WO2010035764A1 - Optical laminate and hardcoat film - Google Patents

Optical laminate and hardcoat film Download PDF

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WO2010035764A1
WO2010035764A1 PCT/JP2009/066568 JP2009066568W WO2010035764A1 WO 2010035764 A1 WO2010035764 A1 WO 2010035764A1 JP 2009066568 W JP2009066568 W JP 2009066568W WO 2010035764 A1 WO2010035764 A1 WO 2010035764A1
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hard coat
layer
film
resin
optical
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PCT/JP2009/066568
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French (fr)
Japanese (ja)
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村田 力
和也 大石
将臣 桑原
英輝 森内
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株式会社巴川製紙所
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/105Protective coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings

Abstract

Disclosed is an optical laminate having a high surface hardness, in which cracking- or cure shrinkage-derived curling can be suppressed, and which can provide a good screen visibility and can be suitably used for LCD or PDP TVs. The optical laminate comprises a light-transparent base and an optical functional layer provided on one side or both sides of the base either directly or through another layer.  The optical laminate is characterized in that the optical functional layer has a thickness of 3 to 50 μm and contains a light-transparent resin and light-transparent particles, and the light-transparent resin has been formed by applying an ionizing radiation to a resin composition containing an ionizing radiation curable polyfunctional acrylate and an ionizing radiation curable fluorinated acrylate in an amount of 5 to 50% by weight of the total weight of the solid content of the optical functional layer.

Description

The optical laminate and the hard coat film

The present invention (alpha) relates to an optical laminate provided in a liquid crystal display (LCD) and plasma displays (PDP) display surface such as, in particular, scratch resistance, chemical resistance, optical laminate for improving the visibility of the screen on.
The present invention (beta) relates hard coat film, in particular, relates to a hard coat film can be preferably used in a liquid crystal display (LCD) and plasma displays (PDP) display surface such.

There is a LCD in Tsu various types of image displays, but TV high viewing angle of the LCD, high definition, high-speed response, along with the innovation related to such as color reproducibility, even applications that use the LCD from your laptop or monitor to and is changing. The basic structure of the LCD is provided for by tabular gap constant interval between the glass spacer with a two transparent electrodes, there, the liquid crystal material is injected, sealed, tabular glass a polarizing plate is adhered on the front and back surfaces. Since the polarizing plate is easy scratched, conventionally, fitted with a cover plate made of glass or plastic LCD surface and with the aim of preventing damage to the polarizing plate is attached to the LCD surface. However, when mounting the cover plate costs, which is disadvantageous in terms of weight, has become polarizer optically functional layer processing has been performed is used increasingly surface. Hard coat treatment is typically performed by providing a hard coat film having a hard coat layer on a transparent plastic film substrate on the surface of the polarizing plate.

The optical functional layer is usually formed as a thin coating of about several μm on a transparent plastic film with an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. However, the thickness of the optical function layer is not sufficient, under the influence of the transparent plastic film substrate as an underlying, accidentally get scratched the optical function layer surface. The LCD applications, but primarily triacetylcellulose (TAC) film is used as the transparent plastic film substrate, the above case, the pencil hardness (JIS K5600) of a representative assay for evaluating the scratch resistance of the hard coat surface in, about 2 ~ 3H were common.

Although remarkable is spread to the LCD and PDP TV market, according to the general consumer of household TV, even for these displays, similar to the conventional CRT TV, such as severe handling (physical, mechanical, and chemical stimulation load) is expected. For example, dirt such as dust and fingerprints adhering to the display surface, a glass cleaner or wiping rag soaked with (surfactant system, an organic solvent-based, etc. variety), rub the surface children with toys, hit and the like. CRT CRT is made of glass having excellent chemical resistance, moreover, the surface hardness is about 9H in pencil hardness was durability sufficient for these loads. However, the hard coat film surface mounted on the display has a low pencil hardness, chemical resistance not be said to be satisfactory, improvements are demanded.

Further, when stuck to the hard coat film in various image display devices, a display surface, i.e., reduction in contrast due to reflection of light of the hard coat film surface, and the light caused by variations in the small thickness of the hard coat layer due interference unevenness (details described later), visibility also had deteriorated. Therefore, the hard coat film, it is also required improvement of visibility in addition to the surface hardness.

As a method of improving the surface hardness of the hard coat layer, and a method for simply increasing the thickness of the hard coat layer is considered. However, in the method although hardness becomes hard, because with wrinkles and curling becomes large by curing shrinkage of the hard coat layer tends to occur cracks or peeling of the hard coat layer, was not practically used. In recent years, hard as to achieve high hardness of the coated film, cracking and curing method of solving the problem of curling due to shrinkage has been proposed several hard coat layer (Patent Documents 1 to 4).

