JP4701492B2 - Structure - Google Patents

Description

【００７２】
［実施例５〜７および比較例３］
実施例５〜７では、ハードコート層に添加するシリカ粒子の数平均粒子径の影響を検討した。
すなわち、表２に示すように、実施例１におけるハードコート層に添加するシリカ粒子の数平均粒子径を２２ｎｍから、１００ｎｍ（実施例５）、２００ｎｍ（実施例６）、および３００ｎｍ（実施例７）にそれぞれ変更して構成した反射防止膜積層体について、耐擦傷性等の評価を行った。
一方、比較例３では、表２に示すように、ハードコート層に添加するシリカ粒子の数平均粒子径を１，０００ｎｍと本発明の上限を超える値とした以外は、実施例１と同様の反射防止膜積層体を作製して、耐擦傷性等の評価を行った。
得られた結果を表２に示す。
【００７３】
【表２】

【００７４】
［実施例８〜１０］
実施例８〜１０では、ハードコート層に添加するシリカ粒子に対する表面処理の影響を検討した。
すなわち、表３に示すように、実施例１におけるハードコート層に添加したアクリル変性したシリカ粒子を、ジメチルジメトキシシラン（東レ・ダウコーニング・シリコーン（株）製、商品名：ＡＹ−４３−００４）で表面処理したシリカ粒子（実施例８）、γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング・シリコーン（株）製、商品名：ＳＨ６０４０）で表面処理したシリカ粒子（実施例９）、および表面処理を施していないシリカ粒子（実施例１０）にそれぞれ変更して構成した反射防止膜積層体について、耐擦傷性等の評価を行った。
得られた結果を表３に示す。
【００７５】
【表３】

【００７６】
［実施例１１〜１３］
実施例１１〜１３では、ハードコート層に添加するシリカ粒子の添加量および硬度の関係を検討した。
すなわち、表４に示すように、実施例１におけるハードコート層に添加するシリカ粒子の添加量を、３７重量％から、１９重量％（実施例１１）、５６重量％（実施例１２）、および６６重量％（実施例１３）にそれぞれ変更して構成した反射防止膜積層体について、耐擦傷性や硬度等の評価を行った。
得られた結果を表４に示す。
【００７７】
【表４】

【００７８】
［実施例１４〜１６］
実施例１４〜１６では、ハードコート層を構成する紫外線硬化樹脂に含まれるアクリル酸エステルの種類の影響を検討した。
すなわち、表５に示すように、実施例１で使用したアクリル酸エステルとしてのトリメチロールプロパントリアクリレート（ＴＭＰＴＡと略する。）およびトリメチロールプロパントリオキシエチルアクリレート（ＥＯ−ＴＭＰＴＡと略する。）を、ＴＭＰＴＡ単独（実施例１４）、ジペンタエリスリトールペンタアクリレート（ＤＰＰＡと略する。）（実施例１５）、およびペンタエリスリトールトリアクリレート（ＰＥＴＡと略する。）（実施例１６）にそれぞれ変更して構成した反射防止膜積層体について、耐擦傷性等の評価を行った。
得られた結果を表５に示す。
【００７９】
【表５】

【００８０】
【発明の効果】
本発明の構造体によれば、基材上に、特定の（Ａ）ハードコート層と、（Ｂ）中間層と、（Ｃ）表面層とを含み、（Ａ）〜（Ｃ）層の構成内容を考慮するとともに、（Ｂ）層における表面粗さの値を考慮することにより、簡易な構造でありながら、耐擦傷性や透明性に優れた構造体を提供することができるようになった。
したがって、屈折率を低下させるために表面層にフッ素化合物や、ケイ素化合物の耐擦傷性に乏しい樹脂を使用したとしても、本発明により、透明性を損なうことなく、優れた耐擦傷性を示す構造体を提供することができるようになった。
【図面の簡単な説明】
【図１】本発明の反射防止膜積層体例の断面図である。
【図２】本発明の反射防止膜積層体の断面写真である（その１）。
【図３】本発明の反射防止膜積層体の断面写真である（その２）。
【符号の説明】
１２ 基材
１３ 高屈折率膜の侵入部分
１８ ハードコート層
２０ 高屈折率膜（中間層）
２２ 低屈折率膜（表面層）
２４ 反射防止膜積層体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a structure, and more particularly to a structure excellent in scratch resistance and transparency suitable for an antireflection film laminate and the like.
[0002]
[Prior art]
As a material for forming the antireflection film, for example, thermosetting polysiloxane compositions are known, and Japanese Patent Application Laid-Open Nos. 61-247743, 6-25599, 7-331115, and 10-232301 and the like.
However, the antireflection film obtained using such a thermosetting polysiloxane composition has a problem of poor scratch resistance and, as a result, poor durability.
Moreover, in manufacturing such an antireflection film, it is necessary to perform heat treatment at a high temperature for a long time, and there has been a problem that productivity is low or the types of applicable base materials are limited.
[0003]
Therefore, as disclosed in JP-A-8-94806, a low refractive index film comprising a high refractive index film in which fine particles are localized in a high refractive index binder resin on a substrate and a fluorine-based copolymer. An optical functional film in which a refractive index film is sequentially laminated has been proposed. More specifically, in order to form a high refractive index film, a fine particle layer such as a metal oxide particle of 200 nm or less is formed in advance on the process paper, and this is applied to the high refractive index binder resin on the substrate. The fine particle layer is embedded and localized in the high refractive index binder resin.
For the low refractive index film, fluorine having a fluorine content of 60 to 70% by weight obtained by copolymerization of a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. 100 to 10 parts by weight of the containing copolymer, 30 to 150 parts by weight of the polymerizable compound having an ethylenically unsaturated group, and 0.5 to 10 parts by weight of a polymerization initiator when the total amount thereof is 100 parts by weight. Is cured into a thin film having a thickness of 200 nm or less.
[0004]
[Problems to be solved by the invention]
However, the optical functional film disclosed in JP-A-8-94806 has a complicated manufacturing process for a high refractive index film, and as a result, it is difficult to produce an optical functional film exhibiting uniform characteristics. It was. In addition, the optical functional film does not consider the surface roughness value of the high refractive index film, and there is a problem that the scratch resistance of the low refractive index film is poor.
Accordingly, the inventors of the present invention have made extensive studies, and as a result, (A) a hard coat layer, (B) an intermediate layer (high refractive index film), and (C) a surface layer (low refractive index film) on the substrate. ) And the structure (antireflection film laminate) including the above-described problems only by considering the contents of the layers (A) to (C) and considering the value of the surface roughness in the layer (B). It was found that can be solved.
That is, an object of the present invention is to provide a structure excellent in scratch resistance and transparency while having a simple structure.
[0005]
[Means for Solving the Problems]
According to the present invention, a structure formed by laminating the following layers (A) to (C) is provided, and the above-described problems can be solved.
