JP4505346B2 - Antireflection film, polarizing plate, and display device - Google Patents

Description

  The present invention relates to a curable composition for obtaining an antifouling cured film and an optical film used for optical applications using the same, particularly an antireflection film provided with an antifouling cured film, a polarizing plate, and The present invention relates to a display device using them, an antifouling hard coat film, and an optical information recording carrier using the antifouling hard coat film. Specific examples of the optical film include, for example, an optical compensation film for a liquid crystal display device, a brightness enhancement film, an optical compensation film for a projection display device, and various functional films applied to an organic EL display.

  In general, anti-reflection films are installed on the surface of optical products, etc. to reduce reflectivity by using the principle of optical interference in order to prevent contrast degradation and image reflection due to reflection of external light, and are particularly good In an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), or a liquid crystal display (LCD) that requires high visibility, it is disposed on the outermost surface of the display surface.

  In many usual examples, such an antireflection film can be produced by forming a low refractive index layer having an appropriate thickness on a high refractive index layer. A low refractive index layer material is desired to have a refractive index as low as possible from the viewpoint of antireflection performance. The In addition, the uniformity of the film thickness is also important in order to exhibit low reflectance performance, and in the coating type material, the coating property and leveling property are also important factors.

  In order to realize high scratch resistance in a thin film having a thickness of around 100 nm, it is important to increase the strength of the coating itself and the adhesion to the lower layer. As means for lowering the nodule rate of the material, there are means such as (1) introduction of fluorine atoms and (2) reduction of density (introduction of voids). Is also in the direction of damage.

  On the other hand, base materials such as metal, glass, and resin have been widely used as automobile parts, OA equipment, home appliances, etc., but the surface of these base materials is free from dust that floats in the car, office, room, etc. Because it adheres, oily substances that are difficult to wipe off that are mixed with food, oil for equipment, etc. adhere to it, and fingerprints adhere by human hands during use, making it difficult to adhere dirt, The dirt once attached has been devised for scratch resistance and antifouling so that it can be easily removed without damaging the film surface.

  In particular, fingerprints, sebum, sweat, and cosmetics are used by humans for optical components such as antireflection films, polarizing plates, optical filters, optical lenses, liquid crystal displays, CRT displays, projection televisions, plasma displays, and EL displays. In many cases, such as dirt adheres. Such dirt is not easy to remove once attached, and in particular, in the optical member with an antireflection film, the attached dirt becomes conspicuous and becomes a problem.

Accordingly, various antifouling protective layers containing a siloxane component and a fluorine atom-containing copolymer have been proposed in order to protect the surface of the substrate from dirt and improve the scratch resistance.
For example, Patent Document 1 discloses a curable composition containing a siloxane compound containing at least two hydroxyl groups in the molecule and having perfluoroalkyl groups bonded to both ends and a curing agent. A polymer film of a copolymer of an ether component and a vinyl silane compound is disclosed.
However, even in these antifouling layer forming techniques, the antifouling property is insufficient, and in particular, dirt such as fingerprints, sebum, sweat, cosmetics, etc. is difficult to wipe off, and the antifouling performance is greatly reduced with use.

  In particular, it has been conventionally performed to provide an antifouling film on the surface of an optical member that can prevent a decrease in contrast and reflection of an image due to reflection of external light. Such an antifouling layer installed on the outermost surface of the optical member is required to have an antireflection function as well as an antifouling function. In order to impart an antireflection function, it is required to be a low refractive index layer that reduces the reflectance by using the principle of optical interference without impairing the optical characteristics. Therefore, a surface layer having a low refractive index and having excellent antifouling properties and scratch resistance can be used for antireflection purposes and antifouling purposes. It is useful because it can be widely applied to usage.

  As a means for improving the scratch resistance while maintaining a low refractive index, it is effective to impart slipperiness to the surface. For imparting slipperiness, techniques such as introduction of a fluorine compound and introduction of a silicone compound are effective, and these means reduce the surface tension, so that an effect can also be expected to impart leveling ability. When a fluorine-containing polymer is used for the low refractive index layer, it itself has slipperiness, but it has a short side chain in which about 50 mol% of a hydrocarbon-based copolymer component is introduced to solubilize the coating solvent. A system material alone does not provide sufficient slipperiness, and has been conventionally combined with a silicone compound.

  By adding a small amount of a silicone compound to the low refractive index layer material, the effect of improving the slipping property and the effect of improving the scratch resistance are remarkably exhibited. In addition to slipperiness, effects such as water repellency and antifouling properties are also exhibited. However, on the other hand, compatibility with low refractive index layer materials (transparency of coating), bleeding out over time or high temperature conditions, transfer of silicone component to contact medium, performance degradation accompanying these, degradation of production line There were various problems such as contamination. Particularly in an antireflection film, the generation of haze due to incompatibility is a serious problem because it deteriorates optical performance. Further, when the coated film is wound up, the adhesion of silicone to the back surface of the film is a serious problem because it hinders subsequent processing steps. That is, there is a demand for a technique in which only the silicone part is effectively segregated on the surface and the remaining part bonded to the silicone is effectively anchored in the low refractive index layer film.

Next, the optical information record carrier will be described.
Conventionally, a record carrier called CD-R is widely known as a write-once type optical information record carrier capable of recording information only once with a laser beam. The CD-R has an advantage that it can be reproduced using a commercially available CD player, and recently, the demand for the CD-R has increased with the spread of personal computers. Further, as an information recording carrier capable of recording a larger capacity than a CD-R, a write-once digital versatile disc (DVD-R) for supporting digital high-definition recording has been put into practical use.

  As these recordable optical information recording carriers, for example, on a disc-like support, a light reflecting layer made of Au or the like, a recording layer made of an organic compound, and a light-transmitting layer (recording layer) for protecting the recording layer And a cover layer are also sequentially stacked. Recording and reproduction are performed by irradiating a laser beam from the light-transmitting layer side. be able to. Information is recorded on the write-once type optical information record carrier when the laser light irradiation portion of the recording layer absorbs the light and locally generates heat (for example, generation of pits). On the other hand, information reproduction is usually performed by irradiating a write-once optical information recording carrier with a laser beam having the same wavelength as the recording laser beam, so that the recording layer is heated and deformed (recorded portion) and not deformed ( This is done by detecting the difference in reflectance from the unrecorded portion.

  Recently, networks such as the Internet and high-definition TV are rapidly spreading. Also, HDTV (High Definition Television) has started to be broadcast. Under such circumstances, there is a need for a large-capacity optical information record carrier capable of recording image information inexpensively and easily. The DVD-R plays a role as a large-capacity record carrier at present, but the demand for larger capacity and higher density is increasing, and the development of a record carrier that can meet these demands is also necessary. It is. For this reason, as an optical information record carrier, high density recording can be performed with light of a shorter wavelength, and development of a larger capacity record carrier is underway. In particular, write-once type optical information record carriers capable of recording information only once are frequently used for long-term storage or backup of large-capacity information, and thus there is a strong demand for development.

  Usually, the density of optical information record carriers is increased by reducing the beam spot by shortening the wavelength of the recording and reproducing laser and increasing the NA of the objective lens used for the pickup (Numerical Aperture). be able to. Recently, development has rapidly progressed from red semiconductor lasers with wavelengths of 680 nm, 650 nm, and 635 nm to blue-violet semiconductor lasers with wavelengths of 350 nm to 500 nm (hereinafter referred to as blue-violet lasers) that enable ultra-high density recording. Therefore, development of optical information record carriers corresponding to this is also underway. In particular, since the release of the blue-violet laser, development of an optical recording system using the blue-violet laser and a high NA pickup has been studied. A rewritable optical information recording carrier and optical recording system having a phase-change recording layer are: It has already been announced as a DVR system (for example, see Non-Patent Document 1). Thereby, a certain result was obtained with respect to the problem of high density in the rewritable optical information record carrier.

The optical information recording carrier used in the optical recording system using the blue-violet laser and the high NA pickup as described above is a laser for focusing the high-NA objective lens when the recording layer is irradiated with the blue-violet laser light. It is preferable to thin the light-incident layer from the surface of the information record carrier on which light is incident, that is, the translucent layer. Therefore, according to the standard, the thickness of the light transmitting layer is set to 100 μm. Since such an optical information record carrier uses a high NA pickup as described above, the distance between the pickup and the translucent layer is small, and the pickup and the translucent layer are in contact with each other due to surface blurring of the optical information record carrier. As a result, the light-transmitting layer is likely to be damaged.
In order to solve this problem, a method for preventing scratches on the light-transmitting layer by providing a scratch-preventing layer or a hard coat layer on the light-transmitting layer using a spin coating method or a vacuum deposition method has already been proposed (for example, patents). References 3 and 4). However, since these scratch-preventing layers and hard coat layers are provided in a single-wafer type on the light-transmitting layer, there is a problem that productivity is low. Further, when these scratch-preventing layers and hard coat layers are provided by the spin coating method, the outer peripheral layer thickness tends to increase due to centrifugal force, and the thickness accuracy is not sufficient.

On the other hand, there is a method of forming a light-transmitting layer by using a transparent and thin film such as a cellulose acylate film and adhering to a recording layer using an adhesive or a pressure-sensitive adhesive. The thickness of the light transmitting layer is usually about 100 μm including the adhesive layer or the adhesive layer formed by curing the adhesive or the adhesive, but is optimized by the wavelength of the irradiated laser and the NA. Although the information recording carrier constituted by such a method is excellent in productivity, the commercially available cellulose acylate film has at least one of 15 to 20% by mass of phosphate ester and phthalate ester. The plasticizer is contained, and under high temperature and high humidity conditions, the size may change due to the migration of plasticizer or decrease due to volatilization, resulting in problems such as curling and deterioration of adhesive strength. As a result, there is a problem that information cannot be recorded or recorded information cannot be read.
Further, the optical information recording carrier using a film made of cyclic polyolefin for the light-transmitting layer cannot be said to have sufficient surface scratch resistance.
International Publication No. 95/33001 JP-A-9-157582 Japanese Patent No. 311467 JP 2000-67468 A Optical Memory International Symposium (ISOM2000) Proceedings, p. 210-211

An object of the present invention is to provide a coating composition and an antifouling optical film which have good antifouling properties and excellent antifouling durability and scratch resistance. By using this coating composition as a low refractive index layer material, an antireflection film having a low reflectivity and excellent in antifouling property, antifouling durability and scratch resistance can be obtained.
Another object of the present invention is to provide an anti-fouling property and anti-fouling by providing a hard coat layer containing the above coating composition on a light-transmitting layer in an information recording carrier capable of reproducing an information signal by optical means. An object of the present invention is to provide an information record carrier that is excellent in durability and scratch resistance and that can be recorded and reproduced satisfactorily.