Patent Document 1, the cured coating film layer protective film for polarizing plate to form a (optical function layer) comprising a composition containing at least an ultraviolet curable polyol acrylate resin on one surface of the transparent plastic film substrate has been proposed. The ultraviolet-curable polyol acrylate resin, hexaacrylate to dipentaerythritol are mainly illustrated. If the resin was coated on a plastic film substrate, but the pencil hardness by the thickness of the cured coating layer than 10μm is possible to ensure a hardness of at least 4H, curling due to the curing shrinkage it is difficult to simultaneously suppress.

Patent Document 2, on at least one surface of the transparent plastic film substrate is provided with a buffer layer composed of a single layer or multi-layer having a thickness of 3 ~ 50 [mu] m, further by forming a hard coat layer having a thickness of 3 ~ 15 [mu] m on the buffer layer the hard coat film has been proposed to be. The transparent plastic film substrate, each of the pencil hardness of the buffer layer and the optical functional layer has an increased value in this order, thereby being designed to have a pencil hardness 4H ~ 8H overall hard coating film . However, in Patent Document 2, it is necessary to buffer layer in addition to the optical functional layer, complicated production process because it is required to at least two-layer structure, there is a disadvantage that production cost is increased.

Patent Document 3, at least one surface of a transparent plastic film or sheet substrate, after providing a cured optically functional layer containing an internal crosslinking ultrafine inorganic or organic as a first hard coat layer, further a second hard those in which a thin film of a clear curable resin containing no internal crosslinked particles of inorganic or organic as coating layer is proposed. However, the production process by also Patent Document 3 similarly two-layer structure of Patent Document 2 is complicated, there is a disadvantage that production cost is increased.

Patent Document 4, on at least one surface of the transparent plastic film substrate, a hard coat film The hard coat layer of at least one layer is formed, a hard coat layer-forming material of the resin per 100 parts by weight inorganic fine particles contains 20 to 80 parts by weight, the hard coat layer total thickness and a 10 [mu] m ~ 50 [mu] m, and the pencil hardness of the surface have been proposed at least 4H. However, as used Patent Document 4, the hard coat layer-forming material containing the above proportions of the inorganic fine particles to the resin, such as polyester acrylate or polyurethane acrylate, a hard coat layer with a thickness of more than 10μm on a transparent plastic film substrate in the case of forming the can, it is difficult to balance the suppression of curling by ensuring the cure shrinkage of sufficient hardness.

As a method of improving the visibility of the hard coat film on a transparent plastic film substrate, urethane acrylate, isocyanuric acid acrylate, and (JP hard coat film has been proposed which has a hard coat layer containing an inorganic translucent fine particles 5). This is because the inorganic translucent fine particles, it is intended to adjust the difference in refractive index of the transparent plastic substrate and the hard coat layer, those contents such preventing interference fringes of the reflected and the light of the hard coat film. Indeed, by the refractive index adjustment of the hard coat layer of an inorganic translucent fine particles, although the reflection of the hard coat film is reduced, film-forming properties for compatibility and dispersibility of the hard coat layer component is insufficient worse, since the hard coat layer thickness varies subtly, interference fringes overcome difficult. Also, was not it can be said that the satisfactory workability from the film-forming properties of the poor.

The pencil hardness increase of the surface must be thicker hardcoat layer but, since the adhesion between the hard coat layer and the transparent plastic film substrate when the thickness of the hard coat layer is deteriorated, curling and wrinkles on the hard coat film We had a problem that occurs. The problem is, in forming the hard coat layer by curing an ionizing radiation curable resin which is the material of the hard coat layer, the ionizing radiation curable resin that was contributed to shrinkage on curing. Examples Carl wrinkle measures proposed to fill the inorganic fine particles such as silica to the hard coat layer have been made (Patent Document 6). When used as polarization substrate, upon polarization-board processing must advance subjected to a saponification treatment. However, by the saponification treatment, the silica is eluted in the saponified solution, it had a problem that the effect of the silica is lost.

Hard coat film becomes provided such a surface and the display surface of the casing, by improving the surface hardness, it is possible to prevent scratching of the components. Hard coat film, or a hard coat layer on a resin film is laminated one layer or more layers, having a separate layer between the resin film and the hard coat layer.
Hard coat film on the resin film, after the ionizing radiation curable resin such as thermosetting resin or an ultraviolet curable resin was applied as a hard coat layer is formed by curing. Several μm approximately the thickness of the hard coat layer, the surface hardness of the hard coat layer by a pencil hardness (JIS K5400), because H ~ 3H is common.
Further, from the viewpoint of effective utilization of the resin film, it is common to so as to cover all of the one or both surfaces of the resin film to form a hard coat layer.