(A) Hard coat layer having a film thickness of 1 to 30 μm containing silica particles having a number average particle diameter of 5 to 300 nm
(B) An intermediate layer having a film thickness of 0.05 to 0.5 μm containing inorganic oxide particles having a number average particle diameter of 5 to 300 nm, and having a surface roughness Rz (based on JIS B0601) of 0.01 to 2 μm. Middle layer
(C) A surface layer having a film thickness of 0.05 to 0.5 μm containing a fluorine compound and a silicon compound, or any one of them
[0006]
That is, by considering the value of the surface roughness of the intermediate layer in this way, the unevenness provided on the surface of the intermediate layer appropriately enters the surface layer, and as a result, the scratch resistance in the surface layer is significantly improved. be able to.
Further, since a specific hard coat layer is provided below the intermediate layer, the movement of the intermediate layer can be restricted, and as a result, the scratch resistance of the surface layer can be further improved.
Furthermore, since the surface layer is composed of a fluorine compound or a silicon compound, excellent peelability, heat resistance, antifouling properties, and the like can be obtained.
[0007]
Moreover, when comprising the structure of this invention, it is preferable to make content of the silica particle contained in a hard-coat layer (A) into the value within the range of 5-70 weight%.
By limiting the content of silica particles in this way, the hardness of the hard coat layer can be easily adjusted to a predetermined range, and the movement of the intermediate layer can be constrained. As a result, the scratch resistance in the surface layer can be reduced. Further improvement can be achieved.
[0008]
In constituting the structure of the present invention, the silica particles contained in the hard coat layer (A) are preferably reactive silica particles bonded to an organic compound having a polymerizable unsaturated group.
With such a hard coat layer, excellent adhesion with the intermediate layer can be obtained, and therefore the movement of the intermediate layer can be further restrained, and as a result, the scratch resistance in the surface layer can be further improved. .
[0009]
Further, in constituting the structure of the present invention, the hard coat layer (A) is composed of trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate, penta It is preferably a cured product of an ultraviolet curable resin containing at least one polyfunctional (meth) acrylate selected from the group consisting of erythritol penta (meth) acrylate.
With such a hard coat layer, better adhesion with the intermediate layer can be obtained, and as a result, the scratch resistance of the surface layer can be further improved.
In addition, if the hard coat layer is formed from an ultraviolet curable resin, it can be formed quickly and is economical.
[0010]
Further, in constituting the antireflection film laminate of the present invention, it is preferable that the hardness of the hard coat layer (A) (based on JIS K5400) is H or more on a polyethylene terephthalate (PET) substrate.
With such hardness, the movement of the intermediate layer can be further restricted, and as a result, the scratch resistance in the surface layer can be further improved.
[0011]
In constructing the laminate of the present invention, the surface resistance value is 1 × 10. ^Three ~ 1x10 ¹² A value within the range of Ω / □ is preferred.
With such a surface resistance value, the structure is difficult to be charged, so that it is less likely to attract dust in the air.
[0012]
In constructing the structure of the present invention, the reflectance at a wavelength of 400 to 800 nm is preferably 2.0% or less.
Such a reflectance can be suitably applied to uses such as an antireflection film laminate.
This reflectance is defined as the minimum reflectance in the wavelength region.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The embodiment of the structure of the present invention will be specifically described by taking the antireflection film laminate 24 shown in FIG. 1 as an example.
The antireflection film laminate 24 of FIG. 1 is an antireflection film laminate including a hard coat layer 18, a high refractive index film 20, and a low refractive index film 22 in this order on the substrate 12.
In the antireflection film laminate 24 of FIG. 1, the high refractive index film 20 and the low refractive index film 22 mean an intermediate layer and a surface layer, respectively, in the following description.
[0014]
1. Base material
(1) Kind
The type of base material for providing the hard coat layer is not particularly limited. For example, polyester resin, triacetyl cellulose resin, polycarbonate resin, allyl carbonate resin, polyether sulfone resin, polyacrylate resin, norbornene resin, The base material which consists of acrylic styrene resin and glass etc. can be mentioned.
For example, by using an antireflection film laminate including these base materials, a wide range of antireflection films such as a color filter in a camera lens unit, a television (CRT) screen display unit, or a liquid crystal display device can be used. In addition, not only the antireflection effect but also excellent scratch resistance and transparency can be obtained, and excellent mechanical strength and durability can be obtained.
[0015]
(2) Thickness
Moreover, it is preferable to make the thickness of a base material into the value within the range of 0.02-10 mm.
This is because if the thickness of the substrate is less than 0.02 mm, it may be difficult to firmly fix the hard coat layer or the high refractive index film, while the thickness of the substrate is If it exceeds 10 mm, it may be difficult to produce, or the structure may be excessively thick.
Accordingly, the thickness of the base material is more preferably set to a value within the range of 0.05 to 5 mm, and further preferably set to a value within the range of 0.1 to 3 mm.
[0016]
2. Hard coat layer
(1) Hard coating layer curable composition
Moreover, although it does not restrict | limit especially also about the kind of curable composition for hard-coat layers, It is preferable that it is a hardened | cured material which consists of a photocurable resin composition and a thermosetting resin composition.
[0017]
Moreover, when using a photocurable resin composition, it is preferable to consist of the following structural components, for example.
(1) Silica particles
(2) Acrylic compounds
(3) Photopolymerization initiator
[0018]
(1) Silica particles
The type of silica particles is not particularly limited, but for example, silica sol dispersed in methyl ethyl ketone, water, alcohol, or the like is preferable.
Moreover, it is preferable to make the number average particle diameter of a silica particle into the value within the range of 5-300 nm.
The reason for this is that when the number average particle diameter of the silica particles is less than 5 nm, the hardness of the hard coat layer decreases, and as a result, it may be difficult to improve the scratch resistance of the low refractive index film. Because.
On the other hand, when the number average particle diameter of the silica particles exceeds 300 nm, the dispersibility is lowered and the hardness of the hard coat layer may be lowered.
Therefore, the number average particle diameter of the silica particles is more preferably set to a value within the range of 10 to 200 nm, and further preferably set to a value within the range of 20 to 150 nm.
In addition, the number average particle diameter of a silica particle is an average value of the particle diameter measured with an electron microscope.
[0019]
Moreover, it is preferable to make content of a silica particle into the value within the range of 5-70 weight% with respect to the whole quantity of a hard-coat layer.
The reason for this is that when the content of the silica particles is less than 5% by weight, the hardness of the hard coat layer is lowered, and as a result, the adhesion and binding force to the intermediate layer may be lowered. .
On the other hand, if the content of the silica particles exceeds 70% by weight, the hard coat layer may become brittle.
Accordingly, the content of the silica particles is more preferably set to a value within the range of 10 to 65% by weight, and further preferably set to a value within the range of 20 to 60% by weight.