［４］
前記フッ素原子を含むテロマー型アクリレートが下記ａ−７〜ａ−１０から選ばれる少なくともいずれか１種であることを特徴とする［１］〜［３］のいずれかに記載の反射防止フィルム。

［５］
偏光層とこれを挟む２枚の保護フィルムからなる偏光板であって、［１］〜［４］のいずれかに記載の反射防止フィルムを、該２枚の保護フィルムの少なくとも一方に用いたことを特徴とする偏光板。
［６］
［１］〜［４］のいずれかに記載の反射防止フィルムを有し、該反射防止フィルムの低屈折率層が視認側になるように配置したことを特徴とするディスプレイ装置。
なお、本発明は上記［１］〜［６］に関するものであるが、参考のため例えば下記１〜８など、その他の事項についても記載した。
１．基材上に、フッ素原子を含むテロマー型アクリレートを２質量％〜１０質量％含有する放射線硬化樹脂を含む組成物から形成された層を有することを特徴とする光学フィルム。
２．基材上に、反射防止層を有し、かつフッ素原子を含むテロマー型アクリレートを２質量％〜１０質量％含有する放射線硬化樹脂を含む組成物から形成された層を有することを特徴とする反射防止フィルム。
３．偏光層とこれを挟む２枚の保護フィルムからなる偏光板であって、上記２に記載の反射防止フィルムを、該２枚の保護フィルムの少なくとも一方に用いたことを特徴とする偏光板。
４．上記２に記載の反射防止フィルムを有し、該反射防止フィルムの低屈折率層が視認側になるように配置したことを特徴とするディスプレイ装置。
５．基材上にハードコート層を有するハードコートフィルムであって、該ハードコート層が上記１に記載の放射線硬化樹脂の硬化皮膜からなり、スチールウールによる摩擦前後のヘイズ値の差（ΔＨ）が５％〜０．０１％であることを特徴とするハードコートフィルム。
６．硬化皮膜内部のＦ／Ｃと、硬化皮膜表面のＦ／Ｃの比が１／２０〜１／１であることを特徴とする上記５に記載のハードコートフィルム。ここで、Ｆ／Ｃとは、ハードコートフィルムをエッチングＥＳＣＡで測定した際のＦのスペクトル強度とＣのスペクトル強度の比である。
７．支持体上に記録層および透光層を具備する光情報記録担体において、該透光層に上記５ないし６に記載のハードコートフィルムを用いることを特徴とする光情報記録担体。
８．３５０ｎｍ〜５００ｎｍの波長を有する光により記録されることを特徴とする上記７に記載の光情報記録担体。 The above object of the present invention, reflection preventing film are shown in the following, are achieved by the polarizing plate, and a display device.
[1]
Having a low refractive index layer formed from a composition comprising a radiation curable resin having an antireflection layer and containing 2% by mass to 10% by mass of a telomer acrylate containing a fluorine atom on the substrate; The radiation curable resin is a radical polymerizable compound as a polyfunctional compound containing 2 to 10 polymerizable groups, and the reflectance of the low refractive index layer is 1.20 to 1.49, An antireflection film, wherein the refractive index layer has a thickness of 10 to 400 nm.
[2]
Content of the said telomer type acrylate containing the fluorine atom in the said composition is 3 mass%-8 mass%, The antireflection film as described in [1] characterized by the above-mentioned.
[3]
The antireflection film as described in [1] or [2], wherein the telomer acrylate containing a fluorine atom is at least one selected from the following a-1 to a-10.

[4]
The antireflective film according to any one of [1] to [3], wherein the telomer acrylate containing a fluorine atom is at least one selected from the following a-7 to a-10.

[5]
A polarizing plate comprising a polarizing layer and two protective films sandwiching the polarizing layer, wherein the antireflection film according to any one of [1] to [4] is used for at least one of the two protective films A polarizing plate characterized by.
[6]
A display device comprising the antireflection film according to any one of [1] to [4], and disposed so that a low refractive index layer of the antireflection film is on a viewing side.
In addition, although this invention is related to said [1]-[6], other matters, such as the following 1-8, were also described for reference.
1. An optical film comprising a layer formed from a composition containing a radiation curable resin containing 2% by mass to 10% by mass of a telomer acrylate containing a fluorine atom on a substrate.
2. A reflection comprising an antireflection layer on a substrate and a layer formed from a composition containing a radiation curable resin containing 2% by mass to 10% by mass of a telomer acrylate containing a fluorine atom Prevention film.
3. A polarizing plate comprising a polarizing layer and two protective films sandwiching the polarizing layer, wherein the antireflection film described in 2 is used for at least one of the two protective films.
4). 3. A display device comprising the antireflection film as described in 2 above, wherein the low refractive index layer of the antireflection film is disposed on the viewing side.
5). A hard coat film having a hard coat layer on a substrate, the hard coat layer comprising the cured film of the radiation curable resin described in 1 above, and a difference (ΔH) in haze value before and after friction with steel wool is 5 % To 0.01% of a hard coat film.
6). 6. The hard coat film as described in 5 above, wherein the ratio of F / C inside the cured film and F / C on the surface of the cured film is 1/20 to 1/1. Here, F / C is the ratio of the spectral intensity of F and the spectral intensity of C when the hard coat film is measured by etching ESCA.
7). An optical information recording carrier comprising a recording layer and a translucent layer on a support, wherein the hard coat film described in 5 to 6 is used for the translucent layer.
8. The optical information record carrier as described in 7 above, which is recorded with light having a wavelength of 350 nm to 500 nm.

Antireflective film excellent in antifouling property, antifouling durability and scratch resistance by using a radiation curable resin containing 2% by mass to 10% by mass of a telomer type acrylate containing a fluorine atom as a low refractive index layer material When the ratio of F / C in the cured film to F / C on the surface of the cured film is 1/20 to 1/1, particularly high antifouling durability is obtained.
Furthermore, the polarizing plate excellent in antifouling property, antifouling durability, and abrasion resistance can be obtained by laminating the antireflection film of the present invention to the polarizing plate.
Further, in the optical information recording carrier, an optical information recording excellent in antifouling property, antifouling durability, scratch resistance and recording characteristics by providing a hard coat layer containing the radiation curable resin on the light transmitting layer. A carrier is provided.

  Hereinafter, the antifouling coating composition (antifouling agent) having good antifouling property and excellent antifouling durability and scratch resistance used for forming the antifouling coating film (antireflection film) of the present invention. Will be described in detail.

[Radiation curable resin]
The radiation curable resin used in the present invention is a radical polymerizable compound as a polyfunctional compound containing 2 to 10 polymerizable groups. As a specific example, an unsaturated carboxylic acid (for example, acrylic acid) is used. Methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
In the present invention, among the radiation curable resins, telomer acrylate containing fluorine atoms is distinguished as an antifouling agent, and 2 mass% to 10 mass% of telomer acrylate containing fluorine atoms is contained with respect to the radiation curable resin. Thus, a radiation-cured film excellent in antifouling property, antifouling durability and scratch resistance can be obtained.
[Telomer-type acrylate containing fluorine atoms]
The radiation curable resin as a component of the antifouling coating composition (antifouling agent) characterized by containing a telomer acrylate containing a fluorine atom has, for example, a polymerization degree n represented by the following general formula (1) of k. This is a mixture of fluorine-containing (meth) acrylic acid esters (hereinafter also referred to as “telomer acrylate containing fluorine atoms” or simply “telomer”). This mixture has a degree of polymerization n of k, k + 1, k + 2,. . . Is a mixture of telomers. However, this mixture may inevitably contain telomers where n is smaller than k, depending on the conditions of telomerization and the separation conditions of the reaction mixture.
By curing such a curable resin to form a low refractive index layer, a hard coat layer, or an antifouling layer of an antireflection film, fluorine can be present on the surface and inside of the cured film.
In addition, the content of the telomer acrylate containing a fluorine atom in the composition is preferably 3% by mass to 8% by mass, and more preferably 4% by mass to 6% by mass.

As specific examples of the curable resin as an antifouling agent, n in the group Rf (CF ₂ CF ₂ ) nR ² CH ₂ CH ₂ O— in the following general formula (1) is k, k + 1, k + 2, . . . Is a mixture containing a plurality of fluorine-containing (meth) acrylic acid esters.

General formula (1):
_{Rf (CF 2 CF 2) n} CH 2 CH 2 R 2 OCOCR 1 = CH 2

(In the formula, Rf represents any of a fluoroalkyl group having 1 to 10 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an alkylene group, and n represents a polymerization degree. The degree of polymerization n is k or more (k is any integer of 3 or more).)
Examples of the telomer acrylate containing a fluorine atom in the general formula (1) include a (meth) acrylic acid moiety or a fully fluorinated alkyl ester derivative.

  Specific examples of the telomer acrylate containing a fluorine atom used in the present invention are shown below, but the present invention is not limited thereto.

Next, the antireflection film of the present invention will be described.
[Layer structure of antireflection film]
A typical layer structure of the antireflection film of the present invention will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing a preferred layer structure of a preferred antireflection film. The embodiment shown in FIG. 1A has a layer structure in the order of a transparent support 4, a hard coat layer 3, a high refractive index layer 2, and a low refractive index layer 1. In the antireflection film having the high refractive index layer 2 and the low refractive index layer 1 as shown in (a), as described in JP-A-59-50401, the high refractive index layer is represented by the following formula ( i) It is preferable that the low refractive index layer satisfies the following formula (ii).

In formula (i), m is a positive integer (generally 1, 2 or 3), n ₁ is the refractive index of the high refractive index layer, and d ₁ is the layer thickness (nm) of the high refractive index layer. It is.

In formula (ii), n is a positive odd number (generally 1), n ₂ is the refractive index of the low refractive index layer, and d ₂ is the layer thickness (nm) of the low refractive index layer.

The refractive index n ₁ of the high refractive index layer is generally at least 0.05 higher than that of the transparent film, and the refractive index n ₂ of the low refractive index layer is generally at least 0.1 lower than the refractive index of the high refractive index layer and is transparent. At least 0.05 lower than the film. Further, the refractive index n ₁ of the high refractive index layer is generally in the range of 1.57 to 2.40.

  The embodiment shown in FIG. 1B has a layer structure in the order of a transparent support 4, a hard coat layer 3, a medium refractive index layer 5, a high refractive index layer 2, and a low refractive index layer 1. As shown in (b), the antireflective film having the medium refractive index layer 5, the high refractive index layer 2 and the low refractive index layer 1 has a medium refractive index as described in JP-A-59-50401. It is preferable that the refractive index layer satisfies the following mathematical formula (iii), the high refractive index layer satisfies the following mathematical formula (iv), and the low refractive index layer satisfies the following mathematical formula (v).

In formula (iii), h is a positive integer (generally 1, 2 or 3), n3 is the refractive index of the medium refractive index layer, and d ₃ is the layer thickness (nm) of the medium refractive index layer. is there.

In formula (iv), j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the layer thickness (nm) of the high refractive index layer. It is.

In the formula (v), k is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer, and d ₅ is the layer thickness (nm) of the low refractive index layer.

The refractive index n ₃ of the medium refractive index layer is generally in the range of 1.5 to 1.7, and the refractive index n ₄ of the high refractive index layer is generally in the range of 1.7 to 2.2.

  The embodiment shown in FIG. 1C has a layer structure in the order of a transparent support 4, an antiglare hard coat layer 6, and a low refractive index layer 1. In such an antireflection film, for example, as described in JP-A No. 2001-281410, the low refractive index layer preferably satisfies the following mathematical formula (vi).

In the formula (vi), m is a positive odd number (generally 1), n ₆ is the refractive index of the low refractive index layer, and d ₆ is the layer thickness (nm) of the low refractive index layer.

In the formulas (i) to (vi), λ is the wavelength of light, and when used as an antireflection layer in the visible region, λ is a value in the range of 380 to 680 nm. It is also effective for ultraviolet and infrared rays in the vicinity of the region. The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers. For example, the medium refractive index layer is produced by a method such as changing the content of the high refractive index inorganic fine particles added to the high refractive index layer.
In the antireflection film of the present invention having the above layer structure, at least a low refractive index layer improved according to the present invention is used.

[Low refractive index layer]
The low refractive index layer is arranged on the upper layer of the high refractive index layer as shown in FIGS. 1 (a), (b) and (c). Usually, the upper side of the low refractive index layer is the surface of the antireflection film.
The refractive index of the low refractive index layer is preferably 1.20 to 1.49, more preferably 1.20 to 1.45, and particularly preferably 1.20 to 1.43.
The thickness of the low refractive index layer is preferably 10 to 400 nm, and more preferably 30 to 200 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a 1 kg load pencil hardness test (JIS-K-5400). .

  A particularly preferable embodiment in which the object of the present invention can be achieved is an embodiment in which the low refractive index layer comprises a matrix layer containing the above-described composition containing a telomer acrylate containing fluorine atoms and cured by the following curing agent. In addition, the content of the telomer acrylate containing a fluorine atom in the composition is preferably 3% by mass to 8% by mass, and more preferably 4% by mass to 6% by mass.