As a method of improving the surface hardness of the hard coat layer, a method of increasing the thickness of the hard coat layer. However, although In this method improves the surface hardness of the hard coat layer, and at the same time cracking or peeling of the hard coat layer is liable to occur, and the manufacturing process of the hard coat film, wrinkles Ya in various secondary processing process using it since the problems such as curling occurs, it was not practically used. Additional wrinkle or curl such problems were those likely to occur as the surface hardness of the hard coat layer is increased. Additional wrinkle or curl such problem becomes particularly problematic when used in optical applications. For example, when using a hard coat film as a protective film for polarizing plate, saponified to the hard coat film (acid or alkali) that processes performed are common. Surface modification of the hard coat film is made by saponification is improved coatability of the adhesive or a pressure-sensitive adhesive. Thus through an adhesive or a pressure-sensitive adhesive, a polarizer substrate, adhesion between the hard coat film is improved. However, the saponification process, cracks in the hard coat film, wrinkling or curling had a problem tends to occur due to cure shrinkage.
In addition, productivity can be improved by creating a hard coat film by Roll-to-Roll. However, and the step of producing a hard coat film by Roll-to-Roll, the secondary processing processes (for example, saponification treatment) in the case of performing the cracking to the hard coat film, wrinkling and curling are likely to occur due to the curing shrinkage I had a problem.

Further, for example, Patent Document 1, the protective film for polarizing plate which is formed a cured coating film layer made from a composition comprising at least one surface of dipentaerythritol hexaacrylate and silica fine particles of the transparent resin film has been proposed. When performing coating the resin on a transparent resin film substrate, a pencil hardness can be ensured more hardness 4H by the thickness of the cured coating layer above 10 [mu] m. However, when the thickness of the cured coating layer above 10 [mu] m, it is difficult to suppress the occurrence of curling due to cure shrinkage. Occurrence of curl was made more likely to occur by the saponification process.

Patent Document 2, on at least one surface of a plastic base film, provided with a buffer layer composed of a single layer or multi-layer having a thickness of 3 ~ 50 [mu] m, further by forming a hard coat layer having a thickness of 3 ~ 15 [mu] m on the buffer layer the hard coat film has been proposed to be. The transparent plastic film substrate, each of the pencil hardness of the buffer layer and the hard coat layer has an increased value in this order, thereby being designed to have a pencil hardness 4H ~ 8H overall hard coating film . However, in the invention disclosed in Patent Document 2, because it requires a buffer layer in addition to the hard coat layer, there is a disadvantage that burden the manufacturing process.

JP-9-113728 discloses JP 11-300873 discloses JP 2000-52472 JP JP 2000-112379 JP JP 2006-106427 JP JP 2003-248101 JP

The present invention (alpha), while with excellent surface hardness, have been suppressed curling by cracking or curing shrinkage, and the visibility of the screen is good, optics can be suitably used in LCD or PDP of TV applications and to provide a laminate.

Conventionally, it has a high surface hardness, unlikely to the occurrence of curls and wrinkles, chemical resistance (e.g., alkali-treated in saponification) excellent optical laminated body was present. Accordingly, the present invention (alpha) is excellent in scratch resistance, has high surface hardness (pencil hardness), excellent chemical resistance, less occurrence of curling, an optical functional layer having excellent antifouling property (for example, a hard coat and to provide an optical laminate having or layer, an antiglare layer). Further, in the case of applying a saponification treatment to the optical stack are also translucent fine particles (e.g., silica) are eluted in saponification liquid, that there is no optical laminate effect of light-transmitting particulate material is lost an object of the present invention is to provide.

The present invention (beta) is a layer formed by laminating a hard coat layer 1 layer on a resin film, even if the pencil hardness of the hard coat layer is not less than 4H, the hard hard coat film curling occurs an object of the present invention is to provide.
Further, the present invention (beta) is a hard coat film produced by Roll-to-Roll process and its secondary processing process (e.g., saponification treatment) in the case of performing also provide curl hardly occurs hard coat film also an object of the present invention to.

The present invention (alpha) is the following inventions (1) to (4).

The present invention (1) is on one side or both sides of the light-transparent substrate, directly or via another layer, the optical laminate having a optical function layer,
Wherein the optical functional layer is a thickness of 3 ~ 50 [mu] m,
Contains a translucent resin and the translucent particles,
The resin translucent resin, containing the ionizing radiation-curable polyfunctional acrylate, and ionizing radiation-curable fluorinated acrylate 0.05 to 50% by weight relative to the total weight of the solid components of the optical functional layer characterized in that it is formed by irradiating the ionizing radiation of the composition, an optical laminate.