[0020]
In constituting the antireflection film laminate of the present invention, the silica particles contained in the hard coat layer (A) are preferably reactive silica particles bonded with an organic compound having a polymerizable unsaturated group. .
That is, it is preferable that the silica particles are subjected to surface treatment to form reactive silica particles containing an organic compound having a polymerizable unsaturated group.
For example, an acrylic ester and a silane compound are reacted via an isocyanate compound to produce an organic compound having at least an alkoxysilyl group and a reactive unsaturated bond, and then used to form silica particles. It is preferable to subject the surface to a surface treatment.
[0021]
(2) Acrylic compounds
As the acrylic compound, since it is radically reactive and can be photocured or heat-cured, any (meth) acrylic acid, (meth) acrylic acid ester, or a derivative thereof can be preferably used.
However, since better adhesion can be obtained between the hard coat layer and the high refractive index film (intermediate layer), trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate At least one polyfunctional (meth) acrylate selected from the group consisting of dipentaerythritol penta (meth) acrylate and pentaerythritol penta (meth) acrylate is preferable.
[0022]
(3) Photopolymerization initiator
Examples of the photopolymerization initiator include a photo radical generator and a photo acid generator.
Further, the amount of the photopolymerization initiator used is not particularly limited, but for example, it is preferably set to a value within the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the acrylic compound.
This is because when the amount of the photopolymerization initiator used is less than 0.1 parts by weight, the acrylic compound may be insufficiently cured. On the other hand, when the usage-amount of a photoinitiator exceeds 20 weight part, it is because a photoinitiator remains in a hard-coat layer and hardness may fall.
[0023]
(2) Film thickness
The film thickness of the hard coat layer is set to a value within the range of 1 to 30 μm. This is because when the film thickness of the hard coat layer is less than 1 μm, it is difficult to firmly fix the intermediate layer, and as a result, the scratch resistance of the surface layer may not be improved.
On the other hand, if the film thickness of the hard coat layer exceeds 30 μm, it becomes difficult to produce, or when a structure is formed, warpage is likely to occur or cracks are likely to occur.
Therefore, the thickness of the hard coat layer is more preferably set to a value within the range of 2 to 20 μm, and further preferably set to a value within the range of 3 to 10 μm.
[0024]
(3) Hardness
Moreover, it is preferable that the hardness (based on JIS K5400) of a hard-coat layer shall be H or more on a polyethylene terephthalate (PET) base material.
This is because if the hardness of the hard coat layer is less than H, it is difficult to firmly fix the intermediate layer, and as a result, the scratch resistance of the surface layer may not be improved.
[0025]
(4) Formation method
In forming the hard coat layer, it is preferable to apply (coat) the curable composition for a hard coat layer to a substrate to form a coating film for the hard coat layer.
Such a coating method is not particularly limited. For example, dipping method, spray method, bar coating method, roll coating method, spin coating method, curtain coating method, gravure printing method, silk screen method, or A coating method such as an inkjet method can be used.
Next, since a strong coating film can be formed as a whole, it is preferable that the coating film made of the curable composition for a hard coat layer is UV-cured or thermally cured. In case of UV curing, 0.001 to 10 J / cm using an ultraviolet irradiation device (metal halide lamp, high pressure mercury lamp, etc.) ² It is preferable to carry out under the light irradiation conditions.
This is because, under such irradiation conditions, a hard coat layer having an appropriate hardness can be obtained, while the manufacturing time does not become excessively long.
Therefore, the irradiation condition is 0.01-5 J / cm. ² More preferably, 0.01-1 J / cm ² More preferably.
Moreover, when thermosetting, it is preferable to heat on the conditions of 30-120 degreeC and 1-180 minutes. This is because, under such heating conditions, a hard coat layer can be obtained more efficiently without damaging the substrate.
[0026]
3. High refractive index film
(1) Curable composition 1 for high refractive index film
The curable composition for a high refractive index film for forming the high refractive index film is not particularly limited, but is preferably composed of the following components (A) to (G) as an example.
(A) Inorganic oxide particles
(B) Hydroxyl group-containing polymer
(C) Compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group
(D) Photopolymerization initiator
(E) Acrylate compound
(F) Curing catalyst
(G) Organic solvent
[0027]
(1) (A) Inorganic oxide particles
The number average particle diameter of the inorganic oxide particles as the component (A) is preferably set to a value in the range of 5 to 300 nm.
The reason for this is that when the number average particle diameter of the inorganic oxide particles is less than 5 nm, it becomes difficult to uniformly disperse the inorganic oxide particles in the curable composition for high refractive index film during the production. This is because it may be difficult to uniformly disperse the inorganic oxide particles in the structure.
On the other hand, when the number average particle diameter of the inorganic oxide particles exceeds 300 nm, the transparency of the obtained antireflection film may be lowered, or turbidity (haze value) may be increased.
Therefore, the number average particle diameter of the inorganic oxide particles is more preferably set to a value within the range of 10 to 200 nm, and further preferably set to a value within the range of 20 to 100 nm.
[0028]
The type of inorganic oxide particles (A) is preferably determined in consideration of the ease of refractive index adjustment, transparency, etc. More specifically, silicon oxide (SiO 2 ₂ , Refractive index 1.47), zirconium oxide (ZrO ₂ , Refractive index 2.05), tin oxide (SnO ₂ , Refractive index 2.00), antimony-doped tin oxide (ATO, refractive index 1.95), titanium oxide (TiO 2) ₂ , Refractive index 2.3 to 2.7), zinc oxide (ZnO, refractive index 1.90), tin-doped indium oxide (ITO, refractive index 1.95), cerium oxide (CeO) ₂ , Refractive index 2.2), selenium oxide (SeO) ₂ , Refractive index 1.95), antimony oxide (Sb) ₂ O _Five , Refractive index 1.71), aluminum oxide (Al ₂ O _Three , Refractive index 1.63), yttrium oxide (Y ₂ O _Three , Refractive index 1.87), and zinc antimonate (AZO, refractive index 1.90).
Moreover, it is preferable to perform a silane coupling agent treatment on the inorganic oxide particles. By treating the coupling agent in this way, the bonding force between the inorganic oxide particles in the high refractive index film and the surrounding resin can be increased. As a result, the scratch resistance in the low refractive index film is remarkably improved. This is because it can be improved. In addition, by treating with the coupling agent in this manner, it is possible to improve the dispersibility of the inorganic oxide particles and improve the storage stability of the curable composition for a high refractive index film during production.
In addition, it is preferable to make content of an inorganic oxide particle into the value within the range of 10-90 vol% with respect to the whole quantity of a high refractive index film | membrane.
[0029]
(2) (B) Hydroxyl group-containing polymer
The component (B) can be suitably used as long as it is a polymer having a hydroxyl group in the molecule. More specifically, a single type of polyvinyl acetal resin (polyvinyl butyral resin, polyvinyl formal resin), polyvinyl alcohol resin, polyacrylic resin, polyphenolic resin, phenoxy resin, or a combination of two or more types can be given.