In the composition for forming a low refractive index layer of the present invention, at least one of a curing agent and a curing accelerator is used in combination. These can be used by appropriately selecting conventionally known ones according to the curing reaction of the crosslinkable reactive sites in the composition for forming a low refractive index layer.
For example, the compounds described in Shinzo Yamashita, Tosuke Kaneko, “Crosslinking Agent Handbook” published by Taiseisha (1981) “Polymer Data Handbook Fundamentals” edited by Polymer Society of Japan (1986), etc. Can do.
Specifically, organic silane compounds, polyisocyanate compounds, polyol compounds, polyamine compounds, acid anhydride compounds, polyepoxy group-containing compounds, and epoxy resins (for example, “New Epoxy Resins” written by Hiroshi Horiuchi) (Published in 1985), “Epoxy resin” written by Kuniyuki Hashimoto, “Nikkan Kogyo Shimbun” (published in 1969), melamine resin (for example, “Yulia Melamine Resin” edited by Ichiro Miwa, Hideo Matsunaga, Nikkan Kogyo Shimbun) (Compounds described in 1969), etc.), poly (meth) acrylate compounds (for example, Nobu Okawara, Takeo Saegusa, Toshinobu Higashimura “Oligomer” Kodansha (1976), Eizo Omori “Functional Acrylic” Compounds described in "System Resin" Techno System (1985) and the like.

  In the composition for forming a low refractive index layer of the present invention, it is preferable to use a radical polymerizable compound as a curing agent and a compound that generates radicals by at least one of light irradiation and heating as a curing accelerator. The radically polymerizable compound is preferably a polyfunctional compound containing 2 to 10 polymerizable groups, more preferably 2 to 6 polyfunctional compounds.

  It is preferable that a polymerizable compound having a polymerizable group having good copolymerizability with a radical polymerizable group contained in the composition for forming a low refractive index layer is appropriately selected and combined as a curing agent. Examples of such compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Also, addition reaction products of unsaturated carboxylic acid esters and amides having nucleophilic substituents such as hydroxyl group, amino group and mercapto group with monofunctional or polyfunctional isocyanates and epoxies, hydroxyl group and amino group A dehydration condensation reaction product of an unsaturated carboxylic acid ester / amide having a nucleophilic substituent such as a group / mercapto group and a polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

Examples of the aliphatic polyhydric alcohol compound include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, trimethylolpropane, hexanediol, cyclohexyldiol, cyclohexanedimethanol, pentaerythritol, sorbitol, and the like. Examples thereof include mono-substituted or poly-substituted polymerizable compounds with unsaturated carboxylic acids (crotonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc.).
Examples of other ester curing agents include, for example, vinyl methacrylate, allyl methacrylate, allyl acrylate, aliphatic alcohols described in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231. Esters, those having aromatic skeletons described in JP-A-59-5240, JP-A-59-5241, JP-A-2-226149, and amino groups described in JP-A-1-165613 The thing containing is used suitably.

  Specific examples of monomer curing agents for amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexa. Examples include methylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Examples of other preferable amide monomer curing agents include those having a cyclohexylene structure described in JP-B No. 54-21726.

Further, urethane-based addition polymerizable compounds produced using an addition reaction of isocyanate and hydroxyl group are also suitable as the curing agent, and specific examples thereof are described in, for example, Japanese Patent Publication No. 48-41708. Examples thereof include vinylurethane compounds containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group to a compound having two or more isocyanate groups per molecule.
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418.

  Further, as a curing agent, a radical polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Kinds may be used.

  Examples of other curing agents include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

Furthermore, a fluorine atom-containing monofunctional or polyfunctional compound is also preferable as the curing agent, and examples thereof include compounds described in paragraphs [0059] to [0066] in JP-A 2000-275403.
As the initiator for radical polymerization and crosslinking reaction, any form of those that generate radicals by the action of heat or those that generate radicals by the action of light is possible.

As the initiator by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, onium compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p Examples of the onium compound such as -nitrobenzenediazonium include the same compounds as those described for the hydrolyzable silyl group.

  When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays. Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be preferably used in combination with these photoradical polymerization initiators.

  The amount of the compound that initiates radical polymerization or crosslinking reaction by the action of heat or light may be any amount that initiates polymerization or crosslinking of carbon-carbon double bonds, but is generally a film-forming composition. 0.1-15 mass% is preferable with respect to the total solid content in it, More preferably, it is 0.5-5 mass%.

  When these curing agents are added, like the other curing agents, an addition amount of about 0.5 to 300 parts by mass is preferable per 100 parts by mass of the composition for forming a low refractive index layer. An addition amount of about 5.0 to 100 parts by mass is preferable per 100 parts by mass of the layer forming composition.

  The composition for forming a low refractive index layer of the present invention is usually prepared by dissolving in a suitable solvent. Under the present circumstances, although the density | concentration of the composition for low refractive index layer formation of this invention is suitably selected according to a use, generally it is about 0.01-60 mass%, Preferably it is 0.5-50 mass. %, Particularly preferably about 1% to 20% by mass.

  The solvent is not particularly limited as long as the composition for forming a low refractive index layer according to the present invention is uniformly dissolved or dispersed without causing precipitation, and two or more kinds of solvents can be used in combination. . Preferred examples include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, isopropyl). Alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

  Colloidal inorganic particles may be further added to the composition for forming a low refractive index layer of the present invention in order to improve film strength or coatability. As such colloidal inorganic particles, those having a particle diameter of 5 to 50 nm are preferably used, more preferably those having a particle diameter of 5 to 30 nm, and particularly preferably those having a particle diameter of 8 to 20 nm. Examples of the inorganic particles include silica, alumina, magnesium fluoride and the like. Colloidal silica is preferred. Such colloidal silica is, for example, I.V. M.M. By Thomas, Appl. Opt. 25, 1481 (1986), etc., and can be adjusted by hydrolysis and polycondensation using tetraalkoxysilane as a raw material and a catalyst such as aqueous ammonia. In addition, commercially available products such as Snowtex IPA-ST, MEK-ST manufactured by Nissan Chemical Industries, Ltd., AEROSIL300 manufactured by Nippon Aerosil Co., Ltd., AEROSIL130, AEROSIL50 manufactured by Nihon Aerosil Co., Ltd. (all trade names) can be used. .

  The amount of colloidal inorganic particles added is generally in the range of 5 to 95% by mass, preferably 10 to 70% by mass, particularly preferably 20% of the total solid content after the coating film of the composition for forming a low refractive index layer is cured. It is a case of -60 mass%.

  In addition, additives such as various silane coupling agents, surfactants, thickeners, and leveling agents may be appropriately added to the composition for forming a low refractive index layer as necessary.

[High / Medium Refractive Index Layer]
When the antireflection film of the present invention takes the form of a multilayer film, generally, the low refractive index layer has at least one layer having a higher refractive index than the low refractive index layer (that is, at least one of the high refractive index layer and the middle refractive index layer). Used with any layer).

  As an organic material for forming a layer having a higher refractive index than the above low refractive index layer, a thermoplastic film (eg, polystyrene, polystyrene copolymer, polycarbonate, aromatic ring other than polystyrene, heterocyclic ring, alicyclic ring) A polymer having a group, or a polymer having a halogen group other than fluorine; a film composition (eg, a film composition having a melamine film, a phenol film, or an epoxy film as a curing agent); a urethane-forming composition (eg, A combination of alicyclic or aromatic isocyanate and polyol; and a radically polymerizable composition (modified film or prepolymer that enables radical curing by introducing a double bond into the above compound (polymer, etc.)) Composition). Any of these film-forming compositions may be used, but materials having high film-forming properties are preferred. The layer having a refractive index higher than that of the low refractive index layer can also use inorganic fine particles dispersed in an organic material. As the organic material used for this layer, since inorganic fine particles generally have a high refractive index, those having a refractive index lower than that used when the organic material is used alone can be used. As such materials, in addition to the above-mentioned organic materials, acrylic copolymers, vinyl copolymers, polyesters, alkyd coatings, fibrous polymers, urethane coatings, various curing agents that cure these, and curable functional groups Examples thereof include various organic materials that are transparent and stably disperse inorganic fine particles.

  Further, an organically substituted silicon compound or a hydrolysis product thereof can be contained in the high / medium refractive index layer.

[Hard coat layer]
It can be formed using an acrylic polymer, urethane polymer, epoxy polymer, silicon polymer or silica compound. A pigment may be added to the hard coat layer. The strength of the hard coat layer is preferably a pencil hardness of 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. On the transparent support, in addition to the hard coat layer, an adhesive layer, a shield layer, a sliding layer and an antistatic layer may be provided. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Transparent support]
Unless the antireflection film is directly provided on the CRT image display surface or the lens surface, the antireflection film preferably has a transparent support.
As the transparent support, a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethene Tacrylate and polyether ketone are included. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred. The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass.
As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, Al 2 O 3} , TiO 2, BaSO 4, CaCO 3, talc and kaolin.
The transparent support may be subjected to surface treatment.

  Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

[Formation of antireflection film]
When the antireflection film has a single layer or a multilayer structure as described above, each layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or extrinsic. It can be formed by coating by a rouge coating method (described in US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973). The lower the reflectance of the antireflection film, the better. Specifically, the average reflectance in the wavelength region of 450 to 650 nm is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less. The haze of the antireflection film (when it does not have the antiglare function described below) is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The strength of the antireflection film is preferably 1 or higher, more preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

  The antireflection film may have an antiglare function that scatters external light. The antiglare function can be obtained by forming irregularities on the surface of the antireflection film. When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.

  As a method for forming irregularities on the surface of the antireflection film, any method can be applied as long as these surface shapes can be sufficiently retained. For example, fine particles are used in the low refractive index layer, thereby forming irregularities on the film surface (for example, JP-A No. 2000-271878), lower layer of the low refractive index layer (high refractive index layer, medium refractive index) A relatively large particle (particle size 0.05 to 2 μm) is added to the layer or hard coat layer) to form a surface uneven film, and these shapes are maintained on the surface A method of providing a low refractive index layer (for example, Japanese Patent Application Laid-Open Nos. 2000-281410 and 2000-95893), and a method of physically transferring an uneven shape to the surface of the low refractive index layer (such as an embossing method). 11-268800).

[Polarizing plate / display device]
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

  As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method. That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity. The method for stretching the polarizing film follows the method described in JP-A-2002-86554.

  The antireflection film of the present invention and the polarizing plate of the present invention using the antireflection film so as to be the outermost surface of the low refractive index layer are used for display devices such as liquid crystal display devices (LCD), plasma display panels ( It can be applied to image display devices such as PDP), electroluminescence display (ELD) and cathode ray tube display (CRT). Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device. In the case of the polarizing plate of the present invention, it is used by adhering to the display surface of the display device so that the low refractive index layer becomes the outermost surface of the display device.

  When the antireflection film of the present invention is used as one side of a surface protective film of a polarizing film, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curly compensated bend cell (OCB) or an electrically controlled birefringence (ECB).

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625 (in Japanese Patent Publication No. 176625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening a viewing angle is used as a protective film having two polarizing films on both sides. Of these, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate by using it on the surface opposite to the antireflection film of the present invention.

[Hard coat film]
Next, the hard coat film will be described.
The hard coat film of the present invention is characterized in that a radiation curable resin containing a telomer acrylate containing a fluorine atom characteristic of the present invention is provided on its surface as an antifouling layer. Is the same as the composition of the layer described above as the low refractive index layer of the antireflection film, including additives such as a curing agent that may be added. The application method is also applied to the substrate to be treated for antifouling, and is the same as the method described for the application of the low refractive index layer.

  Furthermore, when this hard coat film was measured by etching ESCA, F / C (ratio of the spectral intensity of fluorine to the spectral intensity of carbon) was 1/1 ≧ (F / C in the cured film) / (the surface of the cured film). High antifouling durability can be obtained when F / C) ≧ 1/20 is satisfied. The F / C ratio is preferably 1/18 or more and 1/1 or less, and more preferably 1/15 or more and 1/1 or less. [F / C is the ratio of the spectral intensity of F to the spectral intensity of C when the hard coat film is measured by etching ESCA. ]

  The F / C on the surface of the cured film is the spectral ratio when etched for 5 seconds at an electron beam intensity of 12 kV / 20 mA in F and C etching ESCA, and the F / C inside the cured film is 100 to 500 under the same conditions. The average spectral ratio when etched for 2 seconds is shown.

There is no restriction | limiting in particular in the to-be-processed base material which the antifouling coating composition of this invention makes the antifouling layer formation object, Glass, resin, ceramics, metal, wood, leather, a stone material etc. are mentioned.
In particular, the optical member is preferably an inorganic substrate such as a glass plate or a glass plate containing an inorganic compound layer, or an organic substrate such as a transparent plastic substrate or a transparent plastic substrate containing an inorganic compound layer. It is done.