The present invention (2), the fluorinated acrylate, from the light-transparent substrate side of the optical functional layer, is unevenly distributed on the surface side, an optical laminate of the invention (1).

The present invention (3) further has a polarization substrate, an optical laminate of the invention (1) or (2).

The present invention (4), the invention (1) or (2) an optical functional layer according to is antiglare film characterized by comprising comprises a surface relief structure.

The present invention (beta) is obtained by solving the above problems by the technical configuration of the invention described below (5) to (9).

(5) Hard coat layer stacked on the resin film, the thickness of the hard coat layer is A (mm), width (ear up from the edge of the resin film to the edge of the hard coat layer when the width) and B (mm), a hard coat film, characterized in that a × 1500 <B (where a 0.003mm ≦ a ≦ 0.020mm).
(6) The hard coat film according to (5) that the elastic modulus of the resin film is 2 GPa ~ 8 GPa.
(7) The hard coat film according to (5) a thickness of the resin film is 5 ~ 100 [mu] m.
(8) The hard coat film according to the hard coat layer contains a radiation-curable resin, wherein the volumetric shrinkage of the radiation curable resin is 5 to 25% (5).
(9) The invention (5) antiglare film to (8) hard coat layer according to any one is characterized by being provided with a surface irregular structure.

In the present specification, the "optical stack," "hard coat film" means the same thing.

According to the present invention (1), as a result of the resin composition of the optical functional layer contains a polyfunctional acrylate and fluorinated acrylate, improved surface hardness, furthermore, to impart slip properties to the optical functional layer surface because it has an effect that scratch resistance is improved. Further, since the resin composition of the optical functional layer contains a fluorinated acrylate, water repellent effect of the components, the effect of improving chemical resistance, antifouling property. Further, by the light-transmitting particle is dispersed between the molecules of the resin matrix, and reduce the cure shrinkage of the UV resins such as polyfunctional acrylate, an effect that can prevent curling.

According to the present invention (2), by fluorinated acrylate is unevenly distributed on the surface side, easily the fluorinated acrylate components are exposed on the surface, improving and scratch resistance due to the improvement of the slipperiness of the surface, the water repellent effect chemical resistance due to the effect such as improvement of antifouling property becomes more prominent. Furthermore, materials with fluorine because it is generally expensive, it is economically advantageous because it can reduce the amount of material having fluorine by localized fluorine on the surface of the optical function layer.

According to the present invention (3), when providing the polarization substrate, even saponification process is performed which essentially performed, translucent fine particles dispersed in the optical function layer (e.g., silica) is saponified because never out practically insoluble in the liquid, preventing curling effect is continued.

According to the present invention (beta), compared with the conventional hard coating film one side or so as to cover the entire both surfaces to form a hard coat layer of the resin film, a hard coat film of the present invention, the hard coat layer thickness since was a (mm) and a × 1500 the relationship of the width of the edge of the resin film to the edge of the hard coat layer B (mm) <B (where, 0.003mm ≦ a ≦ 0.020mm), resin the hard coat layer on the film of a single layer laminated layer structure, it is possible pencil hardness of the hard coat layer is to provide a curling hardly occurs hard coat film even when more than 4H.
Further, the present invention (beta) is a hard coat film produced by Roll-to-Roll process and its secondary processing process (e.g., saponification treatment) in the case of performing also provide curl hardly occurs hard coat film can do.

According to the present invention (6) (7), cracking, it is possible to provide a hard hard coat film occur wrinkles due to curing shrinkage.

Figure 1 is a diagram illustrating a method of measuring the curl of the present invention (alpha). It is a plan view of a hard coat film of the present invention (beta). It is a cross-sectional view of the hard coat film of the present invention (beta). A diagram showing a method of measuring the curl of the present invention (β), (a) a plan view, a partial enlarged view of (b) a side view.

Hereinafter, it will be described with respect to the optical laminate of the present invention (alpha).

Optical laminate according to the best mode, the transparent substrate on, the basic structure of which the optical functional layer is laminated. The optical functional layer according to the best mode is located on the outermost surface of the optical stack, it is preferable to be used as or low refractive index layer is used as a hard coat layer. Here, the optical functional layer may be laminated on one surface of the light-transparent substrate is laminated on both sides. Furthermore, the optical stack may have other layers. Other layers, where, for example, polarization substrate, a hard coat layer (for example, an optical functional layer is provided when used as a low refractive index layer.), Other functionalization layer (e.g., an antistatic layer, the near infrared (NIR), the absorption layer, a neon-cut layer, electromagnetic wave shielding layer, an optical functional layer), and the like. The position of the other layers, for example, in the case of the polarization substrate is a on the light-transparent substrate on the opposite side from said optical functional layer, in the case of other functional imparting layer of the optical functional layer to the lower layer. Also, it may function the optical functional layer as a low-reflection layer. Hereinafter, detail of each component of the optical stack according to the best mode (light-transparent substrate, the optical functional layer, etc.).