In addition, it is preferable to make the addition amount of a hydroxyl-containing polymer into the value within the range of 1-100 weight part with respect to 100 weight part of inorganic oxide particles.
[0030]
(3) (C) Compound (C) component having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group (hereinafter sometimes referred to as a co-compound) may be a functional group capable of reacting with a hydroxyl group. A compound having a group (sometimes referred to as a hydroxyl-reactive functional group) and a photopolymerizable functional group (sometimes referred to as a photopolymerizable functional group) is preferable.
By adding such a combined compound, the combined compound itself can be photocured using a photopolymerizable functional group, or can be reacted with an acrylate compound described later. In addition, by using a hydroxyl-reactive functional group and heating, it is possible to react the hydroxyl group-containing polymer and the combined compound to form a stronger cured film.
Specific examples of the combined compound include t-butylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N-methacryloxy-N, N-dicarboxymethyl-p-phenylene. Examples thereof include diamine, melamine / formaldehyde / alkyl monoalcohol, 4-methacryloxyethyl trimellitic anhydride, or a combination of two or more.
In addition, it is preferable to make the addition amount of a combined compound into the value within the range of 10-300 weight part with respect to 100 weight part of inorganic oxide particles.
[0031]
(4) (D) Photopolymerization initiator
Examples of the component (D) include a photo radical generator and a photo acid generator.
Further, the amount of the photopolymerization initiator used is not particularly limited, but for example, it is preferably set to a value in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the combined compound.
[0032]
(5) (E) Acrylate compound
The component (E) is a (meth) acrylate compound other than the (meth) acrylate compound in the component (C), and is a compound containing at least one (meth) acryloyl group in the molecule.
Therefore, although the kind in particular is not restrict | limited, For example, they are a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound, or any one (meth) acrylate compound.
Further, the amount of the acrylate compound added is not particularly limited, but for example, a value within the range of 0.01 to 1,000 parts by weight per 100 parts by weight of the inorganic oxide particles is preferable.
[0033]
(6) (F) Curing catalyst
Component (F) is a thermal acid generator or the like, and is aliphatic sulfonic acid, aliphatic sulfonate, aliphatic carboxylic acid, aliphatic carboxylate, aromatic sulfonic acid, aromatic sulfonate, aromatic One kind or a combination of two or more kinds of carboxylic acid, aromatic carboxylate, metal salt, phosphate ester, etc. may be mentioned.
Further, the addition amount of the curing catalyst is not particularly limited, but when the total of the hydroxyl group-containing polymer and the combined compound is 100 parts by weight, the addition amount of the curing catalyst is 0.1-30. A value within the range of parts by weight is preferred.
[0034]
(7) (G) Organic solvent
In the curable resin composition, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, n-butanol, ethyl cellosolve, ethyl lactate (EL), diacetone alcohol (DAA), propylene glycol monomethyl ether (PGME) ), Acetylacetone (AcAc), and at least one organic solvent selected from the group consisting of ethyl acetoacetate (EAcAc) is preferably used.
This is because the use of such an organic solvent makes it easy to control the surface roughness (Rz) of the high refractive index film when forming the high refractive index film from the curable composition for high refractive index film. It is because it becomes.
The amount of the component (G) is not particularly limited, but the amount of the organic solvent added is 50 to 20,000 parts by weight with respect to 100 parts by weight of the inorganic oxide particles (A). A value within the range is preferable.
[0035]
(8) Additive
In the curable composition for high refractive index film, in the range not impairing the purpose and effect of the present invention, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, It is also preferable to further contain additives such as a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.
[0036]
(2) Curable composition 2 for high refractive index film
Moreover, the curable composition obtained by making the following (a-1) and (a-2) react in an organic solvent as another curable composition for high refractive index films | membranes for forming a high refractive index film | membrane. It is also preferable that it is a thing.
(A-1) Conductive metal oxide particles having a primary particle diameter of 0.1 μm or less and a powder resistance of 100 Ω · cm or less
(A-2) In the molecule, urethane bond [—O—C (═O) NH—] and thiourethane bond [—S—C (═O) NH—], or any one urethane bond, unsaturated Alkoxysilane compound having a double bond
Such a curable composition for a high refractive index film is excellent in antistatic properties, transparency, hardness, scratch resistance, and adhesion, and can form a coating film (film) having a high refractive index. it can.
[0037]
(3) Surface roughness (R2)
The surface roughness in the high refractive index film, that is, Rz based on JIS B0601 is defined as R2, and the R2 is set to a value in the range of 0.01 to 2 μm.
The reason for this is that when the surface roughness is less than 0.01 μm, the ratio of the high refractive index film that penetrates into the low refractive index film decreases, and the scratch resistance is remarkably reduced. 2 and 3 show cross-sectional photographs of the antireflection film laminate, and it is understood that a part of the high refractive index film penetrates into the low refractive index film.
On the other hand, when the surface roughness exceeds 2 μm, the surface roughness in the low refractive index film becomes relatively large and light scattering is likely to occur, resulting in a decrease in reflectance and transparency.
Therefore, the surface roughness is preferably set to a value in the range of 0.02 to 1 μm, and more preferably set to a value in the range of 0.05 to 0.5 μm.
[0038]
In the present invention, the ratio (R2 / D1) between the surface roughness (R2) of the high refractive index film and the thickness (D1) of the low refractive index film described later is a value within the range of 0.06 to 2. It is preferable that
The reason for this is that when the ratio of R2 / D1 is less than 0.06, the effect of the surface roughness of the high refractive index film on the low refractive index film is not exhibited, and the scratch resistance is significantly reduced. Because there is. On the other hand, when the ratio of R2 / D1 exceeds 2, the surface roughness in the low refractive index film becomes relatively large and light scattering is likely to occur, resulting in a decrease in reflectance and transparency. Because there is.
Therefore, the ratio of R2 / D1 is preferably set to a value within the range of 0.2 to 2, and more preferably set to a value within the range of 0.4 to 2.
[0039]
(4) Refractive index
Moreover, it is more preferable to make the refractive index (the refractive index of Na-D line, measurement temperature 25 degreeC) in a high refractive index film | membrane into the value within the range of 1.45-2.1.
The reason for this is that when the refractive index is less than 1.45, when combined with a low refractive index film, the antireflection effect may be significantly reduced. This is because usable materials may be excessively limited.
Therefore, the refractive index of the high refractive index film is more preferably set to a value within the range of 1.55 to 2.0, and further preferably set to a value within the range of 1.6 to 1.9. .
[0040]
(5) Film thickness
Moreover, the film thickness of the high refractive index film is not particularly limited, but for example, a value in the range of 0.05 to 0.5 μm is preferable.
The reason for this is that when the film thickness of the high refractive index film is less than 0.05 μm, when combined with the low refractive index film, the antireflection effect and the adhesion to the substrate may decrease, This is because if the film thickness exceeds 0.5 μm, it may be difficult to produce or the ratio of light absorption may increase.