Among these, as an inorganic base material, a glass plate can mainly be mention | raise | lifted. Examples of the inorganic compound forming the glass plate containing the inorganic compound layer include metal oxides [silicon oxide (silicon dioxide, silicon monoxide, etc.), aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide. , Antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (Indium Tin Oxide), etc.], metal halides (magnesium fluoride, calcium fluoride, sodium fluoride, lanthanum fluoride, fluoride) Cerium, lithium fluoride, thorium fluoride, etc.).
The inorganic base material or inorganic compound layer composed of these inorganic compounds can be a single layer or a multilayer structure, and these are wet coating methods (dip coating method, spin coating method, flow coating method, spray coating method, roll coating method). , Gravure coating method, etc.), PVD (Physical Vapor Deposition) method (vacuum deposition method, sputtering method, ion plating method), CVD (Chemical Vapor Deposition) method and the like.

In addition, among the organic base materials to be processed, examples of the transparent plastic base material include base materials made of various organic polymers.
In particular, base materials used as optical members are cellulose esters (eg, triglycerides) from the viewpoint of optical properties such as transparency, refractive index, and dispersibility, and physical properties such as impact resistance, heat resistance, and durability. Acetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1) , 2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpe). Nthene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate and polyetherketone. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred. The light transmittance of the substrate is preferably 80% or more, and more preferably 86% or more. The haze of the substrate is preferably 2.0% or less, and more preferably 1.0% or less.

  When the substrate is a transparent substrate, the refractive index is preferably 1.4 to 1.7. Those obtained by adding known additives (for example, antistatic agents, ultraviolet absorbers, plasticizers, slip agents, colorants, antioxidants, flame retardants, etc.) to the organic polymers constituting these organic base materials Can be used. The amount of these additives added is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the base material.

  Moreover, you may implement surface treatment to a base material. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred.

The shape of the inorganic substrate or organic substrate used as the substrate to be treated is not particularly limited. Usually, the transparent plastic substrate used as an optical member is in the form of a film or sheet. The hard coat film of the invention can also be a substrate to be treated in the form of a film or a sheet. The film or sheet substrate may be a single layer or a laminate of a plurality of organic polymers. Moreover, although the thickness is not specifically limited, 0.01-5 mm is preferable.
Moreover, as the said inorganic compound layer of the to-be-processed base material which formed the inorganic compound layer on the above organic base materials, it is the same using the inorganic compound similar to the inorganic compound layer which comprises the above-mentioned inorganic base material. It can be formed by a technique.

  As in the case of the above-described antireflection film, a primer layer, a moisture-proof layer, an antistatic layer, and an undercoat layer may be provided on the transparent plastic substrate used in the present invention in the hard coat film. The functions and configurations of these layers are the same as those described for the antireflection film.

The hard coat layer was mentioned in the section of the antireflection layer, but more specifically, it is not particularly limited as long as it has transparency, appropriate hardness and mechanical strength. For example, ionizing radiation or ultraviolet rays can be used. A cured resin or a thermosetting resin by irradiation can be used, and it can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer, a silica compound, or the like. A pigment may be added to the hard coat layer. The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Two or more kinds of polymers may be used in combination. As the silica compound, colloidal silica is preferably used. The strength of the hard coat layer is a pencil hardness with a 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.
It is more preferable that these resins have the same or similar refractive index as that of the transparent plastic substrate.

If the film thickness of the hard coat layer is 3 μm or more, the strength is sufficient, but a range of 5 to 50 μm is preferable from the viewpoint of transparency, coating accuracy, and handleability.
In addition, it is preferable to mix and disperse inorganic or organic particles having an average particle size of 0.01 to 3 μm in the hard coat layer because the mechanical strength of the film can be improved. These fine particles are not particularly limited as long as they are transparent, but a low refractive index material is preferable, and silicon oxide and magnesium fluoride are preferable in terms of stability, heat resistance, and the like.
As long as the hard coat layer is applied uniformly, any method may be used.

  There is no particular limitation on the method for forming a hard coat layer using the telomer acrylate containing fluorine atoms of the present invention on the substrate to be treated. Wet coating method (dip coating method, air knife method, spin coating method, curtain coating) Method, wire bar coating method, flow coating method, spray coating method, roll coating method, gravure coating method, etc., and dry coating method (vacuum deposition method (resistance heating method, electron beam method, high frequency heating method, ion beam) Etc.), sputtering method, CVD method (plasma CVD method, photo CVD method, thermal CVD method, etc.)].

  A transparent support may not be required as in the case where the hard coat layer is provided directly on the CRT image display surface or the lens surface. On the other hand, it is also a preferred embodiment that the hard coat layer has a transparent support. As the transparent support, a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl It includes methacrylate and polyether ketone. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass. As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, Al 2 O 3} , TiO 2, BaSO 4, CaCO 3, talc and kaolin.
The transparent support may be subjected to surface treatment.

  The formation by applying the hard coat layer will be described. When the hard coat layer has a single layer structure or a multilayer structure as described above, each layer is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extensible method. It can be formed by coating by a rouge coating method (described in US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973). The haze of the hard coat film (when there is no anti-glare function described below) is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The strength of the hard coat film is H or more with a pencil hardness of 1 kg load. Preferably, it is 2H or more, more preferably 3H or more.

  The hard coat layer thus obtained preferably has a difference (ΔH) in haze value before and after abrasion with steel wool of 5% or less, particularly 1% or less. The difference in haze value (ΔH) between before and after abrasion by steel wool in the present invention means that the surface of the hard coat layer, which is a surface protective layer, is worn by rubbing 100 reciprocations with a load of 300 g using steel wool # 0000. The haze value before and after wear was measured using a haze measuring device “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd., and the haze value before wear was subtracted from the haze value after wear.

[Optical information record carrier]
Next, the optical information record carrier will be described.
The information record carrier of the present invention is an information record carrier capable of reproducing an information signal by optical means. The basic structure of the information record carrier of the present invention comprises a support, a recording layer formed on the support and capable of recording information signals, and a light-transmitting layer formed on the recording layer and transmitting light. Each component may be interchanged or combined with each other as long as the content of the invention is not impaired. Each of them needs to exist at least one, but each of them may exist in a plurality of layers, or one layer may be composed of a plurality of layers having different compositions and characteristics. Specifically, two recording layers and a light-transmitting layer are provided on one side of the support, such as support / recording layer / light-transmitting layer / recording layer / light-transmitting layer, or light-transmitting layer / recording layer / supporting. A recording layer and a light-transmitting layer may be disposed on both sides of the support, such as a body / recording layer / light-transmitting layer. In addition to the above configuration, a known antistatic layer, lubricating layer, protective layer, reflective layer, and the like may be provided. Further, label printing may be performed on the side of the support opposite to the recording layer.
The information record carrier of the present invention may be one mounted in the cartridge. In addition, the size is not limited, and in the case of a disc-shaped information record carrier, for example, various sizes with a diameter of 30 to 300 mm can be taken, and diameters 32, 51, 65, 80, 88, 120, 130, 200 , 300 mm, etc.

In the information record carrier of the present invention, the support is a base having a function of mechanically holding a recording layer, a light transmitting layer, and the like, which will be described later.
The constituent material may be any of synthetic resin, ceramic, metal and the like. Typical examples of synthetic resins include polycarbonate, polymethyl methacrylate, polystyrene, polycarbonate-polystyrene copolymer, polyvinyl chloride, alicyclic polyolefin, polymethylpentene, and other thermoplastic resins, thermosetting resins, and various radiation curable resins ( UV curable resins and visible light curable resins are included). In addition, these may be a synthetic resin blended with metal powder or ceramic powder. As typical examples of ceramic, soda lime glass, soda aluminosilicate glass, borosilicate glass, quartz glass, and the like can be used. Aluminum, copper, iron or the like can be used as the metal.
Among these, polycarbonate and amorphous polyolefin are preferable from the viewpoint of moisture resistance, dimensional stability, and price, and polycarbonate is most preferable.
The thickness of the support is preferably 0.3 to 3 mm, preferably 0.6 to 2 mm, and most preferably in the range of 1.1 mm ± 0.3 mm, because of the need to mechanically hold the other layers. Used for.

On the surface of the support, irregularities (pregrooves) representing information such as tracking grooves or address signals are usually formed. The pregroove is preferably formed directly on the support when a resin material such as polycarbonate is injection molded or extruded.
Further, the pregroove may be formed by providing a pregroove layer. As a material of the pregroove layer, a mixture of at least one monomer (or oligomer) of acrylic acid monoester, diester, triester, tetraester, pentaester and hexaester of polyol and a photopolymerization initiator is used. be able to. For example, the pregroove layer is formed by, first, applying a mixed liquid composed of the above-described acrylic ester and polymerization initiator on a precisely formed master (stamper), and further, supporting the support on the coating liquid layer. After mounting, the coating layer is cured by irradiating ultraviolet rays through the support or the matrix, and the support and the coating layer are fixed. Subsequently, it can obtain by peeling a support body from a mother mold. The thickness of the pregroove layer is generally in the range of 0.01 to 100 μm, preferably in the range of 0.05 to 50 μm.

In the present invention, the track pitch of the pregroove of the support is preferably in the range of 200 to 400 nm, and more preferably in the range of 250 to 350 nm.
The groove depth of the pregroove is preferably in the range of 10 to 150 nm, more preferably in the range of 20 to 100 nm, and still more preferably in the range of 30 to 80 nm. Moreover, it is preferable that the half value width exists in the range of 50-250 nm, and it is more preferable that it is the range of 100-200 nm.

When the light reflecting layer described later is provided on the information recording carrier of the present invention, an undercoat layer is formed on the surface of the support on the side where the light reflecting layer is provided for the purpose of improving flatness and adhesion. It is preferable.
Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfone. Polymer materials such as chlorinated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate; silane coupling agents And the like.

  The undercoat layer is prepared by dissolving or dispersing the above materials in an appropriate solvent to prepare a coating solution, and then applying this coating solution to the surface of the support by a coating method such as spin coating, dip coating, or extrusion coating. Can be formed. In general, the thickness of the undercoat layer is preferably in the range of 0.005 to 20 μm, more preferably in the range of 0.01 to 10 μm.

  The light reflecting layer can be optionally provided between the support and the recording layer for the purpose of improving the reflectance during information reproduction. The light reflecting layer can be formed on the support by depositing, sputtering, or ion plating a light reflecting material having a high reflectance to the laser beam. The thickness of the light reflecting layer is generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm. Note that the reflectance of the light reflective material is preferably 70% or more.

  As a light reflective material having a high reflectance, Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd , Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, and other metals, metalloids, and stainless steel. These light reflecting substances may be used alone, in combination of two or more kinds, or may be used as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred is Au, Ag, Al or an alloy thereof, and most preferred is Au, Ag or an alloy thereof.

  In the information recording carrier of the present invention, the recording layer is a layer having a function capable of recording or rewriting information by recording an information signal on the layer by optical or magnetic recording means, and optically. An information signal can be reproduced from the layer by a simple reproducing means (laser light or the like). The recording layer uses a high-reflectance material when the information record carrier is a reproduction-only information record carrier, and in the case of a recording / reproduction type information record carrier, the recording layer is a dye recording material or phase according to the recording or reproduction principle. A change recording material or a magneto-optical recording material is selected and used. The thickness of the recording layer is preferably 2 to 300 nm, and particularly preferably 5 to 200 nm.

Gold, silver, or the like is used as the light reflectivity material used for the recording layer.
Specific examples of recording materials for dye recording include cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, azo dyes, naphthoquinone dyes, fulgide dyes, polymethine dyes, acridine dyes, and the like.
Recording materials for phase change recording include alloys such as indium, antimony, tellurium, selenium, germanium, bismuth, vanadium, gallium, platinum, gold, silver, copper, tin, arsenic (alloys are oxides, nitrides, Carbides, sulfides, fluorides, etc.) can be used, and it is particularly preferable to use GeSbTe, AgInSbTe, CuAlTeSb, or the like. A recording layer may be formed using a laminated film of an indium alloy and a tellurium alloy.

