験を暴露面について行った。
【０１１５】
（ｆ）耐熱性：７０℃の温風中に１時間さらし、さらに−５℃で１５分、６０℃で１５分のサイクルを５回繰り返した後も表面状態に変化のないものを良とした。
【０１１６】
（ｇ）耐衝撃性：ＦＤＡ規格に基づき、中心厚１．０ｍｍのレンズに、１２７ｃｍ上方より鋼球（直径１５．９ｍｍ、重量１６．３ｇ）を落下させ、ＦＤＡ規格の評価基準に合格したものを良とした。
【０１１７】
（ｈ）外観：染色を施さないレンズ（白レンズ）の着色の有無を肉眼で評価した。
【０１１８】
結果を表３に示す。
【０１１９】
【表３】

【０１２０】
表３の結果より、密着性改善層を形成しない場合（比較例１）、密着性が悪く、そのため耐温水性、耐久性、耐光性が悪いことが認められる。また、従来の湿式法でハードコート層を形成した場合（比較例２）、密着性は良好であるものの、耐擦傷性がそれほど良くなく、耐熱性、外観もそれほど良くない。
【０１２１】
これに対して、本発明の光学製品（実施例１〜４）は、密着性改善層、屈折率調整層を設け、さらに、ハードコート層を真空蒸着とプラズマＣＶＤを併用して形成しているので、耐擦傷性に非常に優れ、密着性、耐温水性、耐久性、耐熱性、耐衝撃性に優れると共に、外観にも優れることが認められる。
【０１２２】
【発明の効果】
本発明の光学製品は、真空蒸着法とプラズマＣＶＤ法とを併用して形成された光透過層を備えるため、この光透過層は、これらの成膜方法の長所が組み合わされ、例えば、密着性と耐擦傷性に優れたハードコート層や、生産の容易な屈折率調整層を備える。
【０１２３】
また、本発明の光学製品は、プラズマを用いない成膜方法で形成された密着性改善層を樹脂基板上に備えるため、密着性改善層の上に成膜されたプラズマを用いる成膜方法のプラズマから樹脂基板を保護し、密着性が改善されている。
【０１２４】
また、本発明の光学製品は、密着性改善層、真空蒸着法とプラズマＣＶＤ法とを併用して形成された屈折率調整層、及び真空蒸着法とプラズマＣＶＤ法とを併用して形成されたハードコート層を有するので、耐擦傷性、密着性などの性能に優れている。
【０１２５】
また、本発明の光学製品の製造方法によれば、真空蒸着法とプラズマＣＶＤ法とを併用して光透過層を形成するため、これらの成膜方法の長所が組み合わされ、例えば、密着性と耐擦傷性に優れたハードコート層を形成でき、また、屈折率調整層を容易に形成することができる。
【０１２６】
また、本発明の光学製品の製造方法によれば、プラズマを用いない成膜方法で密着性改善層を樹脂基板上に形成するため、密着性改善層の上に成膜されたプラズマを用いる成膜方法のプラズマから樹脂基板を保護でき、密着性を改善することができる。
【０１２７】
さらに、本発明の光学製品の製造方法によれば、密着性改善層、屈折率調整層、ハードコート層をいずれも乾式法で成膜できるため、生産性が良好である。
【図面の簡単な説明】
【図１】実施例で用いた真空成膜装置を示す概略構成図である。
【図２】実施例１で得られた光学製品の層構造を示す概念図である。
【図３】（ａ）は実施例１で得られた光学製品の分光特性を示すグラフであり、（ｂ）は実施例４で得られた光学製品の分光特性を示すグラフである。
【符号の説明】
１０…真空成膜装置
１１…チャンバー
２０…プラズマ源
２１…アノード
２２…カソード
２３…電磁コイル
３１…第１蒸着源
３２…第２蒸着源
４０…レンズホルダー
Ｗ… 樹脂基板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical product such as a plastic lens formed by forming a light transmission layer on a resin substrate and a method for manufacturing the same.
[0002]
[Prior art]
In order to supplement the mechanical strength of the surface of an optical product such as a plastic lens for spectacles and improve the scratch resistance, a hard coat layer is widely formed.
[0003]
In general, the hard coat layer is formed by forming a coating film on a plastic lens substrate by dipping or spinning using a hard coating solution containing silicon dioxide fine particles and a silane coupling agent. It is performed by a wet method of drying and curing.
[0004]
As a method for forming a hard coat layer by a dry method, a method of forming a silicon dioxide film by a vacuum deposition method has been known for a long time. In recent years, JP-A-9-68601 and JP-A-8-190002 have proposed the formation of a hard coat layer only by a plasma CVD process using a silica-based organic metal.
[0005]
On the other hand, in recent years, plastic lens substrates have increased in refractive index, and recently, high refractive index lenses exceeding 1.7 have been developed. If the resin substrate and the hard coat layer have different refractive indexes, there is a problem that interference fringes are generated due to the difference in refractive index.
[0006]
Therefore, in the wet method, the hard coat liquid is adjusted so that the refractive index of the hard coat layer is equal to the refractive index of the substrate.
[0007]
Further, in the dry method, in order to adjust the refractive index difference between the hard coat layer composed of a silicon dioxide film having a refractive index of 1.44 to 1.48 and the plastic lens substrate, Japanese Patent Laid-Open No. 9-68601, In JP-A-8-190002, the refractive index changes sequentially between the plastic lens substrate and the hard coat layer in the thickness direction, and is substantially equal to the refractive index of the substrate on the substrate side, and the refractive index of the hard coat on the hard coat side. It has been proposed to form a refractive index adjusting layer having substantially the same refractive index by plasma CVD. In these publications, in order to increase the refractive index of the refractive index adjusting layer, plasma CVD is performed using an organic metal for high refractive index containing Ti or an organic metal for high refractive index containing Zr and Ta.
[0008]
[Problems to be solved by the invention]
However, the conventional technology described above has many problems. That is, the method of forming the hard coat layer by the wet method adjusts the hard coat solution so that the refractive index after curing is equal to the refractive index of the substrate. On the other hand, it is premised that one kind of hard coat liquid is prepared, and there is a problem that efficiency is poor.
[0009]
In addition, a large amount of equipment is required to apply and dry a hard coat solution on a plastic lens substrate using dipping or spin coating, which increases the manufacturing cost. Moreover, since organic solvents are used, the organic solvent evaporates, and the hard coat liquid has a pot life, and the hard coat liquid that has passed the pot life must be completely replaced. There is a problem that comes out a lot. Furthermore, since it hardens | cures by heating, there exists a problem of consuming energy and going against energy saving in recent years.