Therefore, the film thickness of the high refractive index film is more preferably set to a value within the range of 0.1 to 0.3 μm, and further preferably set to a value within the range of 0.12 to 0.2 μm.
[0041]
(6) Formation method
In forming the high refractive index film, it is preferable to form a coating film of the curable composition for the high refractive index film, and then perform ultraviolet curing or electron beam curing. In this case, for example, using an ultraviolet irradiation device (a metal halide lamp, a high-pressure mercury lamp, etc.), 0.001 to 10 J / cm ² It is preferable to carry out under the light irradiation conditions.
This is because, under such irradiation conditions, a sufficiently cured high refractive index film can be obtained, while the manufacturing time does not become excessively long.
Therefore, the irradiation condition is 0.01-5 J / cm. ² More preferably, 0.1 to 3 J / cm ² More preferably.
In addition, light irradiation is performed by appropriately changing the conditions such as the kind of particles in the curable composition for high refractive index film, the average particle diameter, the amount of particles added, the solvent type, or the film thickness of the high refractive index film. It is possible to provide irregularities on the surface of the high refractive index film.
[0042]
4). Low refractive index film
(1) Curable composition for low refractive index film
Although it does not restrict | limit especially as a curable composition for low refractive index films | membranes for forming a low refractive index film | membrane, As an example, it is preferable to comprise from the following (a)-(d) component. .
(A) Fluorine-containing copolymer having a hydroxyl group
(B) a thermosetting agent having a functional group capable of reacting with a hydroxyl group
(C) Curing catalyst
(D) Organic solvent
[0043]
(1) (a) Fluorine-containing copolymer having a hydroxyl group
As the component (a), any fluorine-containing copolymer having a hydroxyl group in the molecule can be preferably used. More specifically, it can be obtained by copolymerizing a monomer containing a fluorine atom and a monomer containing a hydroxyl group. Moreover, it is also preferable to add ethylenically unsaturated monomers other than these monomers as needed.
Monomers containing fluorine atoms include tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, (fluoroalkyl) vinyl ether, (fluoroalkoxyalkyl) vinyl ether, One kind or a combination of two or more kinds of fluoro (alkyl vinyl ether), perfluoro (alkoxy vinyl ether), fluorine-containing (meth) acrylic acid ester, etc. may be mentioned.
In addition, although the compounding quantity of the monomer containing a fluorine atom is not restrict | limited in particular, For example, it is preferable that it is a value within the range of 10-99 mol%, More preferably, it is 15-97 mol%. It is a value within the range.
[0044]
Moreover, as a monomer containing a hydroxyl group, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyethyl allyl ether, hydroxybutyl allyl ether, glycerol monoallyl ether, allyl alcohol, One kind of hydroxyethyl (meth) acrylic acid ester or a combination of two or more kinds may be mentioned.
In addition, although the compounding quantity of the monomer containing a hydroxyl group is not restrict | limited in particular, For example, it is preferable that it is a value within the range of 1-20 mol%, More preferably, it is 3-15 mol%. The value is within the range.
[0045]
(2) (b) a thermosetting agent having a functional group capable of reacting with a hydroxyl group
As a thermosetting agent having a functional group capable of reacting with a hydroxyl group (hereinafter sometimes simply referred to as a thermosetting agent), a melamine compound having two or more methylol groups and / or alkoxylated methyl groups in the molecule Is preferably used.
More specifically, methylol melamine compounds such as hexamethyl etherified methylol melamine compounds, hexabutyl etherified methylol melamine compounds, methylbutyl mixed etherified methylol melamine compounds, methyl etherified methylol melamine compounds, butyl etherified methylol melamine compounds, and the like are more preferable. .
Moreover, it is preferable to make the addition amount of a thermosetting agent into the value within the range of 1-70 weight part with respect to 100 weight part of fluorine-containing copolymers which have a hydroxyl group.
[0046]
(3) (c) Curing catalyst
The curing catalyst can be suitably used as long as it promotes the reaction between the hydroxyl group-containing polymer and the curing agent, but the same curing as the curing catalyst in the curable composition for high refractive index film. It is preferred to use a catalyst.
Further, the addition amount of the curing catalyst is not particularly limited, but the total amount of the above-described fluorine-containing copolymer having a hydroxyl group and the thermosetting agent having a functional group capable of reacting with the hydroxyl group is 100 parts by weight. The amount of the curing catalyst added is preferably set to a value in the range of 0.1 to 30 parts by weight.
[0047]
(4) (d) Organic solvent
As the organic solvent used for the curable composition for a low refractive index film, it is preferable to use the same kind as the organic solvent used for the curable composition for a high refractive index film.
In addition, it is preferable to make the addition amount of an organic solvent into the value within the range of 500-10,000 weight part with respect to 100 weight part of fluorine-containing copolymers which have a hydroxyl group.
[0048]
(2) Surface roughness
It is preferable that the surface roughness in the low refractive index film, that is, Rz based on JIS B0601 is defined as R1, and the R1 is set to 2 μm or less.
This is because when the surface roughness exceeds 2 μm, the scratch resistance may be remarkably lowered.
Therefore, the surface roughness is more preferably set to a value of 1.4 μm or less, and further preferably set to a value within the range of 0.02 to 1 μm.
[0049]
The ratio (R1 / D1) between the surface roughness (R1) in the low refractive index film and the film thickness (D1) described later is preferably set to a value in the range of 0.01 to 2.
The reason for this is that when the ratio of R1 / D1 is less than 0.01, the film thickness of the low refractive index film becomes relatively thick, and the influence of the surface roughness of the high refractive index film is not exhibited. This is because the scratch resistance may be significantly reduced. On the other hand, when the ratio of R1 / D1 exceeds 2, the surface roughness in the low refractive index film becomes relatively large and light scattering is likely to occur, resulting in a decrease in reflectance and transparency. Because there is.
Therefore, the ratio of R1 / D1 is preferably set to a value within the range of 0.014 to 1, and more preferably set to a value within the range of 0.014 to 0.8.
[0050]
Further, the ratio (R1 / R2) between the surface roughness (R1) in the low refractive index film and the surface roughness (R2) in the high refractive index film is set to a value in the range of 0.005 to 1. Is preferred.
This is because when the ratio of R1 / R2 is less than 0.005, the effect of the surface roughness of the high refractive index film on the low refractive index film is not exerted, and the scratch resistance is remarkably reduced. is there. On the other hand, if the ratio of R1 / R2 exceeds 1, the surface roughness in the low refractive index film becomes relatively large and light scattering is likely to occur. As a result, the reflectivity and transparency may be lowered. Because there is.
Therefore, the ratio of R1 / R2 is preferably set to a value within the range of 0.1 to 1, and more preferably set to a value within the range of 0.2 to 1.