  Recording materials for magneto-optical recording include alloys such as terbium, cobalt, iron, gadolinium, chromium, neodymium, dysprosium, bismuth, palladium, samarium, holmium, proseodymium, manganese, titanium, palladium, erbium, ytterbium, lutetium, tin, etc. (Alloys include oxides, nitrides, carbides, sulfides, and fluorides), and are composed of transition metal and rare earth alloys as represented by TbFeCo, GdFeCo, DyFeCo, and the like. Is preferred. Furthermore, a recording layer may be formed by using an alternating laminated film of cobalt and platinum.

  These recording layers have auxiliary films such as silicon, tantalum, zinc, magnesium, calcium, aluminum, chromium, zirconium and the like (oxides) for the purpose of improving reproduction output, rewriting frequency, and storage stability. , Nitrides and carbides) and highly reflective films (aluminum, gold, silver, etc.) may be used in combination.

  The recording layer using the recording material for dye recording preferably contains a dye having maximum absorption in the wavelength region of the laser beam used for reproduction, and in particular, recording and reproduction can be performed with a laser having a wavelength of 500 nm or less. As such, it is more preferable to contain a dye having a maximum absorption in the wavelength region. Examples of the dye used include cyanine dyes, oxonol dyes, metal complex dyes, azo dyes, and phthalocyanine dyes. Specifically, JP-A-4-74690, JP-A-8-127174, JP-A-11-53758, JP-A-11-334204, JP-A-11-334205, JP-A-11-334206. , JP-A-11-334207, JP-A-2000-43423, JP-A-2000-108513, JP-A-2000-158818, or triazole, triazine, Examples of the pigment include cyanine, merocyanine, aminobutadiene, phthalocyanine, cinnamic acid, viologen, azo, oxonol benzoxazole, and benzotriazole, and pigments such as cyanine, aminobutadiene, benzotriazole, and phthalocyanine are preferable.

When a recording material for dye recording is used for the recording layer, a coating solution is prepared by dissolving the above-described dye and, if desired, a binder in an appropriate solvent, and then this coating solution is used to prepare a coating material for the aforementioned support. It can form by apply | coating to a groove surface or the light reflection layer surface, forming a coating film, and then drying. Furthermore, various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added to the coating solution depending on the purpose.
In addition, as a method for dissolving the dye and the binder, methods such as ultrasonic treatment, homogenizer treatment, disper treatment, sand mill treatment, stirrer stirring treatment, and the like can be applied.

  Examples of the solvent for the coating solution include esters such as butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; amides such as dimethylformamide Hydrocarbons such as cyclohexane; ethers such as tetrahydrofuran, ethyl ether and dioxane; alcohols such as ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol; fluorine such as 2,2,3,3-tetrafluoropropanol; Solvents: Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc. Door can be. The above solvents may be used alone in consideration of the solubility of the dye and binder to be used, or two or more kinds may be used in combination as appropriate.

  Examples of binders include, for example, natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin, rubber; and hydrocarbon resins such as polyurethane, polyethylene, polypropylene, polystyrene, polyisobutylene, polyvinyl chloride, poly Vinyl resins such as vinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymers, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resins, butyral resins, rubber derivatives, phenols A synthetic organic polymer such as an initial condensate of a thermosetting resin such as formaldehyde resin can be mentioned. When a binder is used in combination as the recording layer material, the amount of binder used is preferably in the range of 0.01 to 50 times (mass ratio) to the dye, and 0.1 to 5 times the amount. More preferably, it is the range. It is possible to improve the storage stability of the recording layer by incorporating a binder into the recording layer.

  Thus, the density | concentration of the pigment | dye in the coating liquid prepared is in the range of 0.01-10 mass% generally, Preferably it exists in the range of 0.1-5 mass%.

Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method.
The application temperature is not particularly limited as long as it is 23 to 50 ° C, but is preferably 24 to 40 ° C, and more preferably 25 to 37 ° C.

  The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range of 20 to 500 nm, preferably in the range of 50 to 300 nm.

The recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer.
As the antifading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19587, and 60-35054. 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, JP-A-60-47069, JP-A-63-209995, JP-A-4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent No. 350399, and Japan Examples include those described in Chemical Society Journal, October 1992, page 1141.
The content of the anti-fading agent such as a singlet oxygen quencher is usually in the range of 0.1 to 50% by mass, preferably in the range of 0.5 to 45% by mass, based on the total solid content of the recording layer. More preferably, it is the range of 3-40 mass%, Most preferably, it is the range of 5-25 mass%.

An intermediate layer (barrier layer) may be formed on the surface of the recording layer in order to improve adhesion to the light-transmitting layer and storage stability of the dye. The barrier layer is a layer made of a material such as an oxide, a nitride, a carbide, or a sulfide made of any one or more of Zn, Si, Ti, Te, Sm, Mo, Ge, and the like. The barrier layer may be hybridized like ZnS—SiO ₂ . The barrier layer can be formed by sputtering, vapor deposition ion plating, or the like, and the thickness is preferably 1 to 100 nm.

In the information record carrier of the present invention, the translucent layer has a function of physically guiding the converged reproduction light to the recording layer, and at the same time, a function of chemically and mechanically protecting the recording layer. The translucent layer of the present invention is preferably made of a film that is thinner than the thickness of the support.
In the present invention, “translucent” is practically transparent (transmittance of 70% or more, desirably) with respect to the wavelength of light (for example, light of 600 to 800 nm or 350 to 450 nm) of optical means used for recording and reproduction. Means 80% or more).

  The translucent layer of the present invention has a translucent film having a hygroscopic expansion coefficient of 8 ppm /% RH or more and 62 ppm /% RH or less. If the hygroscopic expansion coefficient is outside the above range, the record carrier may be deformed due to environmental changes. This is presumably because the difference in the hygroscopic expansion coefficient between the translucent film and the substrate is particularly large. When the information record carrier is deformed, the recording layer is affected, the recording / reproduction suitability is deteriorated, and the recording / reproduction stability is deteriorated. More preferably, the hygroscopic expansion coefficient is 8 ppm /% RH or more and 50 ppm /% or less, and more preferably 8 ppm /% RH or more and 40 ppm /% RH.

In the present invention, the hygroscopic expansion coefficient means the dimensional change rate of the film when the environment is changed from 25 ° C. 20% RH to 25 ° C. 80% RH. That is, when the film size at 25 ° C. and 20% RH is L20, and the size at 25 ° C. and 80% RH is L80, [[(L80−L20) / L20] / (80-20)] × 100 is a hygroscopic expansion coefficient (unit: ppm /% RH). For example, the film can be obtained by cutting the film into a rectangle such as 5 cm wide and 28 cm long and measuring the film length at 25 ° C., 20% RH and 25 ° C., 80% RH.
The hygroscopic expansion coefficient of the translucent film can be adjusted by appropriately selecting the kind and amount of the film material and the additive to the film. Specifically, a cellulose acylate film containing a specific deterioration inhibitor, a cellulose acylate film containing a chlorinated organic solvent content, a cellulose acylate film containing a specific polyhydric alcohol ester, and a cyclic shape A polyolefin film or polycarbonate is preferably used as the translucent film.

  As a translucent film used for a translucent layer in this invention, the thing which is not manufactured by extending | stretching is preferable. This is because, when manufactured using stretching, optical anisotropy may occur in the stretching direction, and in that case, it is not preferable as the light-transmitting layer of the information recording carrier of the present invention. Further, anisotropy may occur in the thermal expansion due to stretching, which is not preferable from the viewpoint of long-term storage stability.

  The translucent film used in the translucent layer of the present invention is preferably a film made of a cellulose derivative (particularly cellulose acylate), a cyclic polyolefin or a polycarbonate.

Cellulose has a basic molecular structure of a six-membered ring, and has three hydroxyl groups (OH) in this basic unit. Cellulose acylate can be synthesized by esterifying cellulose with glacial acetic acid, propionic acid, butyric acid, acetic anhydride, propionic anhydride, etc., and cellulose acylate can be synthesized. Depending on the synthesis conditions, some of the three hydroxyl groups can be synthesized. Or all can be esterified. Among these, cellulose acylate substituted with two or more hydroxyl groups can be processed into a thin sheet by a casting method using a solvent or a melt extrusion method. The synthesized cellulose acylate has a refractive index of 1. A transparent body of around 5 has a characteristic that the intrinsic birefringence is small and the dependency on the light incident angle is also small. The cellulose acylate film obtained by applying tension to the cellulose acylate is a tough film that inherits the intrinsic birefringence of the material and suppresses the birefringence difference in the longitudinal and transverse directions. Therefore, it is suitable as the translucent film of the present invention.
Cellulose acylate preferably has a transmittance of λ = 350 to 450 nm substantially transparent (transmittance is preferably 70% or more, more preferably 80% or more) by adjusting the synthesis conditions of the cellulose derivative. . Cellulose acylate may be yellowed or whitened depending on the synthesis conditions of the cellulose derivative. However, when an information record carrier is formed using such a material, the reflectance may decrease and the reproduction signal output may deteriorate. Because.

  The cellulose acylate film has low tear strength and folding strength as it is, and has a drawback that it becomes very brittle and easily tears particularly under low humidity conditions. Conventionally, a low molecular plasticizer has been added to provide flexibility. Examples of these include triphenyl phosphate, tricresyl phosphate, triethyl phosphate, diphenyl biphenyl phosphate and the like as phosphate ester, and dimethyl phthalate, diethyl phthalate, dimethoxyethyl phthalate and the like as phthalate ester. Examples of glycolic acid esters include ethylphthalylethyl glycol and the like, and other than these, toluenesulfonamide, triacetin (glycerin triacetate) and the like have been used.

  However, the plasticizers listed above are low molecular weight substances, and even those having a high boiling point do not exceed 300 ° C. On the other hand, cellulose acylate is known as a polymer having low compatibility with other substances, and even a compatible plasticizer has a fatal defect that its boiling point is low as described above. Since the plasticizer migrates violently, the plasticizer distribution is uneven in the thickness direction of the resulting film, which may cause curling of the film or the plasticizer oozes out on the surface of the film. Is known to cause significant problems. Therefore, in order to eliminate the above-mentioned drawbacks conventionally, that is, the folding strength and tear strength are large at room temperature and low temperature, the tensile strength and the like are relatively unchanged from those when a low molecular plasticizer is added, and the optical transmittance is excellent. In order to obtain a tough cellulose acylate film, a high molecular weight plasticizer such as polyester ether, polyester-urethane, polyester, or a combination of these high molecular weight plasticizer and low molecular weight plasticizer is mixed with cellulose acylate. (See, for example, JP-B-47-760, JP-B-43-16305, JP-B-44-32672, and JP-A-2-292342), and the object is almost achieved. is there. However, when these supports are used, the stability under long-term storage is significantly reduced compared to a support containing only a low molecular plasticizer (for example, triphenyl phosphate), and coloring, molecular chain breakage, etc. It has been found that there is a drawback that it is likely to occur.

In the present invention, in order to achieve long-term storage stability in the cellulose acylate film, the cellulose acylate film is added with (A) a peroxide decomposing agent,
(B) a radical chain inhibitor,
(C) a metal deactivator, and (D) an acid scavenger,
Among these, it is preferable to contain at least one kind of deterioration preventing agent.
Alternatively, the amount of the organic chlorine solvent contained in the cellulose acylate film is 10 ppm or less, or the cellulose acylate film contains a polyhydric alcohol ester of an aliphatic polyhydric alcohol and one or more monocarboxylic acids. It is also preferred to achieve long-term storage stability.
Examples of the deterioration preventing agent that can be preferably used in the present invention include [0063] to [0064] of JP-A-5-197073, US Pat. Nos. 4,483,918, 4,555,479, and 4,585,728, 4,639,415, European Patent 264,730, JP-A-58-102231, 59-229557, 61-73152, 63-98662 Nos. 63-115167 and 63-267944, and the like.

  As the polycarbonate film used in the present invention, those described in [0023] of JP-A No. 2003-157579 can be preferably used.