[0010]
On the other hand, in the formation of the hard coat layer by the dry method, there is no problem with the wet method, but there is another problem. That is, the silicon dioxide film formed by the vacuum evaporation method shows excellent scratch resistance from a film thickness of about 1 μm, but if it exceeds 1 μm, the adhesion with the resin substrate is lowered due to the compressive stress of the silicon dioxide film, Therefore, there is a problem that the scratch resistance cannot be satisfied, and it is hardly used at present.
[0011]
In addition, in the method of forming a silicon dioxide film as a hard coat layer by a plasma CVD method using a silica-based organic metal, the inventor's experiment has shown that when an attempt is made to ensure comprehensive durability, the obtained hard coat layer It has been recognized that the scratch resistance is substantially equivalent to that of a hard coat layer obtained by a general wet method.
[0012]
Thus, with the conventional dry method, it is difficult to form a high-quality hard coat layer that achieves both adhesion and scratch resistance.
[0013]
In addition, the plasma CVD method using an organic metal for high refractive index including Ti, Zr, Ta and the like proposed in Japanese Patent Laid-Open Nos. 9-68601 and 8-190002 has a high boiling point, and is hydrolyzed. It is very difficult to handle such as being easily precipitated, toxic and ignitable, and in particular, since these organic metals having high hydrolyzability are used, it is difficult to produce stably in actual production.
[0014]
Furthermore, the refractive index adjusting layer formed by plasma CVD proposed in Japanese Patent Application Laid-Open Nos. 9-68601 and 8-190002 has a problem that the moisture resistance and light resistance are not good.
[0015]
The present invention has been made in view of the above circumstances. First, by a dry method that does not have the problems of the wet method as described above, a hard coat layer that achieves both adhesion and scratch resistance, and an organic metal that is difficult to handle. An object of the present invention is to provide an optical product having a light-transmitting layer such as a refractive index adjusting layer that can be stably formed without using a glass.
[0016]
Secondly, an object of the present invention is to provide an optical product having a light transmission layer such as a refractive index adjusting layer with improved moisture resistance and light resistance on a resin substrate.
[0017]
Thirdly, the present invention is an optical product that can form a hard coat layer having both adhesion and scratch resistance by a dry method, and can stably form a refractive index adjustment layer without using a difficult organic metal. An object is to provide a manufacturing method.
[0018]
Fourthly, an object of the present invention is to provide a method for producing an optical product, in which a light transmission layer such as a refractive index adjusting layer having improved moisture resistance and light resistance can be formed on a resin substrate.
[0019]
[Means for Solving the Problems]
As a result of intensive studies in order to achieve the above object, the present inventor formed a light transmission layer by using a vacuum vapor deposition method and a chemical vapor deposition method using plasma (hereinafter referred to as a plasma CVD method) in combination. I found it effective.
[0020]
That is, the silicon dioxide film formed by using both the vacuum deposition method and the plasma CVD method is a relatively flexible silicon dioxide rich in organic groups formed by the plasma CVD method on the hard silicon dioxide film formed by the vacuum deposition method. Since the films are mixed, the compressive stress of the silicon dioxide film formed by the vacuum deposition method can be reduced, and the film can be given flexibility. Therefore, the adhesion is excellent, and the silicon dioxide film formed by the vacuum deposition method has a sufficient adhesion even as a thick film of about 4 μm, whereas the adhesion is reduced by compressive stress at about 1 μm. Moreover, it is harder than the silicon dioxide film formed only by the plasma CVD method. Therefore, it is possible to form a silicon dioxide film having both adhesion and scratch resistance, that is, a hard coat layer.
[0021]
In addition, when forming a high refractive index layer such as a refractive index adjusting layer, a deposition material for forming the high refractive index layer is deposited by a vacuum deposition method, and a low refractive index layer is formed by a plasma CVD method. Since it is not necessary to use an organic metal for high refractive index, which is very difficult to handle in the plasma CVD method, stable production is possible.
[0022]
Furthermore, if the deposition is performed using the plasma CVD method, the surface of the resin substrate is damaged by the plasma, so that the adhesion between the deposited film by the plasma CVD method and the resin substrate is lowered, and the deposition is performed due to the lowering of the adhesion. It was found that the moisture resistance and light resistance of the film had deteriorated. Therefore, before plasma CVD, an adhesion improving layer is provided on the surface of the resin substrate by a film-forming method that does not use plasma, such as vacuum deposition, and the substrate surface is protected so that the substrate surface is not damaged by the plasma. It has been found that the adhesion between the deposited film formed by CVD and the resin substrate is improved, and the moisture resistance and light resistance are improved.
[0023]
From these examinations, on the resin substrate, the above-mentioned adhesion improving layer, the refractive index adjusting layer formed by using the vacuum deposition method and the plasma CVD method in combination, and the vacuum deposition method and the plasma CVD method were used in combination. By providing a hard coat layer and further an antireflection layer, it becomes an optical product excellent in moisture resistance, light resistance, adhesion, scratch resistance, etc., and since all can be formed by a dry method, productivity should be good. I found out.
[0024]
  Therefore, the invention described in claim 1 includes a resin substrate and a hybrid light transmission layer formed on the resin substrate by using a vacuum vapor deposition method and a chemical vapor deposition method using plasma in combination.As a thin film material in the vacuum deposition method, SiO ₂ , SiO, ZrO ₂ TiO ₂ , TiO, Ti ₂ O _Three , Ti ₂ O _Five , Al ₂ O _Three , Ta ₂ O _Five , CeO ₂ , MgO, Y ₂ O _Three , SnO ₂ , MgF ₂ , WO _Three One or two or more inorganic substances selected from Cr are used, and Si-based organometallic is used as a raw material in the chemical vapor deposition method using plasma.An optical product is provided.
[0025]
A second aspect of the present invention provides the optical product according to the first aspect, wherein the hybrid light transmitting layer is a hard coat layer mainly composed of silicon dioxide.
[0026]
According to a third aspect of the present invention, in the optical product according to the first or second aspect, the hybrid light transmission layer is interposed between the resin substrate and the hard coat layer, and the hard coat is formed from the resin substrate in the thickness direction. An optical product is provided which is a refractive index adjusting layer having a refractive index which changes stepwise or continuously to the refractive index of the layer.
[0027]
  The invention according to claim 4In the optical product according to claim 2 or 3, between the resin substrate and the hybrid light transmission layer,Improvement of adhesion formed by film-forming method without using plasmaLayerAn optical product is provided.
[0029]
  Claim5The described invention is claimed.4The optical product described above is provided with an antireflection layer on the hard coat layer.