[0051]
(3) Refractive index
More preferably, the refractive index of the low refractive index film (the refractive index of Na-D line, measurement temperature 25 ° C.) is set to a value in the range of 1.35 to 1.50.
The reason for this is that when the refractive index is less than 1.35, the type of material that can be used may be excessively limited. On the other hand, when the refractive index exceeds 1.5, when combined with a high refractive index film, This is because the antireflection effect may be significantly reduced.
Therefore, the refractive index of the low refractive index film is more preferably set to a value within the range of 1.3 to 1.45, and further preferably set to a value within the range of 1.3 to 1.42.
[0052]
(4) Film thickness (D1)
Further, the film thickness (D1) of the low refractive index film is not particularly limited, but is preferably a value in the range of 0.05 to 2 μm, for example.
This is because, when the film thickness of the low refractive index film is less than 0.05 μm, the adhesion and scratch resistance to the high refractive index film as the base may be lowered. On the other hand, when the film thickness exceeds 2 μm, it may be difficult to form, and the effect of reflecting the surface roughness of the high refractive index film on the low refractive index film may be reduced.
Therefore, the thickness of the low refractive index film is more preferably set to a value within the range of 0.05 to 0.5 μm, and further preferably set to a value within the range of 0.05 to 0.3 μm.
[0053]
(5) Surface resistance
The surface resistance value of the structure is 1 × 10 ^Three ~ 1x10 ¹² A value within the range of Ω / □ is preferred.
This is because the surface resistance value is 1 × 10. ^Three This is because if the value is less than Ω / □, the types of conductive material that can be used are excessively limited, or the amount of conductive material added may have to be increased. On the other hand, the surface resistance value is 1 × 10. ¹² This is because when it exceeds Ω / □, it becomes easy to be charged and attracts dust in the air.
Therefore, the surface resistance value is 1 × 10 ^Three ~ 1x10 ¹¹ A value within the range of Ω / □ is preferable, and 1 × 10 ^Three ~ 1x10 ^Ten A value in the range of Ω / □ is more preferable.
Such a surface resistance value can be easily achieved by adding a conductive material to the low refractive index film or the high refractive index film or adjusting the amount of the hydrophilic group in these films.
[0054]
(6) Formation method
In forming the low refractive index film, the curable composition for the low refractive index film is coated (coated) on the high refractive index film by using, for example, dipping, spraying, bar coating, etc. It is preferable to form a coating film for film formation.
Next, since a strong coating film can be formed as a whole by reacting with a part of the high refractive index film, it is preferable to thermally cure the coating film made of the curable composition for low refractive index film. In this case, it is preferable to heat at 30 to 120 ° C. for 1 to 180 minutes. This is because, under such heating conditions, an antireflection film laminate having excellent antireflection properties can be obtained more efficiently without damaging the base material and the formed antireflection film. is there.
[0055]
【Example】
Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples. Moreover, unless otherwise indicated, the compounding quantity of each component in an Example means the weight part.
[0056]
[Example 1]
(1) Preparation of curable composition for low refractive index film
(1) Preparation of fluorine-containing polymer having a hydroxyl group
After sufficiently replacing the inside of a stainless steel autoclave with an internal volume of 1.5 liters with a magnetic stirrer with nitrogen gas, 500 g of ethyl acetate, 34.0 g of ethyl vinyl ether (EVE), 41.6 g of hydroxyethyl vinyl ether (HEVE), 75.4 g perfluoropropyl vinyl ether (FPVE), 1.3 g lauroyl peroxide, 7.5 g silicone-containing polymer azo initiator (trade name: VPS1001 manufactured by Wako Pure Chemical Industries, Ltd.), reactive emulsifier (Asahi Denka Kogyo Co., Ltd., trade name: NE-30) was charged with 1 g, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.
Next, 119.0 g of hexafluoropropylene (HFP) was further charged, and the temperature increase was started. The pressure when the temperature in the autoclave reaches 70 ° C. is 5.5 × 10 ^Five Pa was shown. Thereafter, the reaction is continued under stirring at 70 ° C. for 20 hours, and the pressure is 2.3 × 10. ^Five When the temperature dropped to Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released, the autoclave was opened, and a polymer solution having a solid content concentration of 30% by weight was obtained. The obtained polymer solution was put into methanol to precipitate a polymer, and further washed with methanol and vacuum dried at 50 ° C. to obtain a fluorine-containing polymer having 170 g of hydroxyl group.
[0057]
It was 0.28 dl / g when the intrinsic viscosity (N, N- dimethylacetamide solvent use, measurement temperature 25 degreeC) was measured about the obtained fluorine-containing polymer which has a hydroxyl group.
Moreover, about this fluorine-containing polymer, it was 31 degreeC when the glass transition temperature was measured on temperature increase rate 5 degree-C / min and the conditions in nitrogen stream using the differential scanning calorimeter (DSC).
Further, with respect to such a fluoropolymer, the fluorine content was measured by using the alizarin complexone method and found to be 51.7%.
Furthermore, when the hydroxyl value of this fluoropolymer was measured by an acetylation method using acetic anhydride, it was 102 mgKOH / g.
[0058]
(2) Preparation of curable composition for low refractive index film
In a vessel equipped with a stirrer, 100 g of the fluorine-containing copolymer having a hydroxyl group obtained in (1), Cymel 303 (Mitsui Cytec Co., Ltd., alkoxylated methylmelamine compound) 11.1 g, methyl isobutyl ketone ( (Hereinafter referred to as MIBK) 3,736 g was added and stirred at 110 ° C. for 5 hours to cause the fluorine-containing copolymer having a hydroxyl group to react with Cymel 303.
Next, 11.1 g of catalyst 4040 (manufactured by Mitsui Cytec Co., Ltd., solid content concentration: 40% by weight) is further added and stirred for 10 minutes, for a low refractive index film having a viscosity of 1 mPa · s (measurement temperature 25 ° C.). A curable composition (hereinafter sometimes referred to as coating solution A) was obtained.
[0059]
In addition, the refractive index of the low refractive index film | membrane obtained from the obtained curable composition for low refractive index films | membranes was measured. That is, the curable composition for a low refractive index film was coated on a silicon wafer (film thickness: 1 μm) using a wire bar coater (# 3) and air-dried at room temperature for 5 minutes to form a coating film. .
Next, the coating film was heated and cured in a hot air dryer at 140 ° C. for 1 minute to form a low refractive index film having a thickness of 0.3 μm. The refractive index of the Na-D line in the obtained low refractive index film was measured using a spectroscopic ellipsometer at a measurement temperature of 25 ° C. As a result, the refractive index was 1.40.
The evaluation of the film thickness was obtained by observing the cross section with a transmission electron microscope, and the film thickness of the coating film with a non-flat interface was the average distance between the lines obtained as a measurement length of 1 μm in the roughness curve defined by JIS B0601. Defined by the distance.
