JP2001059902A - Reflection preventing laminated body and its manufacture - Google Patents
Reflection preventing laminated body and its manufactureInfo
- Publication number
- JP2001059902A JP2001059902A JP11235761A JP23576199A JP2001059902A JP 2001059902 A JP2001059902 A JP 2001059902A JP 11235761 A JP11235761 A JP 11235761A JP 23576199 A JP23576199 A JP 23576199A JP 2001059902 A JP2001059902 A JP 2001059902A
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- Japan
- Prior art keywords
- layer
- refractive index
- boundary
- laminate
- index layer
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は反射防止積層体に関
するもので、ガラスやプラスチックなどの透明基材など
に光干渉多層膜を塗工して、反射防止性を付与した積層
体およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-reflection laminate, and more particularly to a laminate having an anti-reflection property by applying a light interference multilayer film to a transparent substrate such as glass or plastic, and a method for producing the same. About.
【０００２】[0002]
【従来の技術】従来、ガラスやプラスチックなどの基材
に、酸化チタンや酸化ケイ素などの無機酸化物を蒸着法
あるいはスパッタ法などのドライコーティングによって
薄膜を形成して反射防止膜などの光干渉による光学多層
膜を形成する方法が知られており、その光学設計は基材
表面から順次高屈折率層／低屈折率層（光学膜厚がλ／
４−λ／４）積層した２層構成、中／高／低（λ／４−
λ／４−λ／４）の３層構成などが知られている。2. Description of the Related Art Conventionally, a thin film is formed on a base material such as glass or plastic by an inorganic oxide such as titanium oxide or silicon oxide by a dry coating such as a vapor deposition method or a sputtering method, and the thin film is formed by light interference such as an antireflection film. A method of forming an optical multilayer film is known, and the optical design thereof is performed by sequentially forming a high refractive index layer / a low refractive index layer (optical thickness is λ /
4-λ / 4) laminated two-layer structure, middle / high / low (λ / 4
(λ / 4−λ / 4) are known.
【０００３】しかし、このようなドライコーティングプ
ロセスでは装置が高価で、成膜速度が遅く、生産性が高
くないなどの課題を有している。[0003] However, such a dry coating process has problems in that the equipment is expensive, the film forming speed is slow, and the productivity is not high.
【０００４】これに対して金属アルコキシドなどを出発
組成とし、基材に塗工して光学多層膜を形成する方法が
知られており、高屈折率材料としてはＴｉやＺｒなどの
アルコキシドを用い、低屈折率材料としてはＳｉなどの
アルコキシドやＦ系のアクリル化合物などを用いる方法
が提案されている。On the other hand, there is known a method of forming an optical multilayer film by coating a base material with a metal alkoxide or the like as a starting composition, and using an alkoxide such as Ti or Zr as a high refractive index material. As a low refractive index material, a method using an alkoxide such as Si or an F-based acrylic compound has been proposed.
【０００５】しかしこれらの塗膜では、乾燥重合に高
温、長時間を必要とするため生産性に問題がある。また
ある程度の反射防止膜を得ることはできるが、硬度や耐
擦傷性、基材との密着性などの物理的強度が不十分であ
り、光学多層膜は最外層に使用されるため、強度が不十
分では実用に耐えることができないといった欠点を有し
ている。However, these coating films require a high temperature and a long time for dry polymerization, and thus have a problem in productivity. Although some degree of anti-reflection film can be obtained, the physical strength such as hardness, scratch resistance, and adhesion to the substrate is insufficient, and the optical multilayer film is used as the outermost layer. If it is insufficient, it has a drawback that it cannot withstand practical use.
【０００６】これらを改善するために、金属アルコキシ
ドとアクリル化合物との複合材料などが提案されている
（特開平８−２９７２０１など）。[0006] In order to improve these, a composite material of a metal alkoxide and an acrylic compound has been proposed (Japanese Patent Application Laid-Open No. 8-297201).
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、これら
の複合膜組成物は、硬度や耐擦傷性などの物理的強度を
向上させようとするとアクリル系モノマー成分比率を高
くする必要があり、光学特性を決定するＴｉ系などのア
ルコキシドを出発組成とする高屈折率酸化物の体積比が
抑制され高屈折率化をはかることができないという欠点
を有し、この材料を用いた反射防止膜では十分な強度
（硬度や耐擦傷性、密着性などの物理的強度）を維持し
かつ反射防止性能に優れる積層体は見出されていない。However, in order to improve physical strength such as hardness and abrasion resistance, it is necessary to increase the ratio of acrylic monomer components in these composite film compositions, and to improve optical characteristics. It has the disadvantage that the volume ratio of the high-refractive-index oxide starting from an alkoxide such as a Ti-based compound to be determined is suppressed and the refractive index cannot be increased, and the antireflection film using this material has sufficient strength. (Physical strength such as hardness, scratch resistance and adhesion) and a laminate excellent in antireflection performance have not been found.
【０００８】そこで、本発明は、高い反射防止性能を有
しかつ物理的的強度にも優れ、安価で、生産性に優れた
反射防止積層体およびその製造方法を提供することを目
的とする。Accordingly, an object of the present invention is to provide an antireflection laminate having high antireflection performance, excellent physical strength, low cost, and excellent productivity, and a method for producing the same.