[0030]
  Claim6The described invention relates to an optical product having a combined film forming step of forming a hybrid light transmission layer on a resin substrate by using a vacuum vapor deposition method and a chemical vapor deposition method using plasma in a single chamber. In the manufacturing method,As a thin film material in the vacuum deposition method, SiO ₂ , SiO, ZrO ₂ TiO ₂ , TiO, Ti ₂ O _Three , Ti ₂ O _Five , Al ₂ O _Three , Ta ₂ O _Five , CeO ₂ , MgO, Y ₂ O _Three , SnO ₂ , MgF ₂ , WO _Three One or two or more inorganic substances selected from Cr are used, and Si-based organometallic is used as a raw material in the chemical vapor deposition method using plasma.An optical product manufacturing method is provided.
[0031]
  Claim7The described invention is claimed.6In the optical product manufacturing method described above, the combined film forming step is a hard coat film forming step of forming a hard coat layer mainly composed of silicon dioxide. .
[0032]
  Claim8The described invention is claimed.6Or7In the manufacturing method of the optical product according to the above, the combined film-forming step changes the refractive index stepwise or continuously from the refractive index of the resin substrate to the predetermined refractive index in the thickness direction on the resin substrate. Provided is a method for manufacturing an optical product, which is a film forming step of a refractive index adjusting layer.
[0033]
  The invention according to claim 9In the manufacturing method of the optical product according to claim 7 or 8, before the combined film forming step,Adhesion improving layer film forming process for forming an adhesion improving layer on the resin substrate by a film forming method that does not use plasma.AboutA method for producing an optical product is provided.
[0035]
  Claim10The described invention is claimed.9The method for manufacturing an optical product according to the above-described method includes the step of forming an antireflection layer for forming an antireflection layer on the hard coat layer.
[0036]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.
[0037]
As described above, the optical product of the present invention has a resin substrate and a hybrid light transmission layer formed on the resin substrate by using both the vacuum vapor deposition method and the plasma CVD method.
[0038]
Examples of the resin substrate include a resin substrate used as a base material for plastic optical products such as eyeglass plastic lenses, optical plastic lenses, antireflection films, and vehicle windows. There is no restriction | limiting in the kind and shape of the material of a resin substrate.
[0039]
The vacuum evaporation method is a method in which a thin film material is heated and evaporated in a high vacuum, and the evaporated particles are deposited on a resin substrate to form a thin film. Thin film material heating methods include resistance heating, electron beam heating, and arc heating. In the vacuum deposition method for the resin substrate, the inorganic material that can be used is limited due to the heat resistance of the resin substrate.₂, SiO, ZrO₂TiO₂, TiO, Ti₂O_Three, Ti₂O_Five, Al₂O_Three, Ta₂O_Five, CeO₂, MgO, Y₂O_Three, SnO₂, MgF₂, WO_ThreeCr and the like can be exemplified, and these inorganic substances can be used alone or in admixture of two or more. Especially for resin substrates, the deposition temperature can be lowered SiO, SiO₂, ZrO₂TiO₂, Ti_ThreeO_FiveCr can be preferably used.
[0040]
In the plasma CVD method, a raw material gas is chemically activated by plasma discharge under reduced pressure, and a film is deposited by a chemical reaction that is difficult by normal thermal excitation. Electrons and gas molecules accelerated by the electric field collide inelastically, and the molecules are ionized, dissociated or excited to form chemically active species. Since it is a non-equilibrium reaction, films having various compositions can be deposited at a considerably lower temperature than the thermal CVD method and are suitable for forming a resin substrate having low heat resistance. A high frequency is often used to generate plasma, but there is also a method of applying a DC voltage. In addition, plasma generated using a magnetic field is diffused.
[0041]
In the present invention, the plasma CVD method is used in combination with the vacuum vapor deposition method to form a hybrid light transmission layer. Therefore, the vacuum vapor deposition method can be provided with a deposition material that gives a high refractive index. Si-based organometallic that can be stably produced can be used. This eliminates the need for using an organic metal for high refractive index containing Ti, Zr, Ta, etc., which is very difficult to handle.
[0042]
Examples of the Si-based organic metal include tetramethyldisilazane, tetramethoxysilane, tetraethoxysilane, tetramethylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, ethyltrimethylsilane, allyltrimethylsilane, isopropoxytrimethylsilane, methyltrivinylsilane, hexamethyldisiloxane, hexamethyldisilane, 1,3-dimethoxy Tetramethyldisiloxane, dimethyltrimethylsilylamine, acetoxymethyltrimethylsilane, allyldimethylsilane, bis (dimethylamino) methylsilane , T-ethoxytrimethylsilane, divinyldimethylsilane, hexamethylcyclotrisiloxane, hexamethyldisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, trimethylsilyl isocyanate, vinyl-t-butyldimethylsilane Etc.
[0043]
Although it does not restrict | limit especially as a hybrid light transmission layer formed combining the vacuum evaporation method and plasma CVD method in this invention, A silicon dioxide film (hard-coat layer) and a refractive index adjustment layer can be illustrated.
[0044]
In the formation of the hard coat layer, silicon dioxide is heated and evaporated as a deposition material by vacuum deposition, and silicon dioxide is deposited directly on the surface of the resin substrate. At the same time, Si-based organic metal is used as a source gas by plasma CVD. Silicon dioxide is deposited on the surface of the resin substrate by decomposition of itself or reaction with oxygen.
[0045]
The silicon dioxide film obtained by vacuum deposition is good quality, very hard, and exhibits excellent scratch resistance from about 1 μm thickness, but due to the compressive stress, the film becomes thicker than 1 μm, resulting in poor adhesion. Scratch resistance cannot satisfy market quality. On the other hand, the silicon dioxide film obtained by the plasma CVD method is flexible and has low compressive stress because it contains an organic group in the film, but it is relatively soft and inferior in scratch resistance. It shows the same level of scratch resistance as a hard coat film obtained by a wet method.
[0046]
In the present invention, since the vacuum deposition method and the plasma CVD method are used in combination, the resulting silicon dioxide film is a mixture of the one by vacuum deposition and the one by plasma CVD. Therefore, the obtained silicon dioxide film is harder than the silicon dioxide film obtained by the plasma CVD method, and the effect and flexibility of reducing the compressive stress by the plasma CVD method on the hard silicon dioxide film obtained by the vacuum deposition method. Is given. As a result, even if the film thickness is increased to 4 μm, the adhesion does not decrease, and in addition to this, it is hard, and thus exhibits excellent scratch resistance. The silicon dioxide film having a thickness of 4 μm by the combined method of the present invention has much better scratch resistance than the silicon dioxide film by vacuum deposition having a thickness of 1 μm and the silicon dioxide film obtained by a wet method having a thickness of 4 μm or a plasma CVD method.
[0047]
In addition, the combined use of the vacuum deposition method and the plasma CVD method can improve the film formation rate and improve the productivity.