[0060]
(2) Preparation of curable composition for high refractive index film
(1) Production of reactive alkoxysilane
20.6 g of isophorone diisocyanate was added dropwise to a solution composed of 7.8 g of mercaptopropyltrimethoxysilane and 0.2 g of dibutyltin dilaurate in a container under conditions of 50 ° C. and 1 hour in dry air, and then 60 ° C. The mixture was further stirred for 3 hours.
71.4 g of pentaerythritol triacrylate was added dropwise thereto at 30 ° C. for 1 hour, and the mixture was further stirred at 60 ° C. for 3 hours to obtain a reaction solution.
The product in the reaction solution, that is, the amount of residual isocyanate in the reactive alkoxysilane was measured by FT-IR. As a result, it was 0.1% by weight or less, and it was confirmed that each reaction was performed almost quantitatively. Moreover, it confirmed that it had a thiourethane bond, a urethane bond, an alkoxysilyl group, and a reactive unsaturated bond in a molecule | numerator.
[0061]
(2) Preparation of curable composition for high refractive index film
In a vessel equipped with a stirrer, antimony-doped tin oxide dispersion (manufactured by Ishihara Techno Co., Ltd., SNS-10M, dispersion solvent methyl ethyl ketone, antimony-doped tin oxide content 27.4% by weight, solid content 30% by weight, dynamic light scattering Weight average particle diameter of 40 nm, number average particle diameter of 22 nm, and sometimes referred to as ATO fine particle dispersion.) 260 g, 25 g of the reactive alkoxysilane produced in (1), 0.3 g of distilled water, p-Hydroxyphenyl monomethyl ether (0.03 g) was mixed and heated and stirred at 65 ° C. After 5 hours, 8 g of orthoformate methyl ester was added, and the mixture was further heated for 1 hour.
As a photopolymerization initiator, 6.1 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1,708 g of MIBK were added, and the curable composition for high refractive index film (solid content 5 wt%, solid The amount of ATO fine particles in the minute was 78% by weight, hereinafter, sometimes referred to as coating solution B).
In addition, the refractive index and surface roughness (R2) of the obtained curable composition for high refractive index films were measured in the same manner as the curable composition for low refractive index films. The obtained results are shown in Table 1.
[0062]
(3) Preparation of curable composition for hard coat layer
Under dry air, 8.7 g of the reactive alkoxysilane prepared in (2) (1), methyl ethyl ketone-dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, average particle size 22 nm, silica concentration 30 weight) %) 91.3 g, a mixture of isopropyl alcohol 0.2 g, and ion-exchanged water 0.1 g was stirred at 80 ° C. for 3 hours, and then orthoformate methyl ester 1.4 g was added. Stir at the same temperature for 1 hour.
After cooling to room temperature, 21.9 g of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-TMPT) and trimethylolpropane trioxyethyl acrylate (Shin-Nakamura Chemical Co., Ltd.) Co., Ltd., trade name NK Ester A-TMPT-3EO (10.95 g) and 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) 3.27 g are mixed, and hard A curable composition for a coat layer (hereinafter sometimes referred to as coating solution C) was prepared.
[0063]
(4) Production of structure (antireflection film laminate)
The obtained coating liquid C was applied onto a polyester film A4300 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm) using a wire bar coater (# 20), and in an oven at 80 ° C. for 1 minute. It dried on conditions and formed the coating film. Next, in the atmosphere, using a metal halide lamp, 0.3 J / cm ² The coating film was cured with ultraviolet light under the light irradiation conditions to form a 10 μm thick hard coat layer.
Subsequently, the obtained coating liquid B was applied onto the hard coat layer using a wire bar coater (# 12), and dried in an oven at 80 ° C. for 1 minute to form a coating film. Next, in the atmosphere, using a metal halide lamp, 0.3 J / cm ² The coating film was cured with ultraviolet light under the light irradiation conditions to form a high refractive index film having a thickness of 0.1 μm.
Furthermore, the obtained coating liquid A was applied onto the high refractive index film using a wire bar coater (# 3) and air-dried at room temperature for 5 minutes to form a coating film. This coating film was heated using an oven at 140 ° C. for 1 minute to form a low refractive index film having a thickness of 0.1 μm, thereby obtaining an antireflection film laminate.
[0064]
(5) Measurement of surface roughness (Rz)
The surface roughness (Rz) in the low refractive index film (surface layer), the high refractive index film (intermediate layer), and the hard coat layer was measured in accordance with JIS B0601, and was set as R1, R2, and R3, respectively. That is, the cross section of the structure film was determined by observation with a transmission electron microscope, and was determined as the surface roughness R1, R2, R3 in each layer at a measurement length of 1 μm. When Rz has in-plane directionality, the average of Rzx in the x-axis direction and Rzy in the y-axis direction on the horizontal plane was defined as R1, R2, and R3, respectively. The obtained results are shown in Table 1.
[0065]
(6) Evaluation of antireflection film laminate
The scratch resistance of the obtained antireflection film laminate was evaluated according to the following criteria.
Further, the scratch resistance, reflectance, turbidity (haze value), total light transmittance and flexibility of the obtained antireflection film laminate were measured by the following measuring methods.
[0066]
(1) Scratch resistance
The surface of the obtained antireflection film laminate was loaded with # 0000 steel wool at a load of 200 g / cm. ² By rubbing 30 times under the above conditions, the scratch resistance of the antireflection film laminate was visually evaluated from the following criteria. The obtained results are shown in Table 1.
Evaluation 5: No occurrence of scratches was observed.
Evaluation 4: Generation of 1 to 5 scratches was observed.
Evaluation 3: Generation of 6 to 50 scratches was observed.
Evaluation 2: Generation of 51 to 100 scratches was observed.
Evaluation 1: Coating film peeling was observed.
In addition, if the scratch resistance is evaluation 3 or more, it is practically acceptable, and if the scratch resistance is evaluation 4 or more, it is preferable because practical durability is excellent. If it exists, it can be said that it is further preferable because practical durability is remarkably improved.
[0067]
(2) Reflectance
The reflectance (minimum reflectance in the measurement wavelength range) of the obtained antireflection film laminate was measured using a spectral reflectance measuring device (a spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi, Ltd.). Measured in the wavelength range of 340 to 700 nm in accordance with JIS K7105 (Measurement method A).
That is, the minimum reflectance in the antireflection film laminate (antireflection film) at each wavelength was measured using the reflectance in the aluminum deposited film as a reference (100%). The obtained results are shown in Table 1.
[0068]
(3) Turbidity (haze value) and total light transmittance
About the obtained anti-reflective film laminated body, the haze value and the total light transmittance were measured based on JISK7105 using the color haze meter (made by Suga Test Instruments Co., Ltd.). The obtained results are shown in Table 1.
[0069]
(4) Flexibility
The obtained antireflection film laminate was wound around an aluminum rod having a diameter of 25 mm, and the presence or absence of cracks occurring in the antireflection film laminate was visually determined according to the following criteria.