【０００９】[0009]
【課題を解決するための手段】上述の課題を達成すべく
検討した結果、プラスチックやガラスなどの基材の少な
くとも一方に、ハードコート層／高屈折率層／低屈折率
層あるいはハードコート層／中屈折率層／高屈折率層／
低屈折率層を順次積層してるなる多層構成の反射防止膜
が形成された積層体において、各層の境界の少なくとも
１ヶ所に、該境界を挟んだ上下各層の中間的な屈折率を
もつ中間境界層を形成することで課題を解決できること
を見出し、本発明に至ったものである。As a result of investigations to achieve the above-mentioned objects, as a result, a hard coat layer / high refractive index layer / low refractive index layer or hard coat layer was formed on at least one of substrates such as plastic and glass. Medium refractive index layer / High refractive index layer /
In a laminated body on which a multi-layered antireflection film is formed by sequentially laminating low refractive index layers, an intermediate boundary having an intermediate refractive index between upper and lower layers sandwiching the boundary is provided at least at one of the boundaries of each layer. The inventors have found that the problem can be solved by forming a layer, and have reached the present invention.
【００１０】具体的には、請求項１に係る発明は、基材
の少なくとも一方に、ハードコート層／高屈折率層／低
屈折率層あるいはハードコート層／中屈折率層／高屈折
率層／低屈折率層を順次積層してるなる多層構成の反射
防止膜が形成された積層体において、各層の境界の少な
くとも１ヶ所に、該境界を挟んだ上下各層の中間的な屈
折率をもつ中間境界層が形成されたことを特徴とする反
射防止積層体に関するものである。More specifically, the invention according to claim 1 is characterized in that at least one of the substrates has a hard coat layer / high refractive index layer / low refractive index layer or a hard coat layer / medium refractive index layer / high refractive index layer. / In a laminate having a multilayered antireflection film formed by sequentially laminating low-refractive-index layers, at least one portion of each layer boundary has an intermediate refractive index between the upper and lower layers sandwiching the boundary. The present invention relates to an antireflection laminate having a boundary layer formed thereon.
【００１１】請求項２に係る発明は、前記中間境界層に
おける該層の膜厚方向の屈折率分布が不均一であり、挟
まれた上下層と傾斜的な屈折率を有することを特徴とす
る請求項１に記載の反射防止積層体に関するものであ
る。The invention according to claim 2 is characterized in that the intermediate boundary layer has a non-uniform refractive index distribution in the thickness direction of the layer, and has a gradient refractive index with the upper and lower layers sandwiched therebetween. The present invention relates to the antireflection laminate according to claim 1.
【００１２】請求項３に係る発明は、前記中間境界層の
光学膜厚が上層もしくは下層の目的の光学膜厚の２０／
５０〜１／５０であることを特徴とする請求項１、２何
れかに記載の反射防止積層体に関するものである。According to a third aspect of the present invention, the optical thickness of the intermediate boundary layer is 20/20 of the target optical thickness of the upper or lower layer.
The antireflection laminate according to any one of claims 1 and 2, wherein the thickness is 50 to 1/50.
【００１３】請求項４に係る発明は、前記反射防止積層
体を構成するハードコート層、高屈折層、中屈折率層、
低屈折率層、および中間境界層の各層が、一般式Ｒ’ｘ
Ｍ（ＯＲ）ｙ−ｘ（Ｒ：アルキル基、Ｒ’：末端にビニ
ル基、アクリロイル基、メタクリロイル基などの重合可
能な不飽和結合を有する官能基、ｙは金属の酸化数ｘは
０≦ｘ＜ｙの置換数、ＭはＴｉ，Ｔａ，Ｚｒ，Ｉｎ，Ｚ
ｎ、Ｓｉ、Ａｌのいずれか１種）で表せる有機金属化合
物およびその加水分解物の少なくとも一種と、多官能ア
クリル化合物とを含有するコーティング剤を塗布して形
成されてなる請求項１、２、３何れかにに記載の反射防
止積層体に関するものである。According to a fourth aspect of the present invention, a hard coat layer, a high refractive layer, a medium refractive index layer,
Each layer of the low refractive index layer and the intermediate boundary layer is represented by the general formula R′x
M (OR) y-x (R: an alkyl group, R ': a functional group having a polymerizable unsaturated bond such as a vinyl group, an acryloyl group, a methacryloyl group, etc. at the terminal, y is an oxidation number of a metal x is 0 ≦ x <The number of substitutions of y, M is Ti, Ta, Zr, In, Z
n, Si, or Al), formed by applying a coating agent containing at least one of an organometallic compound represented by the formula (1) and a hydrolyzate thereof and a polyfunctional acrylic compound. 3. The antireflection laminate according to any one of (3) to (3).
【００１４】請求項５に係る発明は、請求項１、２、
３、４何れかにに記載の反射防止積層体が多層ウェット
コーティング法により形成され、該積層プロセスにおい
て、下層が未硬化あるいは不完全硬化の状態で上層を積
層することで、下層の一部が上層により浸食され上下層
の一部が混合された中間層あるいは傾斜層を形成させる
ことを特徴とする反射防止積層体の製造方法に関するも
のである。[0014] The invention according to claim 5 is the invention according to claims 1, 2,
The antireflection laminate according to any one of 3, 4 is formed by a multilayer wet coating method, and in the lamination process, the lower layer is partially cured by laminating the upper layer in an uncured or incompletely cured state. The present invention relates to a method for producing an antireflection laminate, wherein an intermediate layer or an inclined layer in which a part of upper and lower layers is eroded by an upper layer is formed.