[0048]
On the other hand, the refractive index adjusting layer is interposed between the resin substrate and the hard coat layer, and has the same refractive index as that of the resin substrate on the resin substrate side and substantially the same refractive index as that of the hard coat layer on the hard coat layer side. And a layer having a gradient function having a refractive index that changes stepwise or continuously in the thickness direction.
[0049]
By interposing this refractive index adjusting layer as a buffer zone between the resin substrate and the hard coat layer, it is possible to prevent the generation of interference fringes and obtain an optical product having an excellent appearance. Further, even if the refractive index of the resin substrate changes, it is possible to cope with the change in the refractive index of the resin substrate by increasing the refractive index on the resin substrate side of the refractive index adjustment layer. It can be applied to resin substrates of any refractive index simply by changing the conditions. Further, by interposing the refractive index adjusting layer, the optical condition of the hard coat layer, in other words, the manufacturing conditions can be made constant regardless of the refractive index of the resin substrate, and the hard coat layer can be easily manufactured. . Furthermore, since the antireflection layer formed on the hard coat layer can be formed under the same conditions regardless of the substrate refractive index, if the optical conditions of the hard coat layer are constant, There is also an effect that manufacture becomes easy.
[0050]
In recent years, as the refractive index of plastic lenses exceeds 1.7, the refractive index adjustment layer on the resin substrate side needs to have a higher refractive index, and the refractive index of the hard coat layer (1 The step can be arbitrarily adjusted between 44 and 1.48).
[0051]
When the refractive index adjustment layer is formed by using the vacuum deposition method and the plasma CVD method of the present invention together, in vacuum deposition, TiO₂, ZrO₂, Ti_ThreeO_FiveIn the plasma CVD, for example, Si-based organic metal is used as a raw material gas to deposit a high-refractive material directly on the resin substrate surface by heating and evaporating the vapor-deposited material. Silicon dioxide having a low refractive index is deposited on the surface of the resin substrate by decomposition of the metal itself or reaction with oxygen. The refractive index of the obtained film can be adjusted by changing the film formation ratio of these high refractive index vapor deposition material and low refractive index deposited film. That is, when starting the film formation on the resin substrate, a film having a refractive index substantially the same as the refractive index of the resin substrate is formed, and then the refractive index is changed continuously or stepwise, and finally the hard coat layer is almost the same. The film formation amounts of the high refractive material and the low refractive material are selected so as to have the same refractive index. The refractive index can be arbitrarily adjusted by changing the flow rate of the Si-based organometallic vapor and the deposition rate of the vapor deposition material.
[0052]
By using such a vacuum deposition method and a plasma CVD method in combination, a high refractive index deposition material is formed by the vacuum deposition method, and a low refractive index film is formed by the plasma CVD method. Ti, Zr, Ta, etc., which are difficult to handle because they are likely to precipitate due to decomposition, are toxic and ignitable, and are particularly difficult to use stably in actual plasma CVD if they are highly hydrolyzable. It is not necessary to use the high refractive index organic metal contained in the plasma CVD method. Thereby, stable production can be easily achieved.
[0053]
In addition, when a film is formed on a resin substrate using the plasma CVD method, the resin substrate, particularly a high refractive index or ultrahigh refractive index material, is damaged by the plasma. Adhesion with the substrate is deteriorated, and deterioration of adhesion causes a problem that the moisture resistance and light resistance of the film are deteriorated. In the present invention, when the refractive index adjustment layer is formed, since the plasma CVD method and the vacuum deposition method are used in combination, the resin substrate may be damaged by the plasma.
[0054]
Therefore, in the present invention, it is preferable to form the adhesion improving layer on the resin substrate by a film forming method that does not use plasma, for example, a vacuum evaporation method, before the film is deposited on the resin substrate using the plasma CVD method. As a result, the resin substrate is protected and prevented from being damaged by plasma by plasma CVD, the adhesion of the film formed by the plasma CVD method can be improved, and the moisture resistance and weather resistance of the film can be improved. .
[0055]
The adhesion improving layer is selected from the standpoint that the resin substrate can be protected from plasma even if it is thinly formed so as not to affect optically, and the adhesion to the resin substrate is good. The physical film thickness is about 20 to 15 nm at maximum, and the optical film thickness (refractive index × film thickness) is about 33 nm at maximum. As the kind of adhesion improving layer, Al₂O_Three(Refractive index = 1.64, maximum film thickness = 20 nm), SiO (refractive index = 1.9, maximum film thickness = 15 nm), Cr₂O_Three(Refractive index = 2.2, maximum film thickness = 15 nm) can be exemplified.
[0056]
Next, FIG. 1 shows an embodiment of a film forming apparatus that operates vacuum deposition and plasma CVD at the same time. FIG. 1 shows a vacuum film forming apparatus for forming a film by using both a vacuum vapor deposition method and a plasma CVD method in one chamber.
[0057]
In this film forming apparatus 10, one plasma source and two vapor deposition sources are arranged in a chamber 11 that can be evacuated by a roots pump and an oil diffusion pump, and shutters (not shown) that can be opened and closed are arranged respectively. The plasma source 20 is an end-hole type having no grid, and a cathode 22 is coaxially arranged in a cylindrical anode 21. A gap between these electrodes is an argon gas introduction path. In addition, an electromagnetic coil 23 is disposed on the outer peripheral surface of the tip of the anode 21 so that the plasma generated by the direct current between the anode 21 and the cathode 22 is diffused by the magnetic field of the electromagnetic coil 23 so that the plasma intensity becomes uniform. It has become.
[0058]
The plasma CVD source gas can be introduced into the chamber 11 at a predetermined flow rate through a pipe heated from a container (not shown) outside the chamber 11. In addition, oxygen gas for decomposition of the source gas can be introduced into the chamber 11.
[0059]
The positions of the two first vapor deposition sources 31 and the second vapor deposition sources 32 can be changed by rotating a plurality of crucibles on the support bases 311 and 321 that are rotatably supported, each called a hearth, as the support bases rotate. Are arranged as follows. FIG. 1 shows an example in which two crucibles 312 and 313 are arranged in the first vapor deposition source 31 and two crucibles 322 and 323 are arranged in the second vapor deposition source 32. Each crucible can contain different deposition materials, and in FIG. 1, four kinds of deposition materials can be placed. The support tables 311 and 321 are rotated by motors 314 and 324, respectively, and an arbitrary crucible is brought close to the electron guns 315 and 325 disposed adjacent to the support tables, and vapor deposition is heated by the electron guns 315 and 325. Substances can be exchanged. In this apparatus, electron beams 316 and 326 emitted from electron guns 315 and 325 are used as means for heating the vapor deposition material in the crucible. By heating the vapor deposition material in the vicinity of the electron guns 315 and 325 with the electron beams 316 and 326, the vapor deposition material is heated to the melting point or more to evaporate, and the evaporated particles fly upward. .