The obtained results are shown in Table 1.
○: No cracks are generated.
Δ: One or two cracks occurred.
X: Three or more cracks occurred.
[0070]
[Examples 2 to 4 and Comparative Examples 1 to 2]
In Examples 2 to 4 and Comparative Examples 1 and 2, the influence of the thickness of the hard coat layer was examined.
That is, as shown in Table 1, the thickness of the hard coat layer in Example 1 was changed from 10 μm to 1 μm (Example 2), 3 μm (Example 3), and 5 μm (Example 4), respectively. The film laminate was evaluated for scratch resistance and the like.
On the other hand, in Comparative Example 1, as shown in Table 1, the thickness of the hard coat layer was set to 0.05 μm and the value below the lower limit of the present invention, and in Comparative Example 2, the thickness of the hard coat layer was similarly set to 60 μm. Except for the value exceeding the upper limit of the present invention, the same antireflection film laminate as in Example 1 was prepared and evaluated for scratch resistance and the like.
The obtained results are shown in Table 1.
[0071]
[Table 1]

[0072]
[Examples 5 to 7 and Comparative Example 3]
In Examples 5 to 7, the influence of the number average particle diameter of the silica particles added to the hard coat layer was examined.
That is, as shown in Table 2, the number average particle diameter of the silica particles added to the hard coat layer in Example 1 is 22 nm to 100 nm (Example 5), 200 nm (Example 6), and 300 nm (Example 7). The antireflection film laminates formed by changing the above to (1) were evaluated for scratch resistance and the like.
On the other hand, in Comparative Example 3, as shown in Table 2, the number average particle diameter of silica particles added to the hard coat layer was 1,000 nm, which was the same as that of Example 1 except that the value exceeded the upper limit of the present invention. An antireflection film laminate was prepared and evaluated for scratch resistance and the like.
The obtained results are shown in Table 2.
[0073]
[Table 2]

[0074]
[Examples 8 to 10]
In Examples 8 to 10, the influence of the surface treatment on the silica particles added to the hard coat layer was examined.
That is, as shown in Table 3, the acryl-modified silica particles added to the hard coat layer in Example 1 were treated with dimethyldimethoxysilane (trade name: AY-43-004, manufactured by Toray Dow Corning Silicone Co., Ltd.). Silica particles surface-treated with (Example 8), γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd., trade name: SH6040) surface-treated silica particles (Example 9), In addition, the antireflection film laminate formed by changing to silica particles (Example 10) not subjected to surface treatment was evaluated for scratch resistance and the like.
The obtained results are shown in Table 3.
[0075]
[Table 3]

[0076]
[Examples 11 to 13]
In Examples 11 to 13, the relationship between the amount of silica particles added to the hard coat layer and the hardness was examined.
That is, as shown in Table 4, the amount of silica particles added to the hard coat layer in Example 1 was changed from 37% by weight to 19% by weight (Example 11), 56% by weight (Example 12), and The antireflection film laminate formed by changing to 66% by weight (Example 13) was evaluated for scratch resistance, hardness, and the like.
Table 4 shows the obtained results.
[0077]
[Table 4]

[0078]
[Examples 14 to 16]
In Examples 14-16, the influence of the kind of acrylic ester contained in the ultraviolet curable resin which comprises a hard-coat layer was examined.
That is, as shown in Table 5, trimethylolpropane triacrylate (abbreviated as TMPTA) and trimethylolpropane trioxyethyl acrylate (abbreviated as EO-TMPTA) as acrylic acid esters used in Example 1. , TMPTA alone (Example 14), dipentaerythritol pentaacrylate (abbreviated as DPPA) (Example 15), and pentaerythritol triacrylate (abbreviated as PETA) (Example 16). The antireflection film laminate was evaluated for scratch resistance and the like.
The results obtained are shown in Table 5.
[0079]
[Table 5]

[0080]
【The invention's effect】
According to the structure of the present invention, on the base material, a specific (A) hard coat layer, (B) an intermediate layer, and (C) a surface layer are included, and (A) to (C) layers are configured. Considering the contents and considering the value of the surface roughness in the layer (B), it is possible to provide a structure excellent in scratch resistance and transparency while having a simple structure. .
Therefore, even if a fluorine compound or a resin having poor scratch resistance of a silicon compound is used for the surface layer in order to lower the refractive index, the present invention has a structure that exhibits excellent scratch resistance without impairing transparency. The body can now be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of an example of an antireflection film laminate of the present invention.
FIG. 2 is a cross-sectional photograph of an antireflection film laminate of the present invention (part 1).
FIG. 3 is a cross-sectional photograph of the antireflection film laminate of the present invention (part 2).
[Explanation of symbols]
12 Base material
13 Intrusion part of high refractive index film
18 Hard coat layer
20 High refractive index film (intermediate layer)
22 Low refractive index film (surface layer)
24 Antireflection film laminate

Claims (7)

On the base material, the hard coat layer curable composition is applied to form a hard coat layer (A) having a film thickness of 1 to 30 μm containing silica particles having a number average particle diameter of 5 to 300 nm ,
An intermediate layer (B) having a film thickness of 0.05 to 0.5 μm containing inorganic oxide particles having a number average particle diameter of 5 to 300 nm is applied on the (A) layer by applying the curable composition for intermediate layer. And an intermediate layer (B) provided with irregularities having a surface roughness Rz (based on JIS B0601) of 0.01 to 2 μm is formed on the surface,
A curable composition for a surface layer is applied on the surface of the (B) layer provided with irregularities, and a refractive index lower than that of the (B) layer, a fluorine compound and a silicon compound, or any one compound The surface layer (C) having a film thickness of 0.05 to 0.5 μm containing bismuth is formed by allowing the unevenness of the layer (B) to enter the layer (C). (A)-(C) The manufacturing method of the transparent structure which laminated | stacked the layer. Manufacturing method according to claim 1, characterized in that a value within the range of 5 to 70 wt% and the content of the silica particles contained in the hard coat layer (A). The silica particles contained in the hard coat layer (A), manufacturing method of claim 1 or 2, characterized in that the reactive silica particles with an organic compound having a polymerizable unsaturated group. The hard coat layer (A) is selected from the group consisting of trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol penta (meth) acrylate. at least one multifunctional (meth) manufacturing method according to claim 1 which is a cured product of the ultraviolet-curing resin containing acrylate being. Manufacturing method according to any one of claims 1 to 4, the hardness (JIS K5400 compliant) is equal to or is H or on a polyethylene terephthalate (PET) base material of the hard coat layer (A). Manufacturing method according to any one of claims 1 to 5, characterized in that a value within the range of surface resistivity ^{1 × 10 3 ~1 × 10 12} Ω / □ of the structure. Manufacturing method according to any one of claims 1 to 6, wherein the reflectance of the wavelength 400~800nm of the structure is not more than 2.0%.

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