First, as the light-transmitting substrate according to the best mode is not particularly limited as long as it is translucent, and glass such as quartz glass and soda glass can be used, polyethylene terephthalate (PET), triacetyl cellulose ( TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene-containing resins, polyether sulfone, cellophane, can be suitably used various resin films such as aromatic polyamides. These films also those of non-oriented, it is also possible to use those having been subjected to stretching. Especially polyethylene terephthalate films biaxially stretched is preferably from the viewpoint of excellent mechanical strength and dimensional stability, unstretched triacetyl cellulose (TAC) is preferable because a very small retardation in the film plane. Incidentally, PDP, when used in LCD, these PET, TAC film is more preferable.

Although the transparency of these light-transmitting substrate, the better the high total light transmittance (JIS K7105) of 80% or more, more preferably 90% or higher. The thickness of the light-transparent substrate, but thinner is preferable from the viewpoint of weight reduction, when considering its productivity and handling properties, a range of 1 ~ 700 .mu.m, preferably used 20 ~ 250 [mu] m it is preferable. When using the optical laminate of the present invention in LCD applications, it is preferred to use the TAC of 20 ~ 80 [mu] m as the light-transparent substrate. In the optical laminate of the present invention, particularly in the case of using the TAC of 20 ~ 80 [mu] m as the translucent substrate, it is possible to prevent curling, suitably used in LCD applications thin and light are required be able to.

Further, the light-transmitting substrate, alkali treatment, corona treatment, plasma treatment, sputtering treatment, and surface treatment of the saponification process and the like, a surfactant, a surface modification treatment such as coating, such as a silane coupling agent, or Si vapor deposition by performing, it is possible to improve the adhesion between the light-transparent substrate and the optical functional layer. By performing these processes, to improve the adhesion between the light-transparent substrate and the optical functional layer, the scratch resistance of the optical functional layer, the surface hardness and chemical resistance can be improved.

Next, it will be described in detail an optical functional layer according to the best mode. Translucent resin contained in the essential in such optical functional layer to the best mode is to ionizing radiation to the resin composition containing the ionizing radiation-curable polyfunctional acrylate and ionizing radiation-curable fluorinated acrylate formed by. The amount of ionizing radiation-curable polyfunctional acrylate, based on the total weight of the solid components of the optical functional layer is preferably 20 to 80 wt%, more preferably 30 to 60 wt%. The amount of ionizing radiation-curable fluorinated acrylate, based on the total weight of the solid components of the optical functional layer, 0.05 to 50 wt% is contained indispensably, is preferably 0.2-50 wt% , more preferably 5 to 50 wt%, it is more preferred 10-40 wt%. If the amount of the ionizing radiation curable multifunctional acrylate is less than 20 wt%, reduces the crosslink density of the optical functional layer, the pencil hardness is deteriorated. Further, when it is more than 80 wt%, easily curling occurs. If the amount of the ionizing radiation-curable fluorinated acrylate is less than 0.05 wt%, water repellency, slipperiness is lowered, scratch resistance, stain resistance, chemical resistance is deteriorated.

Here, it is preferable that the fluorinated acrylate is unevenly distributed on the surface side of the light-transmitting substrate side. By including the structural, scratch resistance, chemical resistance, effects such as antifouling property becomes more prominent. In particular, it is more preferred that the fluorinated acrylate is incrementally present toward the surface side from the light-transparent substrate side of the optical functional layer. In the present specification and claims, cured by (cured component fluorinated acrylate is by ionizing radiation) and polyfunctional acrylate-derived component (multifunctional acrylate ionizing radiation fluorinated acrylate-derived components of the optical functional layer ingredients) just about to be referred to simplify as "fluorinated acrylate" and "polyfunctional acrylate". In the present invention, the fluorinated acrylate is unevenly distributed on the surface side of the light-transparent substrate side, a fluorine element ratio of 10% that is present in a range to a depth of 5nm from the optical functional layer surface containing a fluorinated acrylate It says that is greater than or equal to. It is preferred that the fluorine element ratio is 20% or more. The upper limit is not particularly limited, for example, 80% or less. Fluorine element ratio, X-ray photoelectron spectroscopy (Electron Spectroscopy for Chemical Analysis: hereinafter referred to as "ESCA".) Is measured by. In ESCA, fluorine obtained at a depth 5 nm, carbon, oxygen, and from the peak area such as silicon, to calculate the abundance ratio of fluorine.
Further, the fluorine present in the case where the range to a depth of 200nm from the optical functional layer surface was measured at 5nm increments by ESCA, the depth of 5nm each obtained by measuring at 5nm increments to a depth of 5nm from the optical functional layer surface the element ratio is preferably a value obtained by dividing the average value of the fluorine element ratio existing in depth 200nm from a depth 5nm of the optical functional layer surface is 10 or more, further preferably 20 or more. The upper limit is not particularly limited, for example, 1,000 or less. By the value to 10 or more, since it is possible to present efficiently the fluorine atom in the optically functional layer surface, in the case of using the fluorine-containing material is expensive, provide excellent optical laminate economics can do.