Next, the cyclic polyolefin film used in the present invention will be described.
The cyclic polyolefin film used in the present invention is disclosed in JP-A-5-65350, JP-A-6-107736, JP-A-6-248164, JP-A-10-60048, JP-A-11-129399, JP-A-11-216817, JP-A-11-217446. No. 11-217491, JP-A No. 2001-9859, JP-A No. 2001-163959, JP-A No. 2002-249625, and the like.

  The cyclic olefin used in the present invention has an alicyclic structure in at least one of the main chain and the side chain, and contains an alicyclic structure in the main chain from the viewpoint of mechanical strength, heat resistance, and the like. Those are preferred. Examples of the alicyclic structure of the polymer include a cycloalkane structure and a cycloalkene structure. From the viewpoint of mechanical strength and heat resistance, a cycloalkane structure and a cycloalkene structure are preferable. Since the thing is excellent in a weather resistance and chemical resistance, it is the most preferable. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The properties of heat resistance and moldability are highly balanced and suitable.

  The ratio of the repeating unit having an alicyclic structure in the cyclic olefin used in the present invention may be appropriately selected according to the purpose of use, but is usually 30% by mass or more, preferably 50% by mass or more, more preferably. Is 70% by mass or more. If the proportion of the repeating unit having an alicyclic structure in the cyclic olefin is too small, the heat resistance is inferior. The remainder other than the repeating unit having an alicyclic structure in the cyclic olefin is not particularly limited and is appropriately selected according to the purpose of use. Moreover, a thermoplastic thing is suitable as a cyclic olefin.

  Specific examples of the polymer having such an alicyclic structure include, for example, (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, (4 ) Vinyl alicyclic hydrocarbon polymers and hydrogenated products thereof. Among these, norbornene polymers and hydrogenated products thereof, cyclic conjugated diene polymers and hydrogenated products thereof are preferable, and norbornene polymers and hydrogenated products thereof are more preferable.

(1) Norbornene-based polymer The norbornene-based polymer is not particularly limited, and for example, a norbornene-based monomer (for example, a method disclosed in JP-A-3-14882, JP-A-3-122137, or the like). A polymer obtained by polymerizing a cyclic olefin monomer having a norbornene ring is used. Specific examples include a ring-opening polymer of a norbornene monomer and a hydrogenated product thereof, an addition polymer of a norbornene monomer, and an addition polymer of a norbornene monomer and a vinyl compound. Among these, preferred are ring-opening polymer hydrogenated norbornene monomers, addition polymers of norbornene monomers, addition polymers of vinyl compounds copolymerizable with norbornene monomers, and the like. Particularly preferred are hydrogenated ring-opening polymers of norbornene monomers. The ring-opening polymer hydrogenated norbornene monomer has a large difference between the plasticizing temperature and the decomposition temperature and is suitable for calendering with heating. Therefore, it has excellent mechanical strength and excellent appearance. Can be formed.

  Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (commonly used norbornene) and the like described in paragraph numbers [0010] to [0013] of JP-A-2001-9859. The body is mentioned.

  These norbornene monomers are used alone or in combination of two or more. Among the norbornene monomers, it is preferable that dicyclopentadiene is included, for example, a combination of dicyclopentadiene and tetracyclododecene, dicyclopentadiene, tetracyclododecene and ethyltetracyclododecene. , Dicyclopentadiene and ethyltetracyclododecene, dicyclopentadiene and ethylidenetetracyclododecene, dicyclopentadiene and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene And combinations thereof.

  Examples of vinyl compounds that can be copolymerized with a norbornene monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1-pentene. 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 Ethylene having 2 to 20 carbon atoms such as hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene or α- Olefin; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyrate) ) Cycloolefins such as -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5 -Non-conjugated dienes such as methyl-1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination of two or more.

  The polymerization method and the hydrogenation method of the norbornene monomer or the vinyl compound copolymerizable with the norbornene monomer are not particularly limited and can be performed according to a known method.

(2) Monocyclic Cyclic Olefin Polymers Monocyclic cyclic olefin polymers include, for example, monocyclic cyclic olefins such as cyclohexene, cycloheptene, and cyclooctene disclosed in JP-A No. 64-66216. An addition polymer of a monomer can be used.

(3) Cyclic conjugated diene-based polymer Examples of the cyclic conjugated diene-based polymer include cyclic conjugated dienes such as cyclopentadiene and cyclohexadiene disclosed in JP-A-6-136057 and JP-A-7-258318. A polymer obtained by 1,2- or 1,4-addition polymerization of a monomer and a hydrogenated product thereof can be used.

(4) Hydrocarbon polymer having an alicyclic structure in the side chain Examples of the hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and the like. A hydrogenated product, a hydrogenated product of a styrene polymer, or the like can be used.

  The molecular weight of the cyclic olefin used in the present invention is appropriately selected according to the purpose of use, but the polyolefin measured by gel permeation chromatography method of cyclohexane solution (toluene solution when the polymer resin does not dissolve) is used. The number average molecular weight in terms of isoprene is usually 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, and the mass average molecular weight is usually 10, 000 to 1,000,000, preferably 15,000 to 500,000, more preferably 20,000 to 200,000. MWD (= mass average molecular weight / number average molecular weight) is usually 1.0 to 10, preferably 1.0 to 6, and more preferably 1.1 to 4. By adjusting the molecular weight within such a range, the mechanical strength and moldability of the film are well balanced.

  The glass transition temperature (Tg) of the cyclic olefin used in the present invention may be appropriately selected according to the purpose of use, but is preferably 50 to 200 ° C or higher, more preferably 70 to 150 ° C or higher, most preferably. 80-120 ° C. When Tg is in this range, yellowing due to oxidative deterioration of the film during resin plasticization in calender molding is less likely to occur, and the heat resistance of the resulting film is improved.

  The 5% heat loss temperature of the cyclic olefin used in the present invention (measured at a heating rate of 5 ° C./min in a nitrogen atmosphere) is preferably 280 ° C. or higher, particularly preferably 350 ° C. or higher. It is preferable that the 5% heat loss temperature is in this range because even if the resin temperature is high, decomposition of the resin hardly occurs, and molding defects such as inclusion of bubbles due to decomposition of the resin can be prevented.

The melt viscosity at a temperature of 260 ° C. of the cyclic olefin used in the present invention is usually 1 × 10 ¹ to 1 × 10 ⁵ poise, preferably 1 × 10 ² to 1 × 10 ³ poise. When the melt viscosity is within this range, the film formability and mechanical strength are balanced and suitable.

  The cyclic olefin used in the present invention may include other polymers, antioxidants, anti-aging agents, lubricants, light stabilizers, ultraviolet absorbers, fillers, colorants, crosslinking agents, curing agents, plastics, if necessary. An agent, a foaming agent, etc. can be used individually or in mixture of 2 or more types.

  When using the above-mentioned various additives, they can be added by adding them in the production process of the cyclic olefin resin or in the process of kneading, mixing or melting the cyclic olefin resin after producing the resin.

  In the method for producing a cyclic polyolefin film, the cyclic polyolefin is heated and melted at a temperature 30 to 150 ° C., preferably 70 to 120 ° C. higher than its glass transition temperature. The method of heating and melting can be performed by a known method. For example, it can be carried out using an extruder, a kneader or the like. In the extruder, a strainer is preferable because it can filter out foreign substances that may be contained in the resin and can supply the compound to the calender roll at a uniform temperature. The strainer machine itself has a structure similar to that of an extruder, but a wire mesh of about 20 mesh or more, preferably 60 mesh or more is attached to the tip thereof. There is a mixed strainer that combines a super mixer and an extruder as a special strainer.

  In the method for producing a cyclic polyolefin film, the molten resin is led to a roll gap between a pair of calender rolls arranged side by side and rotating in the opposite direction, and then drawn from the roll gap into a film shape. There are at least two calender rolls, and the same arrangement as that used for rubber or vinyl chloride resin can be used.

  There are three basic forms of arrangement, vertical, horizontal, and inclined. By combining these, there are Z-type, inverted L-type, co-type, camelback type, M-type, and the like. Furthermore, various combinations are possible by changing the number of rolls from two to a dozen or more, and as a device attached to the calendar roll, a cooling roll, a feed roll, a pressure roll, and the like can be combined. Specifically, 2 vertical, 2 inclined, 3 vertical, 4 vertical coating, 2 vertical inverted L4, 2 vertical horizontal 2 3 pairs, 2 vertical inverted L4, 1 cooling, 5 1 co-cooling, 4 camel-back molds, 1 cooling, 3 vertical pairs, 2 reverse L 4 crimps, 2 Z-shaped crimps, 2 horizontal, 3 reverse L-shaped, 4 verticals 4 reverse L-types, 4 camel-back types, 3 vertical coolings, 1 reverse L-type 4 coolings, 1 Z-type 4 coolings, 3 vertical feeds, 1 Z-type 4 coolings Book, reverse L type 4 cooling 5 etc. are mentioned.

  The temperature of the calender roll (a set of rolls into which the molten resin is first introduced) varies slightly depending on the rotation speed of the roll, but the upper limit is usually 230 ° C., preferably in order to prevent the production of a yellowish film. Is 210 ° C., more preferably 200 ° C., and the lower limit is usually 100 ° C., preferably 130 ° C., more preferably 160 ° C. in order to prevent the production of a film having low smoothness. The temperature of the second and subsequent rolls is not particularly limited, and is usually set to a temperature that is the same as or slightly lower than the temperature of the pair of rolls into which the molten resin is first introduced.

  The film drawn from the gap between the calender rolls has a thickness of several microns to several millimeters. The thickness of the film can be controlled by calendar speed, roll temperature, roll nip distance, and the like.

  The film drawn from the gap between the calendar rolls can then be used as the translucent film of the present invention through a take-off roll, a cooling take-up device, a winder and the like. The film obtained here has a yellowness of preferably 2 or less, particularly preferably 1 or less. Thus, since the film obtained by the manufacturing method of the present invention is not yellow discolored, it can be suitably used for optical applications.

  In order to improve the storage stability of the information record carrier of the present invention, the composition of the light transmitting layer is controlled and the light transmittance of the information recording layer and the light transmitting layer is not changed due to various external pressures. Therefore, it is preferable to make the pencil hardness of the surface 2H or higher.

Regarding the pencil hardness, using the test pencil stipulated by JIS-S-6006, according to the pencil hardness evaluation method stipulated by JIS-K-5400, the hardness of the pencil with no scratches observed at a load of 9.8 N Can be sought.
The required pencil hardness is preferably 2H or more, and more preferably 3H or more.

In order to improve the scratch resistance of the surface while achieving such pencil hardness, the translucent layer contains 2% by mass to 10% by mass of the telomer acrylate containing fluorine atoms on the translucent film. It is preferable to have a hard coat layer containing%.
In addition, the content of the telomer acrylate containing a fluorine atom in the composition is preferably 3% by mass to 8% by mass, and more preferably 4% by mass to 6% by mass.
Examples of the hard coat film in which the light-transmitting film of the present invention is used as a support and a hard coat layer is applied on the support include the following.
(1) As described in Japanese Patent No. 1815116, in order to increase the hardness of a layer, the resin-forming component of the layer is a polyfunctional acrylate monomer, and this is filled with powdered inorganic filler such as alumina, silica, titanium oxide, etc. A hard coat film in which a coating composition containing an agent and a polymerization initiator is coated on a support.
(2) A hard coat film in which a photopolymerizable composition containing an inorganic charge material composed of silica or alumina surface-treated with alkoxysilane or the like described in Japanese Patent No. 1416240 is further filled with crosslinked organic fine particles.
(3) A hard coat film in which the hard coat layer described in JP-A-2000-52472 has a two-layer structure, and fine particle silica is added to the first layer.
(4) The hard coat layer described in JP-A-2000-71392 has a two-layer structure, the lower layer uses a cured resin layer made of a blend of a radical curable resin and a cationic curable resin, and only the radical curable resin is used as the upper layer. Hard coat film using a cured resin layer consisting of
(5) A hard coat film produced by melt-kneading and extrusion molding the filler and resin described in JP-A-2002-248619.