[0060]
Above the chamber 11, a dome-shaped lens holder 40 that holds a plurality of resin substrates W is rotatably arranged by a motor 50. The resin substrate W is held with the film formation surface exposed on the inner surface of the lens holder 40 being the lower surface side.
[0061]
The film forming apparatus 10 can perform film formation by simultaneously operating vacuum deposition and plasma CVD, and can operate only vacuum deposition by opening / closing a shutter, or can operate only plasma CVD. Yes.
[0062]
Using such a film forming apparatus 10, only vacuum deposition is performed on the resin substrate, or plasma CVD and vacuum deposition are used together, and the above-described adhesion improving layer, refractive index adjusting layer, hard coat layer, and antireflection are formed on the resin substrate. A method for forming the layer will be described.
[0063]
First, different vapor deposition materials are put in the crucibles of the two vapor deposition sources 31 and 32, respectively. For example, the crucible 312 of the first vapor deposition source 31 is SiO for forming an adhesion improving layer, and the crucible 313 is SiO for forming a hard coat film and an antireflection film.₂Ti for forming a refractive index adjustment layer in the crucible 322 of the second vapor deposition source 32_ThreeO_Five,The crucible 323 has a ZrO film for forming an antireflection film.₂Insert. Then, the resin substrate W is set in the lens holder 40 and carried into the chamber 11.
[0064]
First, an adhesion improving layer film forming step is performed. After the inside of the chamber 11 is evacuated, the shutter of the plasma source 20 is closed, and the lens holder 40 is rotated by the motor 50 and SiO is evaporated by the electron gun 315 of the first evaporation source 31 to form an adhesion improving layer. .
[0065]
Next, a refractive index adjusting layer film forming step is performed. A DC voltage is applied between the anode 21 and the cathode 22 while flowing an argon gas with the shutter closed, and a bias voltage is also applied between the anode 21 and the lens holder 40 to the plasma source 20. Plasma is generated between them. Further, a current is passed through the electromagnetic coil 23. Si-based organic metal is introduced into the chamber 11 as a source gas. On the other hand, with the shutter of the second evaporation source 32 closed, the electron gun 325_ThreeO_FiveKeep heated. Then, with the conditions such as the plasma source 20, the Si-based organometallic flow rate, the electron gun conditions, and the like being met, the respective shutters are opened and film formation is started. The Si-based organometallic flow rate, electron gun conditions, etc. are adjusted so that the refractive index of the film at the start of film formation is approximately equal to that of the resin substrate. While adjusting the voltage or the like, a multilayer film having a refractive index that gradually decreases is formed, and the film formation is continued until the refractive index is substantially equal to the refractive index of the hard coat layer. When a layer having a predetermined refractive index is obtained, the shutter for the plasma source 20 and the shutter for the second evaporation source 32 are closed.
[0066]
Next, a hard coat layer film forming step is performed. With the shutter to the plasma source 20 and the shutters of the deposition sources 31 and 32 closed, the Si gun metal 315 of the first deposition source 31 introduces SiO while introducing Si-based organic metal as a source gas.₂Are heated, and the respective shutters are opened with the conditions such as the plasma source, the Si-based organometallic flow rate, the electron gun conditions, etc., and film formation is started. After the hard coat layer having a predetermined thickness is formed, the shutter for the plasma source 20 and the shutter for the first vapor deposition source 31 are closed, and the introduction of the Si-based organic metal is stopped.
[0067]
Next, an antireflection layer film forming step is performed. With the shutter for the plasma source 20 and the shutters of the vapor deposition sources 31 and 32 closed, the electron gun 315 of the first vapor deposition source 31 is used for SiO 2₂And ZrO with the electron gun 325 of the second evaporation source 32₂Is heated, one of the shutters is opened, and any one of the deposition materials is deposited, and these deposition materials are alternately deposited. Note that the shutter of the plasma source 20 is opened and plasma is irradiated, but no source gas is introduced.
[0068]
In this way, the adhesion improving layer, the refractive index adjusting layer, the hard coat layer, and the antireflection layer can be continuously formed in one chamber 11 while switching the source gas and the evaporation source, and the productivity is extremely good. It is.
[0069]
Note that although a series of film forming steps is performed in one chamber, a plurality of chambers may be used to perform each film forming step or a plurality of film forming steps.
[0070]
FIG. 2 shows an example of the layer structure of the optical product of the present invention in which the above-described adhesion improving layer, refractive index adjusting layer, hard coat layer, and antireflection layer are laminated on a resin substrate. The optical product shown in FIG. 2 is obtained in Example 1 described later.
[0071]
In this optical product, an adhesion improving layer made of SiO having a refractive index of 1.9 formed by a vacuum deposition method is laminated on a resin substrate having a refractive index of 1.67 with a thickness of 7 nm. Yes. On the adhesion improving layer, a refractive index adjusting layer having a refractive index gradually decreasing in 10 steps from 0.067 to 1.46 in 10 steps is laminated with a film thickness of 500 nm. The refractive index adjustment layer includes a plasma CVD method in which silicon dioxide for low refractive index is formed using Si-based organic metal as a raw material, and Ti for high refractive index._ThreeO_FiveIt is formed by the combined use with the vacuum deposition method using as a deposition material. On the refractive index adjusting layer, a hard coat layer made of silicon dioxide and having a refractive index of 1.44 is laminated with a thickness of 3000 nm. This hard coat layer is formed by a combination of a plasma CVD method using Si-based organic metal as a raw material and a vacuum vapor deposition method using silicon dioxide as an evaporation material. On the hard coat layer, ZrO with a thickness of 40 nm is sequentially formed from the hard coat layer formed by vacuum deposition.₂22.2 nm thick SiO₂67.5 nm thick ZrO₂92.5 nm thick SiO₂The antireflection layer comprised by these is laminated | stacked.
[0072]
The refractive index adjustment layer of the optical product shown in FIG. 2 has a structure that is divided into 10 layers whose refractive index changes stepwise, but there is no limit to the number of divisions, and the refractive index is steplessly refracted. It is also possible to change the rate. Since the difference in refractive index between the substrate and the hard coat layer does not appear as a ripple in the case of steplessness, good spectral characteristics can be obtained. Similarly, if the number of divisions is increased, it approaches steplessly and the spectral characteristics are improved.
[0073]
When the refractive index is changed stepwise, the refractive index change in one step is preferably 0.3 or less, particularly 0.2 or less. The film thickness in one step needs to be at least 20 nm, but it is better to make it as thin as possible. The number of divisions, the degree of change in refractive index in one step, and the film thickness are preferably determined in view of the refractive index of the substrate and the interference color quality.