【００１５】[0015]
【発明の実施の形態】本発明によれば、各層の境界に両
者の中間的性質を有する材料を中間境界層として設ける
ことで境界における、硬化時の応力緩和、熱膨張差によ
るサーマルショックなどに起因する層間強度低下に関わ
る因子を低減せしめることができ多層化しても十分な強
度を発現させることができるものである。According to the present invention, a material having intermediate properties between the two layers is provided as an intermediate boundary layer at the boundary between the layers to reduce stress at the boundary during curing, thermal shock due to a difference in thermal expansion, and the like. Factors relating to the decrease in interlayer strength can be reduced, and sufficient strength can be exhibited even if the layers are multilayered.
【００１６】境界層の膜厚方向の屈折率分布を傾斜的に
変化させることで、さらに効果が期待される。Further effects can be expected by changing the refractive index distribution of the boundary layer in the thickness direction in a gradient manner.
【００１７】該境界層を設ける方法として、ウェットコ
ーティングによる手法だと、構成する材料の配合比によ
り屈折率を任意に変えることができるため好適であり、
なかでもＴｉやＳｉなどの金属アルコキシドと分子中に
ビニル基、アクリロイル基、メタクリロイル基などの重
合可能な不飽和結合を少なくとも３個以上を有するアク
リル系化合物とを主成分とすることで、一般式（Ａ）の
金属アルコキシドの加水分解生成物の加熱重合による酸
化物ネットワークの形成とＵＶあるいはＥＢ照射による
被膜中のアクルロイル基などの重合可能な不飽和結合基
の光（ＥＢ）重合による架橋の複合架橋により硬化する
ものであり、アクリル化合物を３官能とすることで被膜
の架橋密度が高くでき好適である。The method of providing the boundary layer by wet coating is preferable because the refractive index can be arbitrarily changed depending on the mixing ratio of the constituent materials.
Among them, a metal alkoxide such as Ti or Si and an acrylic compound having at least three or more polymerizable unsaturated bonds such as a vinyl group, an acryloyl group, and a methacryloyl group in a molecule are mainly used to form a compound represented by the general formula Combination of formation of an oxide network by thermal polymerization of the hydrolysis product of the metal alkoxide of (A) and crosslinking of polymerizable unsaturated bond groups such as aculloyl groups in the coating by UV or EB irradiation by photo (EB) polymerization It is cured by cross-linking, and it is preferable to make the acrylic compound trifunctional so that the cross-linking density of the film can be increased.
【００１８】[0018]
【実施例】本発明の一実施例を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described in detail.
【００１９】本発明の反射防止積層体は、プラスチック
やガラスなどの基材の少なくとも一方に、ハードコート
層／高屈折率層／低屈折率層あるいはハードコート層／
中屈折率層／高屈折率層／低屈折率層を順次積層してる
なる多層構成の反射防止膜が形成された積層体におい
て、各層の境界の少なくとも１ヶ所に、該境界を挟んだ
上下各層の中間的な屈折率をもつ中間境界層が形成され
るものであり、上記各層構成する材料は、Ｔｉ、Ｓｉな
どの金属アルコキシドと多官能アクリル化合物とを主成
分とする組成物からなるものてあり、これを基材に塗工
し、加熱乾燥し、被膜を形成した後、ＵＶなどの光照射
を施すことでを形成されるもので、各層の設計条件にあ
わせて適宜、材料を組合せることができるものである。The antireflection laminate of the present invention comprises a hard coat layer / high refractive index layer / low refractive index layer or hard coat layer on at least one of substrates such as plastic and glass.
In a laminated body in which a multi-layered antireflection film is formed by sequentially laminating a middle refractive index layer / a high refractive index layer / a low refractive index layer, at least one of the boundaries of each layer, the upper and lower layers sandwiching the boundary An intermediate boundary layer having an intermediate refractive index is formed. The material constituting each of the layers is a composition mainly composed of a metal alkoxide such as Ti or Si and a polyfunctional acrylic compound. Yes, this is applied to a substrate, dried by heating, and after forming a film, it is formed by applying light such as UV, and the materials are appropriately combined according to the design conditions of each layer. Is what you can do.