These hard coat films include cases where sufficient hardness cannot be obtained as described in the above specification. In this case, the desired hardness can be obtained by improving the following preparation methods.
(1) Increase in the number of functional groups of the polyfunctional alkyl ester monomer, increase in the amount of inorganic filler and initiator (2) increase in the inorganic filler (3) increase in the amount of silica in the first layer (4) ratio of radical curable resin Increase (5) Increase in filler

In order for the hard coat film to have excellent scratch resistance, it is preferable that the hardness of the hard coat film is large to some extent. From the viewpoint of hardness, the surface modulus of elasticity of the hard coat film is preferably about 4.0 GPa or more, more preferably 4.5 GPa or more. In a hard coat film having a surface elastic modulus of less than 4.0 GPa, sufficient pencil hardness and scratch resistance cannot be obtained. When the surface elastic modulus is expressed in universal hardness, the value is preferably about 250 N / mm ² or more, and more preferably 300 N / mm ² or more.
The surface elastic modulus can be increased by adding inorganic fine particles. When the amount of inorganic fine particles added is increased, the brittleness deteriorates, so the upper limit of the surface elastic modulus is 10 GPa, preferably 9.0 GPa. Therefore, the preferable range of the surface elastic modulus is 4.0 to 10 GPa, and particularly preferably 4.5 to 9.0 GPa.

The surface elastic modulus is a value obtained using a micro surface hardness tester (manufactured by Fisher Instruments: Fisherscope H100VP-HCU). Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.
Further, the surface hardness can be obtained as a universal hardness by using the above-mentioned micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load.
It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

  The haze of the hard coat film of the present invention is preferably 7% or less, more preferably 5% or less, and most preferably 3% or less. The evaluation method of haze is a value automatically measured as haze = (diffused light / total transmitted light) × 100 (%) measured using a turbidimeter “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd. Using.

  The hard coat film in the present invention preferably has a value when curl is expressed by the following formula 7 in the range of minus 15 to plus 15, more preferably in the range of minus 12 to plus 12. Is minus 10 to plus 10. The measurement direction of the curl in the sample at this time is measured with respect to the conveyance direction of the support in the case of application in a web form.

  Curl = 1 / R (where R is the radius of curvature (m))

This is an important characteristic for preventing cracks and peeling of the film in the manufacture, processing and market handling of hard coat films. It is preferable that the curl value is in the above range and the curl is small. It is possible to reduce the curl to a high surface hardness within the above range by setting the volume shrinkage ratio before and after curing of the curable composition for forming the hard coat layer to 15% or less.
The curl is measured using the curl measurement template of Method A in “Measuring Method of Curling of Photographic Film” of JIS-K-7619-1988. The measurement conditions are 25 ° C., relative humidity 60%, and humidity control time 10 hours.
Here, “curl plus” means a curl where the hard coat layer coating side of the film is inside the curve, and “minus” means a curl where the coating side is outside the curve.
In the hard coat film of the present invention, the absolute value of the difference between the curl values when only the relative humidity is changed to 80% and 10% based on the curl measurement method described above is preferably 24 to 0, 15 ~ 0 is more preferable, and 8-0 is most preferable. This is a property related to handling, peeling and cracking when films are attached under various humidity.

  The crack resistance of the hard coat film in the present invention is preferably 50 mm or less, more preferably 40 mm or less, and more preferably 30 mm or less when the hard coat film is rolled with the hard coat layer coating side facing outward. The following are most preferred. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average. This crack resistance is an important characteristic for preventing crack defects in handling such as application, processing, cutting, and sticking of a hard coat film.

  The support used for the hard coat film of the present invention is preferably a transparent film, sheet, or plate-like plastic. Specifically, films and sheets of polyesters such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as triacetyl cellulose and diacetyl cellulose, polycarbonate, polymethyl methacrylate, polycarbonate, polysulfone, polyethersulfone, polyarylate, and cycloolefin polymer Is preferred. The thickness of the film is preferably 20 to 300 μm, more preferably 80 to 200 μm. When the thickness of the support is in the above range, the film strength is strong and the rigidity is moderate. The thickness of the sheet may be in a range that does not impair the transparency, and a sheet having a thickness of 300 μm to several mm can be used.

  The active energy ray curable coating liquid (curing composition coating liquid) is prepared by dissolving the polyfunctional monomer and the polymerization initiator mainly in an organic solvent such as ketone, alcohol, or ester. Furthermore, it can be prepared by adding a surface-modified hard inorganic fine particle dispersion and a soft fine particle dispersion.

The production of the hard coat layer of the present invention involves dipping, spinner, spray, roll coater, gravure, wire bar, slot extrusion coater (single layer, active energy ray curable coating solution on a support. It can be produced by applying by a known thin film forming method such as a multi-layer) or slide coater method, drying, irradiating with active energy rays and curing.
Drying is preferably performed under conditions where the organic solvent concentration in the applied liquid film is 5% by mass or less after drying, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The drying conditions are affected by the thermal strength of the support, the conveying speed, the length of the drying process, etc., but the lower the content of the organic solvent as possible is preferable from the viewpoint of increasing the polymerization rate.

Furthermore, for the purpose of improving the adhesion between the support and the hard coat layer, a surface treatment can be applied to one or both sides of the support by an oxidation method, a concavo-convex method or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
Furthermore, one or more undercoat layers can be provided. Examples of the material for the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, and vinyl ester, or water-soluble polymers such as latex, low molecular weight polyester, and gelatin. Further, the undercoat layer may contain tin oxide, a metal oxide such as tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide, or an antistatic agent such as a quaternary ammonium salt.

  The hard coat layer may have a multi-layer structure, and may be prepared by appropriately stacking in the order of hardness.

  The light-transmitting layer of the present invention is preferably bonded to a substrate including a support or a recording layer via an adhesive layer. In the step of installing the adhesive layer, the adhesive layer can be continuously provided on a surface different from the hard coat layer coating surface of the translucent film in which the hard coat layer is formed on one surface in advance. As a method of providing the adhesive layer, a method of attaching a pre-formed adhesive layer (hereinafter referred to as an indirect method as appropriate), and directly applying an adhesive on the surface of the translucent film and drying it. The method can be roughly divided into two methods (hereinafter referred to as a direct method as appropriate) for forming an adhesive layer.

  In the case of the indirect method, the “method for attaching a pre-formed adhesive layer” means, for example, applying a continuous adhesive to the surface of a release film having the same size as the translucent film and drying it. Then, a method is shown in which an adhesive layer is provided over the entire area of one surface of the release film, and the adhesive layer is attached to the translucent film. As a result, an adhesive layer with a release film is provided on the entire other surface of the translucent film.

  In the direct method, the front end of the translucent film wound in a roll shape is sent to a predetermined application region, and the adhesive is continuously applied from the front end to the end of one side of the translucent film, In this method, after the coating film is formed, the coating film is sequentially dried, and an adhesive layer is provided over the entire other surface of the translucent film.

In the indirect method and the direct method described above, conventionally known coating means can be used as the pressure-sensitive adhesive coating means. Specific examples include a spray method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method.
Moreover, as a drying means, conventionally well-known means, such as heat drying and ventilation drying, can be used.

  As the pressure-sensitive adhesive, acrylic-based, rubber-based, or silicon-based pressure-sensitive adhesives can be used, but acrylic-based pressure-sensitive adhesives are preferable from the viewpoints of transparency and durability. As such an acrylic pressure-sensitive adhesive, 2-ethylhexyl acrylate, n-butyl acrylate and the like are the main components, and in order to improve cohesion, short-chain alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, and methyl methacrylate are used. And acrylic acid, methacrylic acid, acrylamide derivatives, maleic acid, hydroxylethyl acrylate, glycidyl acrylate, and the like, which can be crosslinking points with the crosslinking agent, are preferably used. The glass transition temperature (Tg) and the crosslinking density can be changed by appropriately adjusting the mixing ratio and type of the main component, the short chain component, and the component for adding a crosslinking point.

  Examples of the crosslinking agent used in combination with the pressure-sensitive adhesive include an isocyanate crosslinking agent, an epoxy resin crosslinking agent, a melamine resin crosslinking agent, a urea resin crosslinking agent, and a chelate crosslinking agent. Among these, an isocyanate crosslinking agent is used. An agent is more preferable. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4-4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine isocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, and the like. Isocyanates, products of these isocyanates with polyalcohols, and polyisocyanates formed by condensation of isocyanates can be used. Commercially available products of these isocyanates include Nippon Polyurethane, Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate HTL; Takenate D-102, Takenate D-110N , Takenate D-200, Takenate D-202; manufactured by Sumitomo Bayer, Death Module L, Death Module IL, Death Module N, Death Module HL;

An adhesive layer is formed on the surface of the translucent film other than the hard coat layer, but it is wound up in a roll shape in the subsequent process to prevent the hard coat layer and the adhesive layer from sticking to each other. Therefore, it is preferable that a release film is attached to the surface of the adhesive layer. As described above, in the indirect method, a release film can be applied in advance. On the other hand, in the case of the direct method, it is preferable to newly add a step of attaching a release film to the surface of the adhesive layer after the adhesive layer is formed on the surface of the translucent film.
Here, examples of the release film attached to the surface of the adhesive layer include a polyethylene film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, and a triacetate cellulose film.

  The thickness of the light transmitting layer of the information recording carrier of the present invention is preferably thinner than the thickness of the support. Considering the aberration that increases when the information record carrier is tilted, the thickness is suitably 50 to 300 μm, preferably 60 to 200 μm, more preferably 70 to 120 μm. Further, the variation in the thickness of one surface is ± 3 μm at maximum, desirably ± 2 μm or less. More desirably, it is ± 1 μm or less.

  The optical information record carrier of the present invention records and reproduces information as follows, for example. First, a blue-violet laser (for example, wavelength) is transmitted from the light transmitting layer side through the objective lens while rotating the optical information record carrier at a predetermined linear velocity (0.5 to 10 m / sec) or a predetermined constant angular velocity. 405 nm) or the like. By this irradiation light, the recording layer absorbs the light and the temperature rises locally. For example, information is recorded by generating pits and changing their optical characteristics. The reproduction of the information recorded as described above is performed by irradiating a laser beam from the translucent layer side using a blue-violet laser as an optical means while rotating the optical information record carrier at a predetermined constant linear velocity and reflecting it. This can be done by detecting light.

As a laser light source having an oscillation wavelength of 350 nm to 500 nm serving as an optical means for recording / reproducing, for example, a blue-violet semiconductor laser having an oscillation wavelength in the range of 390 to 415 nm, a blue-violet SHG laser having a central oscillation wavelength of 425 nm, etc. Can be mentioned.
In order to increase the recording density, the NA of the objective lens used for the pickup is preferably 0.7 or more, and more preferably 0.85 or more.

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to the following examples. In addition, Example 2 shall be read as a reference example.

Preparation Example 1 of Antireflection Film
<Preparation of coating solution for hard coat layer>
125 g of a mixture of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) and urethane acrylate oligomer (UV-6300B (trade name), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 125 g was dissolved in 439 g of industrial modified ethanol. To the obtained solution, 7.5 g of a photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (Kaya Cure DETX (trade name), manufactured by Nippon Kayaku Co., Ltd.) were added. A solution dissolved in 49 g of methyl ethyl ketone was added. The mixture was stirred and then filtered through a 1 micron mesh filter to prepare a hard coat layer coating solution.

<Preparation of medium refractive index layer coating solution>
Addition of DPHA 18.08g, photopolymerization initiator (Irgacure 907) 0.920g, photosensitizer (Kayacure DETX) 0.307g, methyl ethyl ketone 230.0g and cyclohexanone 500g to 49.60g titanium dioxide dispersion And stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a medium refractive index layer coating solution.

(Preparation of titanium dioxide dispersion)
Titanium dioxide fine particles having a core / shell structure (TTO-55D (trade name), the shell material is alumina, 9% by mass of the whole particle; manufactured by Ishihara Sangyo Co., Ltd.), 30 parts by mass, a commercially available anionic monomer (PM-21) (Trade name), Nippon Kayaku Co., Ltd.) 4.5 parts by mass, commercially available cationic monomer (DMAEA (trade name), Kojin Co., Ltd.) 0.3 parts by mass and cyclohexanone 65.2 parts by mass Then, it was dispersed by a sand grinder mill to prepare a titanium dioxide dispersion having a mass average diameter of 53 nm.