[0074]
If the film thickness of the hard coat layer is ensured to be at least 1000 nm, including the effect of improving the scratch resistance of the refractive index adjusting layer, it is possible to ensure the same degree of scratch resistance as that of the hard coat layer by the wet method.
[0075]
In the optical product having such a layer structure, since the adhesion improving layer is formed on the resin substrate, the surface of the resin substrate is not damaged by plasma CVD when forming the next refractive index adjustment layer. The refractive index adjustment layer is laminated with good adhesion to the resin substrate via the adhesion improving layer, and the moisture resistance and light resistance are good. Since the adhesion improving layer is thin, the optical performance is not affected. In addition, since the refractive index adjustment layer has a multilayer structure in which the refractive index gradually decreases in the film thickness direction from a refractive index substantially equal to that of the resin substrate to a refractive index substantially equal to that of the hard coat layer, interference fringes are formed. It does not occur and the appearance quality is good. In addition, the hard coat layer is a hard, low-compression silicon dioxide film formed with sufficient film thickness by the combined use of vacuum deposition and plasma CVD. Is good and has excellent scratch resistance. Furthermore, since the antireflection layer is formed, reflection is prevented and the transmittance is good.
[0076]
【Example】
<Example 1>
The optical product shown in FIG. 2 was obtained using the vacuum film forming apparatus 10 shown in FIG. Vapor deposition materials include SiO and Ti_ThreeO_Five, SiO₂, ZrO₂4 types were used. A lens substrate (refractive index = 1.67) w previously cleaned by an ultrasonic cleaner was set in the lens holder 40. 4 × 10 with the vacuum device door closed^-FourIt exhausted with the roots pump and the oil diffusion pump to Pa. At this time, no substrate heating is performed.
[0077]
(1) Adhesion improving layer film forming step
After reaching the predetermined pressure, the adhesion improving substance SiO was deposited with an electron gun. The emission current of the electron gun was precisely controlled by a quartz film thickness meter so that the deposition rate was 0.2 nm / second. When the film thickness reached 7 nm, the shutter was closed and the deposition was completed. During the SiO deposition, no plasma irradiation was performed from the plasma source 20.
[0078]
(2) Refractive index adjustment layer film forming step
A discharge voltage of DC 100 V is applied between the anode 21 and the cathode 22 while Ar gas is supplied at a constant flow rate of 18 sccm with the shutter closed while the shutter is closed. Further, a DC 120 V bias voltage is applied between the anode 21 and the lens holder 40. Was applied. This generated plasma between the electrodes. A current of 3 A was passed through the electromagnetic coil 23 to diffuse the plasma. As the Si-based organic metal, 1,1,3,3-tetramethyldisilazane (hereinafter referred to as TMDS) was used. The glass container filled with TMDS is separated from the vacuum chamber 11 by a valve, and the inside of the glass container is depressurized by opening the valve, and further stable by heating the gas introduction piping system to the vacuum chamber to 40-60 ° C. Thus, the source gas can be introduced into the vacuum chamber 11. At this time, the flow rate of the source gas was set to 150 sccm. Deposition material Ti_Three0_FiveIs heated with an electron gun and the shutter is closed. Ti_ThreeO_FiveThe electron gun conditions were set so that the film deposition rate was 0.3 nm / second.
[0079]
Plasma source, TMDS gas, Ti_ThreeO_FiveWith all of the electron gun conditions in place, the shutter was opened at once, and film deposition started. The film deposition rate at this time was controlled at 1 nm / second. The refractive index at the start of film formation of the refractive index adjusting layer is 1.67 which is substantially equal to the substrate. The film attachment in this state was maintained, and a film thickness of 50 nm was formed with a crystal film thickness meter to form a first layer.
[0080]
When the film thickness of the first layer reached 50 nm, the flow rate of TMDS was increased to 200 sccm, and at the same time, the bias voltage of the plasma source 20 was decreased to 114V. This condition was maintained until the film thickness reached 100 nm, and the second layer was formed.
[0081]
When the film thickness reaches 100 nm, the TMDS flow rate is increased to 250 sccm, and at the same time, the bias voltage of the plasma source 20 is lowered to 108 V, and this condition is maintained until the film thickness reaches 150 nm. Formed.
[0082]
When the film thickness reached 150 nm, the TMDS flow rate was increased to 300 sccm, and at the same time, the bias voltage of the plasma source 20 was lowered, and this condition was maintained until the film thickness reached 200 nm, thereby forming the fourth layer. .
[0083]
When the film thickness reaches 200 nm, the TMDS flow rate is increased to 350 sccm, and at the same time, the bias voltage of the plasma source 20 is decreased to 96 V, and this condition is maintained until the film thickness reaches 250 nm to form the fifth layer. did.
[0084]
When the film thickness reaches 250 nm, the TMDS flow rate is increased to 400 sccm. At the same time, the bias voltage of the plasma source 20 is lowered to 90 V, and this condition is maintained until the film thickness reaches 300 nm. Formed.
[0085]
When the film thickness reaches 300 nm, the TMDS flow rate is increased to 450 sccm, and at the same time, the bias voltage of the plasma source 20 is lowered to 84 V, and this condition is maintained until the film thickness reaches 350 nm. Formed.
[0086]
When the film thickness reaches 350 nm, the TMDS flow rate is increased to 500 sccm, and at the same time, the bias voltage of the plasma source 20 is lowered to 78 V, and this condition is maintained until the film thickness reaches 400 nm to form the eighth layer. did.
[0087]
When the film thickness reaches 400 nm, the TMDS flow rate is increased to 550 sccm, and at the same time, the bias voltage of the plasma source 20 is lowered to 72 V, and this condition is maintained until the film thickness reaches 450 nm to form the ninth layer. did.
[0088]
When the film thickness reaches 450 nm, the flow rate of TMDS is increased to 600 sccm, and at the same time, the bias voltage of the plasma source 20 is lowered to 66 V. When the film thickness reaches 500 nm, the shutter is closed and the tenth layer is formed. Then, the film formation of the refractive index adjustment layer was completed.
[0089]
In each step, the flow rate conditions of the plasma source and TMDS were set so that the refractive index was decreased by 0.023 at a film thickness of 50 nm. The surface refractive index at this point is approximately 1.46.
[0090]
(3) Hard coat layer deposition process
The flow rate of TMDS was set to 300 sccm, and the plasma source 20 was set to the same conditions as the refractive index adjustment layer except that the bias voltage was set to 60V. In addition, SiO₂Were vapor-deposited simultaneously, and the total film deposition rate was controlled at 3 nm / second to provide a hard coat layer up to a thickness of 3000 nm. Under this condition, the refractive index of the hard coat layer is set to 1.44.