【００２０】コーティング材料に含まれる各成分につい
て以下に詳述する。本発明において用いられる、Ｔｉ、
Ｓｉなどの有機金属化合物は一般式Ｒ’ｘＭ（ＯＲ）ｙ
−ｘ（Ｒ：アルキル基、Ｒ’：末端にビニル基、アクリ
ロイル基、メタクリロイル基などの重合可能な不飽和結
合を有する官能基、ｙは金属の酸化数ｘは０≦ｘ＜ｙの
置換数、ＭはＴｉ，Ｔａ，Ｚｒ，Ｉｎ，Ｚｎ、Ｓｉ、Ａ
ｌのいずれか１種）で表せる有機金属化合物で、Ｘ＝０
の化合物は一般式Ｍ（ＯＲ）ｎ（ＭはＳｉ、Ｔｉ，Ｔ
ａ，Ｚｒ，Ｉｎ，Ｚｎのいずれか１種、Ｒはアルキル基
ｎは金属の酸化数）（表１ではＡ１と表示）で表せられ
るものであり、テトラエトキシシラン、テトラ−ｉｓｏ
−プロピルチタネート、テトラ−ｎ−ブチルチタネー
ト、テトラ−ｎ−ブチルジルコネートなどが例示され、
Ｘ≦１のアクリロイル基などを有する有機金属化合物は
一般式Ｒ’ｘＭ（ＯＲ）ｙ（Ｒ：アルキル基、Ｒ’：末
端にビニル基、アクリロイル基、メタクリロイル基など
の重合可能な不飽和結合を有する官能基、ｙは金属の酸
化数ｘは０＜ｘ＜ｙの置換数）（表１ではＡ２と表示）
で表せるもので、ビニルトリメトキシシラン、アクリロ
キシプロピルトリメトキシシラン、メタクリロキシプロ
ピルトリメトキシシラン、メタクリロキシトリイソプロ
ポキシチタネートなどが例示される。Each component contained in the coating material will be described in detail below. Ti used in the present invention,
Organometallic compounds such as Si have the general formula R'xM (OR) y
-X (R: alkyl group, R ': functional group having a polymerizable unsaturated bond such as a vinyl group, acryloyl group, methacryloyl group, etc. at the terminal, y is the oxidation number of the metal x is the substitution number of 0 ≦ x <y , M are Ti, Ta, Zr, In, Zn, Si, A
l), X = 0
Is a compound of the general formula M (OR) n (M is Si, Ti, T
a, Zr, In, or Zn, where R is an alkyl group, n is the oxidation number of the metal (in Table 1, denoted as A1), and includes tetraethoxysilane and tetra-iso.
-Propyl titanate, tetra-n-butyl titanate, tetra-n-butyl zirconate, and the like,
The organometallic compound having an acryloyl group of X ≦ 1 has a general formula R′xM (OR) y (R: alkyl group, R ′: a polymerizable unsaturated bond such as a vinyl group, an acryloyl group, a methacryloyl group at a terminal). A functional group, y is an oxidation number of the metal x is a substitution number of 0 <x <y (in Table 1, indicated as A2)
And examples thereof include vinyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxytriisopropoxytitanate.
【００２１】これらの有機金属化合物は特に例示に限定
されるものでなく、２種以上組み合わせても何ら差し支
えなく、目的の屈折率に合わせて、金属種などを選択す
ることができ高屈折率成分としては、Ｔｉ、Ｚｒなどの
金属が好適で、低屈折率成分としてはＳｉ、Ａｌなどが
好適である。These organometallic compounds are not particularly limited to the exemplified ones, and any combination of two or more kinds may be used without any problem. The metal species can be selected according to the desired refractive index, and the high refractive index component can be selected. Are preferably metals such as Ti and Zr, and low refractive index components are preferably Si and Al.
【００２２】これらの有機金属化合物はコーティング組
成物中にｐ−トルエンスルホン酸などの有機酸触媒を含
有させることで、塗工後に大気中の水分でもって加水分
解反応させて被膜形成しても良いし、またあらかじめ水
（塩酸などの触媒を含む）を添加し加水分解反応させた
ものを用いることもできる。These organometallic compounds may be formed into a coating film by applying an organic acid catalyst such as p-toluenesulfonic acid to the coating composition to cause a hydrolysis reaction with atmospheric moisture after coating. Alternatively, water (including a catalyst such as hydrochloric acid) added in advance and subjected to a hydrolysis reaction may be used.
【００２３】その際に、有機金属化合物の加水分解物
が、該有機金属化合物の全アルコキシル基を加水分解さ
せるのに必要な水の量よりも１／８〜７／８の量の水で
部分加水分解されたものであるとすることで安定な組成
物を得ることができ、余分な水を残すことなく特別な分
離精製せずに用いることができる。At this time, the hydrolyzate of the organometallic compound is partially dissolved with water in an amount of 1/8 to 7/8 of the amount of water required to hydrolyze all the alkoxyl groups of the organometallic compound. By being hydrolyzed, a stable composition can be obtained, and can be used without leaving extra water and without special separation and purification.
【００２４】上記の調整は、アクリル化合物と余分な水
との副反応を抑制したり、金属化合物の加水分解率をコ
ントロールして、金属化合物ポリマーの成長を抑制した
り、相溶性を高めることで、相分離を抑制し均質で分子
架橋密度が高く、分子レベルのハイブリッド膜を形成至
らしめるものである。The above adjustment is performed by suppressing a side reaction between the acrylic compound and excess water, controlling the rate of hydrolysis of the metal compound to suppress the growth of the metal compound polymer, and increasing the compatibility. It is intended to suppress the phase separation and to form a homogeneous, high molecular crosslink density and a molecular level hybrid film.
【００２５】また、アクリル化合物は、その分子中にビ
ニル基、アクリロイル基やメタクリロイル基など重合可
能なの不飽和結合を少なくとも３個以上有するものであ
って、例えばＤＰＨＡなどのモノマー類と、これらのモ
ノマーの変性体、および誘導体、などが使用できる。The acrylic compound has at least three polymerizable unsaturated bonds, such as a vinyl group, an acryloyl group, and a methacryloyl group, in its molecule, and includes, for example, monomers such as DPHA and these monomers. And derivatives thereof can be used.
【００２６】なかでもＤＰＨＡなど多官能アクリルモノ
マー類およびその変性体など平均分子量２００〜１００
０のものであれば、有機金属化合物の加水分解物と相溶
性が良く、被膜形成時に相分離することなく、架橋密度
の高い、均質で透明なハイブリッド被膜が形成できる。Among them, polyfunctional acrylic monomers such as DPHA and modified products thereof have an average molecular weight of 200 to 100.