<Preparation of coating solution for high refractive index layer>
110.0 g of the above titanium dioxide dispersion, 6.29 g of DPHA, 0.520 g of photopolymerization initiator (Irgacure 907), 0.173 g of photosensitizer (Kayacure DETX), 230.0 g of methyl ethyl ketone and 460.0 g of cyclohexanone Was added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

<Preparation of coating solution for low refractive index layer>
DPHA 5.4 g, 0.27 g of telomer acrylate (a-10) containing fluorine atom, colloidal silica MEK-ST (average particle size 10 to 20 nm, solid content concentration 30% by mass, methyl ethyl ketone dispersion; Nissan Chemical Industries, Ltd.) Manufactured) 2.2 g (as solid content), 1.1 g of epoxy curing agent DEX314 (manufactured by Nagase Kasei Kogyo Co., Ltd.) (as solid content), 0.35 g of paratoluenesulfonic acid and 200 g of methyl ethyl ketone were stirred. Thereafter, the solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for a low refractive index layer.

<Preparation of antireflection film>
The above-mentioned coating liquid for hard coat layer was applied on a triacetyl cellulose film (TAC-DU, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater. After drying at 90 ° C., the coating layer was cured by irradiating with ultraviolet rays to form a 6 μm thick hard coat layer.
On the hard coat layer, the medium refractive index layer coating solution was applied using a bar coater. After drying at 60 ° C., the coating layer was cured by irradiating with ultraviolet rays to form a medium refractive index layer (refractive index 1.70, film thickness 70 nm, TTB-55D, 21% by volume). On the middle refractive index layer, the above coating solution for high refractive index layer was coated using a bar coater. After drying at 60 ° C., the coating layer was cured by irradiating with ultraviolet rays to form a high refractive index layer (refractive index 1.95, film thickness 75 nm, TTB-55D, 51 vol%). On the high refractive index layer, the coating solution for the low refractive index layer was applied using a bar coater so that the film thickness after curing was 85 nm. After application, the coating was air-dried for 1 minute, then heated at 120 ° C. for 10 minutes, and then allowed to cool to room temperature to form a low refractive index layer to produce an antireflection film.

Comparative Examples 1-4
In Example 1, the amount of addition of 0.05 g of telomer acrylate (a-10) containing fluorine atoms in the coating solution for the low refractive index layer was 0.05 g, and the amount of addition was 1.20 g. Comparative Example 2, Comparative Example 3 using 0.27 g of silicon atom-containing acrylate X-22-164A (manufactured by Shin-Etsu Chemical Co., Ltd.) instead of telomer acrylate containing fluorine atom (a-10) An antireflective film was prepared as Comparative Example 4 in which the test was not performed.

(Preparation of optical information record carrier)
Example 2
<Preparation of support and recording layer>
A groove of an injection-molded polycarbonate resin (polycarbonate manufactured by Teijin Ltd., trade name: Panlite AD5503) having a spiral groove (depth 100 nm, width 120 nm, track pitch 320 nm), thickness 1.1 mm, diameter 120 mm A light reflecting layer having a thickness of 100 nm was formed on the surface having Ag by sputtering.

Thereafter, 20 g of Orazol Bull GN (Recording Material 1, Phthalocyanine Dye, manufactured by ciba Specialty Chemicals) was added to 1 liter of 2,2,3,3-tetrafluoropropanol and subjected to ultrasonic treatment for 2 hours. It melt | dissolved and the coating liquid for recording layer formation was prepared. The prepared coating solution was applied onto the light reflecting layer by a spin coat method under the conditions of 23 ° C. and 50% RH while changing the rotational speed from 300 to 4000 rpm. Thereafter, the recording layer formed by storing at 23 ° C. and 50% RH for 1 to 4 hours had a thickness of 100 nm. On the recording layer, ZnS—SiO ₂ was sputtered to a thickness of 5 nm to form an intermediate layer (barrier layer).

<Preparation of translucent layer (hard coat film)>
The translucent layer (hard coat film) placed on the recording layer is composed of an adhesive layer, a translucent film, and a hard coat layer in this order from the support side. Here, an example of manufacturing a light-transmitting layer including an adhesive layer, a light-transmitting film, and a hard coat layer is shown.

1. Formation of hard coat layer 1-1. Preparation of hard coat layer coating solution Glycidyl methacrylate is dissolved in methyl ethyl ketone (MEK) and reacted at 80 ° C for 2 hours while dropwise adding a thermal polymerization initiator (V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)). The obtained reaction solution was added dropwise to hexane, and the precipitate was dried under reduced pressure. Polyglycidyl methacrylate (polystyrene equivalent molecular weight was 12,000) dissolved in methyl ethyl ketone at a concentration of 50% by mass was added to 100 parts by mass of the solution. 150 parts by mass of trimethylolpropane triacrylate (Biscoat # 295; manufactured by Osaka Organic Chemical Industry Co., Ltd.), 6 parts by mass of a radical photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) and a photocationic polymerization initiator (Lordsil 2074, Rhodia) 12) Telomer acrylate (a-10) containing 6 parts by mass and fluorine atom Part by mass with stirring which was dissolved in methyl isobutyl ketone 30 parts by weight, to prepare a hard coat layer coating solution.

1-2. Production of hard coat film (application of hard coat layer)
(1) Production of single-layer hard coat film Using a polycarbonate film (PC), a hard coat layer was formed on the film as follows. Using a polycarbonate film wound in a roll (Teijin Pure Ace, thickness: 75 μm, with single-sided release film, hygroscopic expansion coefficient 12 ppm /% RH), it is sent to a predetermined application area and released in advance. After removing the mold film, apply a hard coat solution to form a coating film, and then continuously irradiate the coating film with radiation to cure the radiation curable resin (ultraviolet curable resin) to form a hard coat layer. And wound into a roll.

2. Bonding of Hard Coat Film and Substrate An optical information recording carrier by laminating the hard coat film prepared above via an intermediate layer on the recording layer provided on the support as described above. Was made.
2-1. Formation of adhesion layer Acrylic copolymer (solvent: ethyl acetate / toluene = 1/1) and isocyanate-based crosslinking agent (solvent: ethyl acetate / toluene = 1/1) at 100: 1 (mass ratio). It mixed and the adhesive coating liquid was prepared. Using this pressure-sensitive adhesive coating solution, an adhesive layer was provided on the surface of the release film by an indirect method.
While conveying the polyethylene release film wound in a roll shape, the pressure-sensitive adhesive coating solution was applied to the surface of the release film so that the thickness after drying was 20 μm. Then, it was made to dry at 100 degreeC in a drying area | region, and the release film provided with the adhesion layer was obtained.

2-2. Production of Transparent Sheet for Optical Information Record Carrier A release film provided with an adhesive layer was bonded to the opposite surface of the hard coat film provided with the hard coat layer so that the adhesive layer was in contact. Thereafter, the hard coat film provided with the hard coat layer and the pressure-sensitive adhesive layer was again wound into a roll, and kept in that state in an atmosphere of 23 ° C. and 50% RH for 72 hours.
Then, a hard coat film provided with a hard coat layer and an adhesive layer was sent out and punched into the same shape as the substrate. Thus, a transparent sheet for an optical information recording carrier having an adhesive layer on one side of the translucent film and a hard coat layer on the other side was obtained.

2-3. Production of optical information record carrier (Lamination of hard coat film to support and recording layer) The release film on the adhesive side is peeled off from the disc-shaped transparent sheet for optical information record carrier, and the intermediate layer and adhesive layer are separated. The optical information recording carrier was produced by laminating by a pressing means using a roller.

Comparative Examples 5-8
In Example 2, the amount of telomer acrylate (a-10) containing fluorine atoms in the hard coat layer coating solution was 2.5 parts by mass, Comparative Example 5 and the amount added was 30 parts by mass. Comparative Example 6, Comparative Example 7 with 12.5 parts by mass of silicon atom-containing acrylate UMS-182 instead of telomer acrylate (a-10) containing fluorine atoms, Comparative Example 8 without any addition Similarly, an optical information recording carrier was produced.

〔Measuring method〕
1. F / C ratio between the cured film surface and the cured film surface F / C of the cured film surface is the spectral intensity ratio when etched for 5 seconds at an electron beam intensity of 12 kV / 20 mA in etching ESCA, and the F / C inside the cured film is The average spectral intensity ratio when etching for 100 to 500 seconds under the same conditions was measured.

2. Scratch resistance test The surface of the antireflection film and the optical information recording carrier was worn by rubbing 100 reciprocations with a load of 300 g using steel wool # 0000, and the haze values before and after the wear were measured by haze measurement manufactured by Nippon Denshoku Industries Co., Ltd. Measured using a vessel “NDH-1001DP”, the haze value before wear was subtracted from the haze value after wear.

3. Anti-stain durability Anti-reflection film and quick-drying oil-based ink (Zebra, “Mackey Care” (registered trademark)) written on the surface of the light-transmitting layer of the anti-reflection film and optical information recording carrier, “Toraysee” (registered by Toray Industries, Inc.) (Trademark) was rubbed several times until the written marks were completely wiped off. This was repeated until the written marks remained without being wiped off.

4). Measurement of recording characteristics The optical information record carrier after the above scratch resistance test is mounted on a recording / reproducing apparatus having a pickup composed of a blue-violet laser emitting at λ = 405 nm and an objective lens having a numerical aperture NA of 0.7. Then, recording and reproduction of the D8-15 modulated signal with the shortest pit length set to 0.24 μm was performed, and the signal reproduction jitter was measured. The smaller the jitter, the more preferable. Specifically, 5% or less was rated as ◯, and a value higher than 5% was rated as x.

  Table 1 shows the produced antireflection film / optical information recording medium and various measurement results.

Table 1 shows the following. Antireflective film excellent in antifouling property, antifouling durability and scratch resistance by using a radiation curable resin containing 2% by mass to 10% by mass of a telomer type acrylate containing a fluorine atom as a low refractive index layer material It was found that particularly high antifouling durability was obtained when the ratio of F / C in the cured film to F / C on the surface of the cured film was 1/20 to 1/1.
Furthermore, a polarizing plate excellent in antifouling property, antifouling durability and scratch resistance can be obtained by bonding the antireflection film of the present invention to the polarizing plate described in paragraph No. [0117] of JP-A No. 2001-166104. It was confirmed that
Further, in the optical information recording carrier, an optical information recording excellent in antifouling property, antifouling durability, scratch resistance and recording characteristics by providing a hard coat layer containing the radiation curable resin on the light transmitting layer. It has been found that a carrier is provided.

It is a cross-sectional schematic diagram which shows the laminated constitution of an antireflection film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Low refractive index layer 2 High refractive index layer 3 Hard coat layer 4 Transparent support 5 Medium refractive index layer 6 Anti-glare hard coat layer

Claims (6)

Having a low refractive index layer formed from a composition comprising a radiation curable resin having an antireflection layer and containing 2% by mass to 10% by mass of a telomer acrylate containing a fluorine atom on the substrate; The radiation curable resin is a radical polymerizable compound as a polyfunctional compound containing 2 to 10 polymerizable groups, and the reflectance of the low refractive index layer is 1.20 to 1.49, An antireflection film, wherein the refractive index layer has a thickness of 10 to 400 nm. 2. The antireflection film according to claim 1, wherein the content of the telomer acrylate containing fluorine atoms in the composition is 3% by mass to 8% by mass. The antireflection film according to claim 1, wherein the telomer acrylate containing a fluorine atom is at least one selected from the following a-1 to a-10.

The antireflection film according to any one of claims 1 to 3, wherein the telomer acrylate containing a fluorine atom is at least one selected from the following a-7 to a-10.

A polarizing plate comprising a polarizing layer and two protective films sandwiching the polarizing layer, wherein the antireflection film according to any one of claims 1 to 4 is used for at least one of the two protective films. A polarizing plate. A display device comprising the antireflection film according to claim 1, wherein the antireflection film is disposed so that a low refractive index layer is on a viewing side.

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