[0091]
(4) Antireflection layer deposition process
An antireflection film having the conditions shown in Table 1 is formed on the hard coat layer by SiO.₂(Refractive index = 1.46) and ZrO₂(Refractive index = 2.0) was alternately deposited. During the formation of the antireflection film, plasma was always irradiated under the same conditions as the plasma source 20 irradiated with the hard coat layer. A film was formed from the hard coat side under the conditions shown in Table 1. In the table, λ represents the design wavelength of 520 nm.
[0092]
[Table 1]

[0093]
The spectral characteristics of the plastic lens obtained in Example 1 are shown in FIG.
[0094]
<Example 2>
The material of the adhesion improving layer is Cr₂O_ThreeExcept for the above, in the same manner as in Example 1, the same vacuum film forming apparatus was used to form an adhesion improving layer, a refractive index adjusting layer, a hard coat layer, and an antireflection layer on the same substrate.
[0095]
The spectral characteristics of the plastic lens obtained in Example 2 were almost the same as in Example 1.
[0096]
<Example 3>
The material of the adhesion improving layer is Al.₂O_ThreeExcept for the above, in the same manner as in Example 1, the same vacuum film forming apparatus was used to form an adhesion improving layer, a refractive index adjusting layer, a hard coat layer, and an antireflection layer on the same substrate.
[0097]
The spectral characteristics of the plastic lens obtained in Example 2 were almost the same as in Example 1.
[0098]
<Example 4>
Except for changing the antireflection layer as shown in Table 2, the same vacuum film forming apparatus was used as in Example 1, and the adhesion improving layer, the refractive index adjustment layer, the hard coat layer, and the antireflection layer were applied to the same substrate. A layer was formed.
[0099]
[Table 2]

[0100]
The spectral characteristics of the plastic lens obtained in Example 4 are shown in FIG.
[0101]
<Comparative Example 1>
Except that the adhesion improving layer was not formed in Example 1, the refractive index adjustment layer, the hard coat layer, and the antireflection layer were formed on the same substrate using the same vacuum film forming apparatus 10 as in Example 1. .
[0102]
<Comparative Example 2>
(1) Preparation of coating composition
In a flask equipped with a stirrer, 41.15 g of ethyl cellosolve, 38.44 g of γ-glycidoxypropyltrimethoxysilane, and 4.13 g of tetramethoxysilane were added in order, and then 0.05N aqueous hydrochloric acid 12. 90 g was added and stirred for 30 minutes. Subsequently, 0.04 g of silicon surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7604”) and methyl cellosolve dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (TiO)₂/ ZrO₂/ SiO₂= 68/17/15 (weight ratio), solid content concentration 20.5 wt%, TiO₂And ZrO₂SiO as a solid solution₂After adding 103.39 g of the composite fine particles having a fine particle structure coated with and stirring sufficiently, the mixture was allowed to stand at 0 ° C. for 24 hours to be aged to obtain a coating composition.
[0103]
(2) Fabrication of plastic lens substrate
4-mercaptomethyl-3,6-dithio-1,8-octanedithiol 87 g, m-xylylene diisocyanate 94 g, dibutyltin dilaurate 0.02 g, internal mold release agent 0.15 g, 2- (5-methyl-2-hydroxy 0.09 g of phenyl) benzotriazole was mixed and sufficiently stirred, and then deaerated under a vacuum of 5 mmHg for 60 minutes. Thereafter, it is poured into a mold composed of a glass mold and a gasket, held at 40 ° C. for 7 hours, and then polymerized in a heating furnace heated up from 40 ° C. to 120 ° C. over 10 hours. The gasket was removed to obtain a sulfur-containing urethane resin lens.
[0104]
The obtained lens had a refractive index of 1.66 and an Abbe number of 33.
[0105]
(3) Formation of cured film
The sulfur-containing urethane-based resin lens produced by the above method is immersed in a 5% by weight aqueous sodium hydroxide solution for 5 minutes, washed and dried, and then applied by spin coating using the coating solution prepared in (1). Went. The spin coating conditions were as follows: the hard coat solution was applied during low rotation, and then shaken off at a rotation speed of 2500 rpm and a rotation time of 1 second. After coating, pre-baked at 120 ° C. for 30 minutes, cooled, and coated on the remaining surface under the same conditions, and heated and cured at 120 ° C. for 3 hours to provide a cured coating. The film thickness of the obtained film was 2.3 μm.
[0106]
In addition, the same film was provided about what dye | stained cloth for 3 minutes in a 90 degreeC dyeing | staining bath using the commercially available dyeing | staining agent for plastic lenses (Amber D for Seiko Plax). When the transmittance before and after the film formation was measured using a spectrophotometer (MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.) and the color difference was determined, ΔEab was 0.5, and no significant color tone change was felt.
[0107]
(4) Formation of antireflection film
After the lens having the cured film formed by the above method is exposed in an argon gas plasma having an output of 200 W in a vacuum for 30 seconds, SiO 2 is evaporated from the lens side to the atmosphere side by vacuum deposition.₂, ZrO₂, SiO₂, ZrO₂, SiO₂A five-layer thin film was formed. The optical thickness of the formed antireflection film is in order of SiO₂Is approximately λ / 4, and the following ZrO₂And SiO₂The total film thickness is about λ / 4, and the following ZrO₂Is about λ / 4, and the uppermost SiO₂Is approximately λ / 4 (design wavelength λ is 510 nm).
[0108]
The following performance evaluation test was performed on the synthetic resin lenses obtained in Examples 1 to 4 and Comparative Examples 1 and 2.
[0109]
(A) Scratch resistance: Load of 1kg / cm with # 0000 steel wool²The state of the coating after 10 reciprocations was evaluated as follows.
[0110]
A: Almost scratched; O: Slightly scratched; X: Scratched a lot.
[0111]
(B) Adhesiveness: evaluated by a cross-cut tape test according to JISD-0202. That is, using a knife, cuts are made at intervals of 1 mm vertically and horizontally on the surface of the substrate to form 100 squares of 1 mm 2. Next, cellophane adhesive tape (made by Nichiban Co., Ltd., trade name “cello tape”) is strongly pressed onto it, and after suddenly pulling and peeling from the surface in a 90 degree direction, the cells remaining on the base material are peeled off. I saw a number.
[0112]
(C) Warm water resistance: Even when immersed in warm water at 60 ° C. for 1.5 hours, the one having no change in surface condition was regarded as good.
[0113]
(D) Durability: From the idea that durability is essentially the persistence of adhesion, the tests of (b) are conducted and evaluated after the tests of (c), (e), and (f). Those with no change in the results were considered good.