If it is 0, it has good compatibility with the hydrolyzate of the organometallic compound, and a uniform and transparent hybrid film having a high crosslinking density can be formed without phase separation during film formation.
【００２７】ＵＶ照射による硬化を行う際には、ラジカ
ル重合開始剤を添加すると好適であり、ベンゾインメチ
ルエーテルなどのベンゾインエーテル系開始剤、アセト
フェノン、２、１−ヒドロキシシクロヘキシルフェニル
ケトン、などのアセトフェノン系開始剤、ベンゾフェノ
ンなどのベンゾフェノン系開始剤など特に限定されるも
のではない。When curing by UV irradiation, it is preferable to add a radical polymerization initiator, such as a benzoin ether-based initiator such as benzoin methyl ether, or an acetophenone-based initiator such as acetophenone or 2,1-hydroxycyclohexylphenyl ketone. The initiator and the benzophenone-based initiator such as benzophenone are not particularly limited.
【００２８】さらに、平均粒径１〜５０ｎｍの結晶性の
酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化インジ
ウムから選ばれる高屈折超微粒子、シリカゾル、酸化珪
素微粒子などの低屈折微粒子などを添加することができ
る。これらの微粒子を添加する技術は公知ではあるが、
本発明のハイブリッド系組成物との組み合わせは、単な
る組み合わせではなく、マトリックスであるコート組成
物の無機のネットワークと無機フィラーとの相溶性、親
和性が高く、単に有機樹脂中に分散するより、より良い
分散状態、フィラーとマトリックスとの密着性が高い被
膜が得られ、通常の添加効果よりも高い効果が得られる
ものである。Further, low refractive particles such as crystalline titanium oxide, zirconium oxide, zinc oxide and indium oxide having a high average refractive index of 1 to 50 nm, ultra-fine particles of high refractive index, silica sol and fine particles of silicon oxide may be added. it can. Techniques for adding these fine particles are known,
The combination with the hybrid composition of the present invention is not a mere combination, but has a high compatibility between the inorganic network and the inorganic filler of the coat composition as the matrix and the inorganic filler, and a higher affinity than simply dispersing in the organic resin. A film having a good dispersion state and a high adhesion between the filler and the matrix can be obtained, and an effect higher than the usual effect of addition can be obtained.
【００２９】上述した各成分をいくつか組み合わせてコ
ーティング組成物に加えることができ、さらに、物性を
損なわない範囲で、分散剤、安定化剤、粘度調整剤、着
色剤など公知の添加剤を加えることができる。Some of the above-mentioned components can be added in combination to the coating composition, and known additives such as dispersants, stabilizers, viscosity modifiers, and coloring agents are added as long as the physical properties are not impaired. be able to.
【００３０】コーティング組成物の塗布方法には、通常
用いられる、ディッピング法、ロールコティング法、ス
クリーン印刷法、スプレー法など従来公知の手段が用い
られる。被膜の厚さは目的の光学設計にあわせて、液の
濃度や塗工量によって適宜選択調整することができる。As a method for applying the coating composition, conventionally known means such as a dipping method, a roll coating method, a screen printing method, and a spray method are used. The thickness of the coating can be appropriately selected and adjusted depending on the concentration of the liquid and the amount of coating in accordance with the intended optical design.
【００３１】本発明の境界層は多層化に際し光学特性に
影響のでない程度の膜厚とすることで、境界層を上下層
の一部として計算することができることを見出した。It has been found that the boundary layer according to the present invention can be calculated as a part of the upper and lower layers by setting the thickness of the boundary layer so as not to affect the optical characteristics when forming the multilayer.
【００３２】すなわち境界層と下層もしくは上層のとの
２層で光学的に１層と見なすことができるもので、概ね
その膜厚は目的の光学膜厚（λ／４）の２０／５０〜１
／５０であり、下層もしくは上層もそれに応じて膜厚を
調整する必要がある。That is, two layers, the boundary layer and the lower or upper layer, can be optically regarded as one layer, and the film thickness is generally 20/50 to 1/50 of the target optical film thickness (λ / 4).
/ 50, and it is necessary to adjust the film thickness of the lower layer or the upper layer accordingly.
【００３３】また、本発明の境界層は、上記材料を組み
合わせた組成物をウェットコーティングにより形成され
るものであるが、配合比を組み合わせて別途境界層を設
置してもよいが、さらに好適にはウェットコーティング
の利点を活かして下層の硬化状態（乾燥状態）を乾燥条
件、あるいはＵＶ照射条件を調整することで、半硬化状
態とした上に積層することで、下層と上層の一部で混合
層を形成せしめることで、簡便に形成することができる
もので、本発明の材料組成は熱硬化により架橋する成分
とＵＶ硬化により架橋する成分より構成されるためこの
半硬化状態を容易に形成できるものである。さらに、硬
化条件によっては境界層の屈折率が膜厚方向に傾斜的に
変化させることができるものである。The boundary layer of the present invention is formed by wet coating a composition obtained by combining the above-mentioned materials. A boundary layer may be separately provided in combination with a compounding ratio. Utilizes the advantages of wet coating to adjust the curing state (dry state) of the lower layer to dry or UV irradiation conditions, and then to form a semi-cured state and then laminate the lower layer and part of the upper layer. The semi-cured state can be easily formed because the material composition of the present invention is composed of a component that is crosslinked by heat curing and a component that is crosslinked by UV curing, by forming a layer. Things. Further, depending on the curing conditions, the refractive index of the boundary layer can be inclinedly changed in the film thickness direction.