Here, a multifunctional acrylate, if material number of (meth) acryloyloxy groups in one molecule is two or more is not particularly limited, for example, EO adduct di (meth) acrylate of bisphenol A, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth Acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate-hexane diisocyanate urethane polymer, hexamethylene diisocyanate urethane prepolymer to pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate toluene diisocyanate urethane prepolymer, pentaerythritol tri (meth) acrylate isophorone diisocyanate urethane prepolymer, etc. hexaacrylate to dipentaerythritol may be used. These monomers may be used alone or in combination. The multifunctional acrylate, 3 or more functional are preferred, four or more functional being more preferred.

The fluorinated acrylate is not particularly limited, for example, 2- (perfluoro decyl) ethyl methacrylate, 2- (perfluoro-7-methyl-octyl) ethyl methacrylate, 3- (perfluoro-7-methyl-octyl) -2 - hydroxypropyl methacrylate, 2- (perfluoro-9-methyldecyl) ethyl methacrylate, 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- ( perfluoro decyl) ethyl acrylate, 2- (perfluoro-9-methyldecyl) ethyl acrylate, pentadecafluorooctyl (meth) acrylate, Una decafluoro hexyl (meth) acrylate, nonafluorobutyl pliers (Meth) acrylate, heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, pentafluoropropyl (meth) acrylate, trifluoroethyl (meth) acrylate, tri iso-fluoro-isopropyl (meth) acrylate, trifluoroethyl (meth ) acrylate, the following compounds (i) ~ (xxx) can be used. Incidentally, the following compounds are those all exhibited case of acrylate, acryloyl group in the formula can be changed to a methacryloyl group both.

Figure JPOXMLDOC01-appb-C000001

Figure JPOXMLDOC01-appb-C000002

Figure JPOXMLDOC01-appb-C000003

Figure JPOXMLDOC01-appb-C000004

Figure JPOXMLDOC01-appb-C000005

The above compound (i) ~ (xxx) describes a only one of a hydrogen atom as R in the following general formula (1), both methyl one of the hydrogen atoms in methylene group bonded to the carbonyl carbon It can be changed based on.

Figure JPOXMLDOC01-appb-C000006

These can be used alone or plural kinds in combination. Among the above fluorinated acrylate, multifunctional fluorinated acrylate is preferred. Here, the polyfunctional fluorinated acrylate with two or more (preferably 3 or more, more preferably 4 or more) but having the (meth) acryloyloxy group.

Translucent resin according to the best mode, as an optional component, the isocyanurate of ε- caprolactone-modified consisting the following formula 7 formula, it is preferable to contain at least one. Resin segment portion of the ε- caprolactone mixed, because inorganic pigments, affinity with the additive may, for example, efficient production in paint manufacturing process of the optical functional layer, the film formation stability in the deposition step contribute to, such as gender (reduction of thickness variation). Also, birth flexibility throughout the optical functional layer, it is effective to such relaxation of the internal stress (curl suppression).

Figure JPOXMLDOC01-appb-C000007

Other isocyanurate of ε- caprolactone-modified optically functional layer, thermosetting resin, radiation curable resin is mixed, can be used, radiation-curable resin which can be cured optically functional layer to radiation towards the system using the production efficiency, in terms of energy costs, it preferred advantageous. Examples of the radiation curable resin, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy or Le radically polymerizable functional group such as oxy group, an epoxy group, vinyl ether group, a monomer having a cationic polymerizable functional group such as oxetane group, oligomer composition the prepolymer alone or appropriately mixed is used. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate. Oligomers, as a prepolymer, polyester acrylate, polyurethane acrylate, hexamethylene diisocyanate urethane prepolymer to polyphenylene glycidyl ether, phenyl glycidyl ether triene diisocyanate urethane prepolymer, epoxy acrylate, polyether acrylate, alkyd acrylate, melamine acrylate, silicone acrylate, etc. acrylate compounds, unsaturated polyesters, tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol a diglycidyl ether and various alicyclic epoxy compounds such as epoxy, 3-ethyl -3 - hydroxymethyl oxetane, 1,4-bis { (3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and di [1-ethyl (3-oxetanyl)] oxetane compounds such as methyl ether.