[0114]
(E) Weather resistance: The following evaluation was performed after exposure for 150 hours using a xenon long life fade meter (manufactured by Suga Test Instruments Co., Ltd.). i) Appearance: The presence or absence of coloring of a lens (white lens) that was not dyed was evaluated with the naked eye. ii) Transmittance: After the test, the average visible light transmittance of a lens (white lens) that was not stained with a spectrophotometer was measured. iii) Adhesion: The lens after the test was subjected to the same cross-cut tape test as described above on the exposed surface.
[0115]
(F) Heat resistance: after being exposed to warm air at 70 ° C. for 1 hour, and after repeating a cycle of 15 minutes at −5 ° C. for 15 minutes and 60 ° C. for 5 times, the surface state was not changed. .
[0116]
(G) Impact resistance: Based on the FDA standard, a steel ball (diameter 15.9 mm, weight 16.3 g) was dropped from above 127 cm onto a lens with a center thickness of 1.0 mm, and passed the evaluation standard of the FDA standard. Was good.
[0117]
(H) Appearance: The presence or absence of coloring of a lens (white lens) that was not dyed was evaluated with the naked eye.
[0118]
The results are shown in Table 3.
[0119]
[Table 3]

[0120]
From the results of Table 3, it can be seen that when the adhesion improving layer is not formed (Comparative Example 1), the adhesion is poor, and therefore the warm water resistance, durability and light resistance are poor. Further, when the hard coat layer is formed by a conventional wet method (Comparative Example 2), the adhesion is good, but the scratch resistance is not so good, and the heat resistance and appearance are not so good.
[0121]
On the other hand, the optical product (Examples 1 to 4) of the present invention is provided with an adhesion improving layer and a refractive index adjusting layer, and further, a hard coat layer is formed by using both vacuum deposition and plasma CVD. Therefore, it is recognized that it has excellent scratch resistance, adhesion, hot water resistance, durability, heat resistance, impact resistance and appearance.
[0122]
【The invention's effect】
Since the optical product of the present invention includes a light transmission layer formed by using both the vacuum vapor deposition method and the plasma CVD method, this light transmission layer combines the advantages of these film formation methods. And a hard coat layer with excellent scratch resistance and a refractive index adjusting layer that is easy to produce.
[0123]
Further, since the optical product of the present invention includes an adhesion improving layer formed by a film forming method that does not use plasma on a resin substrate, the optical product of the film forming method that uses plasma formed on the adhesion improving layer is used. The resin substrate is protected from plasma and the adhesion is improved.
[0124]
Moreover, the optical product of the present invention was formed by using an adhesion improving layer, a refractive index adjusting layer formed by using a vacuum deposition method and a plasma CVD method in combination, and a combination of a vacuum deposition method and a plasma CVD method. Since it has a hard coat layer, it has excellent performance such as scratch resistance and adhesion.
[0125]
Further, according to the method for producing an optical product of the present invention, the light transmission layer is formed by using both the vacuum vapor deposition method and the plasma CVD method. Therefore, the advantages of these film formation methods are combined. A hard coat layer having excellent scratch resistance can be formed, and a refractive index adjusting layer can be easily formed.
[0126]
In addition, according to the method for manufacturing an optical product of the present invention, the adhesion improving layer is formed on the resin substrate by a film forming method that does not use plasma, so that the plasma formed on the adhesion improving layer is used. The resin substrate can be protected from the plasma of the film method, and the adhesion can be improved.
[0127]
Furthermore, according to the method for producing an optical product of the present invention, the adhesion improving layer, the refractive index adjusting layer, and the hard coat layer can all be formed by a dry method, so that the productivity is good.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing a vacuum film forming apparatus used in Examples.
2 is a conceptual diagram showing a layer structure of an optical product obtained in Example 1. FIG.
3A is a graph showing the spectral characteristics of the optical product obtained in Example 1, and FIG. 3B is a graph showing the spectral characteristics of the optical product obtained in Example 4. FIG.
[Explanation of symbols]
10 ... Vacuum deposition system
11 ... Chamber
20 ... Plasma source
21 ... Anode
22 ... Cathode
23 ... Electromagnetic coil
31 ... 1st vapor deposition source
32 ... Second deposition source
40 ... Lens holder
W ... Resin substrate

Claims (10)

A resin substrate;
Have a said resin vacuum deposition method on a substrate and hybrid light transmission layer formed by combination of a chemical vapor deposition method using plasma,
Wherein the thin film material in a vacuum deposition _{method, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O ₃ , one or more inorganic substances selected from SnO ₂ , MgF ₂ , WO ₃ and Cr are used,
An optical product characterized in that Si organic metal is used as a raw material in the chemical vapor deposition method using the plasma . The optical product according to claim 1,
An optical product, wherein the hybrid light transmission layer is a hard coat layer mainly composed of silicon dioxide. The optical product according to claim 1 or 2,
The hybrid light transmission layer is interposed between the resin substrate and the hard coat layer,
An optical product comprising a refractive index adjustment layer having a refractive index that changes stepwise or continuously from the resin substrate to the refractive index of the hard coat layer in a thickness direction. The optical product according to claim 2 or 3,
Between the resin substrate and the hybrid light transmission layer,
An optical product comprising an adhesion improving layer formed by a film forming method that does not use plasma. The optical product according to claim 4 .
An optical product comprising an antireflection layer on the hard coat layer. In a manufacturing method of an optical product having a combined film forming step of forming a hybrid light transmission layer on a resin substrate by using a vacuum vapor deposition method and a chemical vapor deposition method using plasma in one chamber.
Wherein the thin film material in a vacuum deposition _{method, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O ₃ , one or more inorganic substances selected from SnO ₂ , MgF ₂ , WO ₃ and Cr are used,
A method for producing an optical product, wherein Si-based organometallic is used as a raw material in the chemical vapor deposition method using plasma . In the manufacturing method of the optical product according to claim 6 ,
The method for manufacturing an optical product, wherein the combined film formation step is a hard coat film formation step of forming a hard coat layer mainly composed of silicon dioxide. In the manufacturing method of the optical product according to claim 6 or 7 ,
The combined film forming step forms a film on the resin substrate while changing the refractive index stepwise or continuously from the refractive index of the resin substrate to a predetermined refractive index in the thickness direction. A method for producing an optical product, which is a process. In the manufacturing method of the optical product according to claim 7 or 8,
Before the combined film forming step,
Method of manufacturing an optical product characterized by having a higher adhesiveness improving layer deposition engineering for forming the adhesion improving layer by a deposition method using no plasma in the resin substrate. In the manufacturing method of the optical product according to claim 9 ,
An optical product manufacturing method comprising an antireflection layer forming step of forming an antireflection layer on the hard coat layer.

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