【００３４】本発明のコーティング組成物を具体的な実
施例をあげて説明する。The coating composition of the present invention will be described with reference to specific examples.
【００３５】＜実施例＞下記組成の材料を表１に示す割
合になるように組み合わせて調液してハードコート層、
高屈折率層、低屈折率層用の各コーティング組成物を作
成し、ＵＶ硬化の開始剤としてアセトフェノン系開始剤
を重合成分に対して２％添加した。<Examples> Materials having the following compositions were combined in the proportions shown in Table 1 to prepare a solution, and a hard coat layer was prepared.
Each coating composition for the high-refractive index layer and the low-refractive index layer was prepared, and an acetophenone-based initiator was added as a UV curing initiator in an amount of 2% based on the polymerization component.
【００３６】基材として８０μｍ厚のＴＡＣを用い、各
材料をＨＣ／高／低の順に、バーコーターにより塗布
し、乾燥機で１００℃−１ｍｉｎ乾燥し、全層積層後に
高圧水銀灯により１，０００ｍＪ／ｃｍ２の紫外線を照
射して硬化させ反射防止積層体を得た。積層に際し、各
層の光学膜厚（ｎｄ＝屈折率ｎ＊膜厚ｄ（ｎｍ））がｎ
ｄ＝５５０／４ｎｍになるよう適宜濃度調整をして、各
種試験用の試験体を得た。Using a TAC having a thickness of 80 μm as a base material, each material was applied in the order of HC / high / low by a bar coater, dried at 100 ° C. for 1 minute with a drier, and after laminating all layers, 1,000 mJ was applied by a high pressure mercury lamp. / Cm 2 to irradiate and cure to obtain an antireflection laminate. At the time of lamination, the optical film thickness (nd = refractive index n * film thickness d (nm)) of each layer is n
The concentration was appropriately adjusted so that d = 550/4 nm to obtain test specimens for various tests.
【００３７】本発明の比較例として積層の際に、各層積
層毎にＵＶ照射を実施して完全硬化状態で積層し境界層
がない試験体を合わせて作成した。As a comparative example of the present invention, at the time of lamination, UV irradiation was performed for each layer lamination, and the layers were laminated in a completely cured state, and were prepared together with a specimen having no boundary layer.
【００３８】境界層の確認はＥＳＣＡにより、各積層体
の深さ方向の分析により実施し、比較例のものは高屈折
率材料のＴｉの比率が深さ方向で層間付近で急激に変化
し、境界層が存在していないのに対し、本実施例の積層
体はＨＣと高屈折率層および高屈折率層と低屈折率層の
各層間に上下層の１／５程度の膜厚に相当する範囲にお
いてＴｉの濃度が傾斜的に変化している境界層が生成さ
れていたのを確認した。The boundary layer was confirmed by ESCA by analyzing the depth direction of each laminate. In the comparative example, the ratio of Ti of the high refractive index material rapidly changed near the interlayer in the depth direction. In contrast to the absence of the boundary layer, the laminate of the present embodiment has a thickness of about 1/5 of the upper and lower layers between the HC and the high refractive index layer and between the high refractive index layer and the low refractive index layer. It was confirmed that a boundary layer in which the concentration of Ti had a gradient change was generated in the range shown in FIG.
【００３９】実施例および比較例の試験体を下記評価方
法にて評価した。表２に結果を示す。The test pieces of Examples and Comparative Examples were evaluated by the following evaluation methods. Table 2 shows the results.
【００４０】＜コーティング組成物の各成分＞ （Ａ）テトライソプロポキシドチタンとメタクリロキシ
プロピルトリメトキシシランを表１に示す固形分比にな
るように所定量混合し、混合物１ｍｏｌに対して０．１
Ｎの塩酸２ｍｏｌとイソプロピルアルコールを添加、室
温で２時間攪拌反応させた、複合加水分解ゾル溶液。各
成分の比率はＡ１を酸化チタン成分、Ａ２をその他の成
分とした。 （Ｂ）ＤＰＨＡのＩＰＡ希釈溶液。 （Ｃ）平均粒径２５ｎｍの市販のシリカゾルＩＰＡ分散
型<Each Component of Coating Composition> (A) A predetermined amount of titanium tetraisopropoxide and methacryloxypropyltrimethoxysilane were mixed so as to have a solid content ratio shown in Table 1, and 0.1% was added to 1 mol of the mixture. 1
A complex hydrolyzed sol solution obtained by adding 2 mol of N hydrochloric acid and isopropyl alcohol and stirring and reacting at room temperature for 2 hours. Regarding the ratio of each component, A1 was a titanium oxide component and A2 was another component. (B) IPA diluted solution of DPHA. (C) Commercially available silica sol IPA dispersion type having an average particle size of 25 nm
【００４１】＜評価試験＞ （１）光学特性 分光光度計により入射角５で５５０ｎｍにおける反射率
を測定し、反射率値か被膜の屈折率を見積もった。<Evaluation Test> (1) Optical Characteristics The reflectance at 550 nm at an incident angle of 5 was measured with a spectrophotometer, and the reflectance value or the refractive index of the film was estimated.
【００４２】（２）密着性 塗料一般試験法ＪＩＳ−Ｋ５４００のクロスカット密着
試験方法に準じて塗膜の残存数にて評価した。(2) Adhesion The paint was evaluated in terms of the number of remaining paint films according to the cross-cut adhesion test method of JIS-K5400.