The amount of the isocyanurate of ε- caprolactone-modified is not particularly limited, the total solid content of the material for forming an optical functional layer is preferably in the range of 5-50%, more preferably in the range of 10-30%. If the amount of ε- coupler port lactone-modified isocyanurate is small, adhesiveness is lowered in light-transparent substrate and the optical functional layer, curling is increased. Further, in the deterioration of film forming property, interference unevenness (interference unevenness by fine thickness unevenness of the optical function layer) occurs, the visibility is deteriorated. Furthermore, thick films of the optical functional layer, there is a case where wrinkles and cracking occurs in the optical function layer. On the other hand, if the amount is too large, scratch resistance of the optical functional layer decreases.

The radiation of curing the system using the above radiation-curable resin, ultraviolet, visible, infrared, may be any of the electron beam. These radiation, even the polarization may be a non-polarized light. In particular, equipment cost, safety, ultraviolet from the viewpoint of running cost are preferred. As the energy ray source of the ultraviolet, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, nitrogen laser, an electron beam accelerator, such as a radioactive element is preferred. The amount of irradiation with the energy radiation source of accumulative exposure at an ultraviolet wavelength of 365 nm, preferably in the range of 100 ~ 5,000mJ / cm 2, 300 ~ 3,000mJ / cm 2 irradiation amount, of less than 100 mJ / cm 2 since the curing becomes insufficient, there is a case where the hardness of the optical functional layer is lowered. If it exceeds 5,000 mJ / cm 2, the optical function layer is transparent and colored to decrease. When performing curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. As the photopolymerization initiator, there can be used those known in the art. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4'-diamino benzophenone, benzoin and its alkyl ethers such as benzyl methyl ketal; acetophenone, 3 - methylacetophenone, 4-chloro benzophenone, 4,4'-dimethoxy benzophenone, acetophenones such as 2,2-dimethoxy-2-cyclohexyl phenyl ketone to 1-hydroxycyclopentyl; methyl anthraquinone, 2-ethylanthraquinone , anthraquinones such as 2-amyl anthraquinone; xanthone; thioxanthone, 2,4-diethyl thioxanthone, thioxanthone such as 2,4-diisopropyl thioxanthone; a DOO acetophenone dimethyl ketal, ketals such as benzyl dimethyl ketal; benzophenone, benzophenones such as 4,4-bis-methylamino-benzophenone and the like; 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1 the on-the like. These may be used alone, or two or more thereof. The amount of the photopolymerization initiator, relative to the radiation curable resin composition, degree 5% in total solids ratio, more preferably 1-4%.

The system of the radiation curable resin composition, may be added using a polymer resin in a range that does not interfere with the polymerization curing. The polymer resin is an organic solvent-soluble thermoplastic resin used in the later-described optical functional layer coating, particularly acrylic resins, alkyd resins, polyester resins, and cellulose derivatives and the like, these the resin, a carboxyl group or a phosphoric acid group, have an acidic functional group such as a sulfonic acid group preferably

Further, a leveling agent, a thickener, an antistatic agent, may be used fillers, additives such as extender pigment. Leveling agent, there is work to fix the defect before film formation achieving tension uniformity of the coating film surface, interfacial tension than the radiation curable resin composition, the surface tension are both less material is used.

The optical function layer is composed of a cured product of such predominantly above resin composition, a method of forming the radiation after coating a coating material comprising a resin composition and an organic solvent, to evaporate the organic solvent ( for example, those of curing by electron beam or ultraviolet radiation) or heat. The organic solvent used here, it is necessary to select those suitable for dissolving the resin composition. Specifically, the wettability of the light-transparent substrate, the viscosity, in view of the coatability such drying rate, alcohol, ester, ketone, ether, either alone or mixed selected from aromatic hydrocarbons it is possible to use a solvent.

The thickness of the optical functional layer is required to be in the range of 3 ~ 50 [mu] m, more preferably in the range of 5 ~ 30 [mu] m, more preferably in the range of 7 ~ 20 [mu] m. If the optical function layer is less than 3μm is abrasion with scratch resistance is degraded, interference unevenness undesirably conspicuous. If thicker than 50μm, the or curling occurs due to cure shrinkage of the optical functional layer, microcracks may occur in the optical function layer surface, or reduced adhesion to the light-transmitting substrate, and further optical transparency reduced or. Then, also causes a cost increase due to an increase in required coating amount with an increase in film thickness.