【００４３】（３）鉛筆硬度 塗料一般試験法ＪＩＳ−Ｋ５４００の鉛筆引っかき値試
験方法に準じて塗膜の擦り傷にて評価した。(3) Pencil hardness The paint was evaluated for scratches on the coating film according to the Pencil Scratch Value Test Method of JIS-K5400.
【００４４】（４）耐擦傷試験 スチールウール＃００００により、２５０ｇ／ｃｍ２の
荷重で往復５回擦傷試験を実施、目視による傷の外観を
検査した。評価は、傷なし◎、かるく傷あり○、かなり
傷つく△、著しく傷つくの４段階とした。(4) Scratch resistance test A steel wool # 0000 was used to perform a reciprocating scratch test 5 times under a load of 250 g / cm 2 to visually inspect the appearance of the scratch. The evaluation was made in four stages: no scratches, slight scratches, considerable damage, and significant damage.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
【００４７】表２に示すように、反射防止特性は実施
例、比較例とも反射率が０．５％以下で良好であるが、
本発明の実施例の用に境界層を設けた積層体は耐擦傷性
などの機械的強度に優れることがわかる。As shown in Table 2, the anti-reflection characteristics of the embodiment and the comparative example are good with a reflectivity of 0.5% or less.
It can be seen that the laminate provided with the boundary layer for the example of the present invention has excellent mechanical strength such as scratch resistance.
【００４８】[0048]
【発明の効果】以上述べたように本発明の積層体は、Ｍ
−Ｏ−Ｍの金属酸化物架橋とアクリル基の架橋を有し金
属酸化物と有機化合物の分子レベルのハイブリッド構造
を呈した被膜により構成され、層間に境界層を設置する
ことで光学特性と物理的強度特性とを兼備した反射防止
膜を形成することができるものである。As described above, the laminate of the present invention has a M
It is composed of a coating having a molecular-level hybrid structure of a metal oxide and an organic compound having a metal oxide cross-link of -OM and a cross-link of an acrylic group, and optical properties and physical properties by providing a boundary layer between the layers. It is possible to form an anti-reflection film which also has a target strength characteristic.
【００４９】すなわち、ディスプレイの反射防止膜など
の基材の最外層に形成され、過酷な環境や取り扱いにも
充分に耐えられる被膜を形成することができ、蒸着など
と比べ装置コストも比較的安価で、成膜（塗工）速度も
１０倍以上で生産性も高く、製造も容易である。That is, a film formed on the outermost layer of a substrate such as an anti-reflection film of a display can form a film that can withstand severe environments and handling sufficiently, and the apparatus cost is relatively low as compared with vapor deposition. Thus, the film forming (coating) speed is 10 times or more, the productivity is high, and the production is easy.
【００５０】また本発明構成する組成物は、光照射など
で硬化するため、低温での塗工が可能なので、フィルム
などのを巻き取り塗工で作成することが可能で、さらに
下層の硬化状態を制御することで、任意に境界層を別途
層を設けることなく作成できるため、安価に、大量生産
できるといった効果を奏する。Since the composition of the present invention is cured by light irradiation or the like, it can be applied at a low temperature. Therefore, it is possible to form a film or the like by winding coating, and furthermore, the cured state of the lower layer , The boundary layer can be arbitrarily created without providing a separate layer, so that there is an effect that mass production can be performed at low cost.
フロントページの続き Ｆターム(参考） 2K009 AA06 AA07 AA10 AA15 BB02 BB11 CC03 CC09 CC21 CC24 CC26 CC42 DD01 DD02 DD05 DD06 4F100 AK25A AK25B AK25C AK25D AR00A AR00B AR00C AR00D BA04 BA07 BA15 BA26 EH462 JA20D JN06 JN18B JN18C JN18D YY00D Continued on the front page F term (reference) 2K009 AA06 AA07 AA10 AA15 BB02 BB11 CC03 CC09 CC21 CC24 CC26 CC42 DD01 DD02 DD05 DD06 4F100 AK25A AK25B AK25C AK25D AR00A AR00B AR00C AR00D BA04 BA07 BA15 BA26 EHN18J20 JD18J20D
Claims (5)
／高屈折率層／低屈折率層あるいはハードコート層／中
屈折率層／高屈折率層／低屈折率層を順次積層してるな
る多層構成の反射防止膜が形成された積層体において、
各層の境界の少なくとも１ヶ所に、該境界を挟んだ上下
各層の中間的な屈折率をもつ中間境界層が形成されたこ
とを特徴とする反射防止積層体。A hard coat layer / high refractive index layer / low refractive index layer or a hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer is sequentially laminated on at least one of the substrates. In a laminate on which an antireflection film having a multilayer structure is formed,
An antireflection laminate, wherein an intermediate boundary layer having an intermediate refractive index between upper and lower layers sandwiching the boundary is formed at at least one position of a boundary between the layers.
屈折率分布が不均一であり、挟まれた上下層と傾斜的な
屈折率を有することを特徴とする請求項１に記載の反射
防止積層体。2. The method according to claim 1, wherein the intermediate boundary layer has a non-uniform refractive index distribution in the thickness direction of the layer, and has a gradient refractive index with the upper and lower layers sandwiched therebetween. Anti-reflective laminate.
下層の目的の光学膜厚の２０／５０〜１／５０であるこ
とを特徴とする請求項１、２何れかに記載の反射防止積
層体。3. The antireflection method according to claim 1, wherein the optical thickness of the intermediate boundary layer is 20/50 to 1/50 of the target optical thickness of the upper or lower layer. Laminate.
ト層、高屈折層、中屈折率層、低屈折率層、および中間
境界層の各層が、一般式Ｒ’ｘＭ（ＯＲ）ｙ−ｘ（Ｒ：
アルキル基、Ｒ’：末端にビニル基、アクリロイル基、
メタクリロイル基などの重合可能な不飽和結合を有する
官能基、ｙは金属の酸化数ｘは０≦ｘ＜ｙの置換数、Ｍ
はＴｉ，Ｔａ，Ｚｒ，Ｉｎ，Ｚｎ、Ｓｉ、Ａｌのいずれ
か１種）で表せる有機金属化合物およびその加水分解物
の少なくとも一種と、多官能アクリル化合物とを含有す
るコーティング剤を塗布して形成されてなる請求項１、
２、３何れかに記載の反射防止積層体。4. A hard coat layer, a high refractive index layer, a medium refractive index layer, a low refractive index layer, and an intermediate boundary layer constituting the antireflection laminate, each having a general formula R′xM (OR) y−x (R:
Alkyl group, R ′: terminal vinyl group, acryloyl group,
A functional group having a polymerizable unsaturated bond such as a methacryloyl group; y is an oxidation number of a metal x is a substitution number of 0 ≦ x <y;
Is formed by applying a coating agent containing at least one of an organometallic compound represented by Ti, Ta, Zr, In, Zn, Si, and Al) and a hydrolyzate thereof, and a polyfunctional acrylic compound. Claim 1, which is made
The antireflection laminate according to any one of 2, 3 and 4.
防止積層体が多層ウェットコーティング法により形成さ
れ、該積層プロセスにおいて、下層が未硬化あるいは不
完全硬化の状態で上層を積層することで、下層の一部が
上層により浸食され上下層の一部が混合された中間層あ
るいは傾斜層を形成させることを特徴とする反射防止積
層体の製造方法。5. The antireflection laminate according to claim 1, 2, 3, or 4, wherein the lower layer is uncured or incompletely cured in the lamination process. A method for producing an antireflection laminate, comprising forming an intermediate layer or an inclined layer in which part of a lower layer is eroded by an upper layer and part of an upper and lower layer is mixed by laminating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23576199A JP4649690B2 (en) | 1999-08-23 | 1999-08-23 | Antireflection laminate and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23576199A JP4649690B2 (en) | 1999-08-23 | 1999-08-23 | Antireflection laminate and method for producing the same |
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|---|---|---|---|
| JP2007235207A Division JP4380752B2 (en) | 2007-09-11 | 2007-09-11 | Method for manufacturing antireflection laminate |
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| Publication Number | Publication Date |
|---|---|
| JP2001059902A true JP2001059902A (en) | 2001-03-06 |
| JP4649690B2 JP4649690B2 (en) | 2011-03-16 |
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ID=16990854
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164117A (en) * | 1999-12-07 | 2001-06-19 | Toppan Printing Co Ltd | High-refractive-index composition and antireflection laminate |
| WO2006098363A1 (en) * | 2005-03-16 | 2006-09-21 | Dai Nippon Printing Co., Ltd. | Optical laminated body |
| WO2011058847A1 (en) * | 2009-11-12 | 2011-05-19 | 凸版印刷株式会社 | Anti-reflection film and method for producing same |
| WO2011089787A1 (en) * | 2010-01-22 | 2011-07-28 | 凸版印刷株式会社 | Anti-reflective film and process for production thereof |
| WO2021020301A1 (en) * | 2019-07-26 | 2021-02-04 | 日本ペイント・オートモーティブコーティングス株式会社 | Layered film and layered member |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001164117A (en) * | 1999-12-07 | 2001-06-19 | Toppan Printing Co Ltd | High-refractive-index composition and antireflection laminate |
| WO2006098363A1 (en) * | 2005-03-16 | 2006-09-21 | Dai Nippon Printing Co., Ltd. | Optical laminated body |
| US7947341B2 (en) | 2005-03-16 | 2011-05-24 | Dai Nippon Printing Co., Ltd. | Optical laminated body |
| JP5340591B2 (en) * | 2005-03-16 | 2013-11-13 | 大日本印刷株式会社 | Optical laminate |
| WO2011058847A1 (en) * | 2009-11-12 | 2011-05-19 | 凸版印刷株式会社 | Anti-reflection film and method for producing same |
| US9285512B2 (en) | 2009-11-12 | 2016-03-15 | Toppan Printing Co., Ltd. | Anti-reflection film |
| WO2011089787A1 (en) * | 2010-01-22 | 2011-07-28 | 凸版印刷株式会社 | Anti-reflective film and process for production thereof |
| US9310526B2 (en) | 2010-01-22 | 2016-04-12 | Toppan Printing Co., Ltd. | Anti-reflection film having layers with a binder matrix |
| WO2021020301A1 (en) * | 2019-07-26 | 2021-02-04 | 日本ペイント・オートモーティブコーティングス株式会社 | Layered film and layered member |
| JPWO2021020301A1 (en) * | 2019-07-26 | 2021-09-13 | 日本ペイント・オートモーティブコーティングス株式会社 | Laminated film and laminated members |
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