The translucent fine particles contained in the optical functional layer, for example, acrylic resin, polystyrene resin, styrene - acrylic copolymer, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluoride, consisting polyfluorinated ethylene resin such as an organic translucent fine particles and titanium oxide, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, zirconium oxide, calcium oxide, indium oxide, antimony oxide, or an inorganic light-transmitting particulate material (inorganic such as these composites it is possible to use the ultra-fine particles) of. Note that these particles may be used alone or in combination of two or more thereof. As translucent fine particles, it is preferred to use a crosslinked organic light-transmitting fine particle and the inorganic light-transparent fine particles. This enhances the pencil hardness of the hard coat film after curing, it is possible to prevent curling. Further, as the translucent particles, the use of silica, reduces the refractive index of the optical functional layer is preferable since uneven interference that affects the image quality of the display is reduced. Further, silica silicate-based material (e.g., vinyl group, methacryl group, an amino group, a silane coupling agent such as alkoxysilane having a functional group such as epoxy group) when treated with elution of the silica during the saponification it is possible to prevent. The particle size of the translucent particles is preferably 1 ~ 100 nm, and more preferably 10 ~ 50 nm. If the particle size is 1nm smaller, or chemical resistance is decreased, or increased production costs of the particles. If 100nm greater than the transmittance may decrease, or haze is increased, the influence on the optical properties such contrast decreases occurs. "Particle size" refers to the average value of the diameters of 100 particles were measured by electron microscopy. Among the total number, the fine powder and coarse powder mixed in the manufacturing process of the fine particles is less than 5% (more preferably less than 1%). The amount of the light-transmitting particle is preferably 5 to 70 wt%, and more preferably 10 to 50 wt%. When the amount is less than 5 wt%, the anti-curl effect, pencil hardness decreases. When the amount is more than 70 wt%, scratch resistance is deteriorated. Light-transmitting particulate material is preferably used in a sol, with a coating material is likely performed to improve the dispersibility of the light-transmitting particulate material in the paint. The sol was translucent fine particles, for example, it can be used an alumina sol or silica sol. The method of forming the sol will be described later.

Incidentally, in such contain an average particle diameter of 0.3 ~ 10 [mu] m translucent fine particles in the optical functional layer, forming a concavo-convex structure on the optical surface of the functional layer, it is possible to use as the antiglare layer preferable. This makes it possible to use as an anti-glare film. Refractive index of the average particle diameter of 0.3 ~ 10 [mu] m translucent fine particles is 1.40 preferably to 1.75, the refractive index is greater than 1.40 or less than 1.75, the light-transmitting substrate Alternatively the difference in refractive index between the resin matrix becomes too large, the total light transmittance decreases. The difference in refractive index between the translucent particles and the resin component is preferably 0.2 or less. The average particle size of the translucent particles is preferably in the range of 0.3 ~ 10μm, 1 ~ 8μm and more preferably. Since the particle size is in the case 0.3μm less than the antiglare property is degraded, and if 10μm greater, as well generates a glare is not preferable because the surface degree of surface irregularity becomes too large becomes whitish. The proportion of the light-transmitting particle contained in the resin is not particularly limited, the resin composition 100 parts by weight, antiglare function to 1 to 20 parts by weight, preferably in order to satisfy the characteristics such as glare , easy to control the fine irregularities and haze value of the optical functional layer surface. Here, "refractive index" refers to the measurements in accordance with JIS K-7142. Further, the "average particle size" refers to the average value of the diameters of 100 particles were measured by electron microscopy.
That is, particle size by a light-transmitting particulate material of 1 ~ 100 nm, a particle diameter optical functional layer containing a light-transmitting fine particle is 0.3 ~ 10 [mu] m and (antiglare layer), improvement of pencil hardness, it is possible to provide an optical laminate that impart anti-curl and anti-glare properties of the (antiglare film).

In the optical laminate of the present invention, difference in refractive index and the optical functional layer of the light-transmitting substrate (Refractive index of the translucent substrate] - [refractive index of the optical functional layer]) is 0.10 or less it is preferably, refractive index of the optical functional layer, more preferably not more than the refractive index of the light-transmitting substrate. By controlling the refractive index difference so that the range, it is possible to suppress the reflection of light at the surface.

The control of the refractive index can by caulking is contained appropriately inorganic translucent fine particles in the optical function layer. Inorganic light-transparent fine particle has a function of adjusting the apparent refractive index of an optical functional layer according to the amount. The refractive index of the refractive index and the optical functional layer of the light-transparent substrate is as described above, it is preferable that the approximation. Therefore, In the preparation of the optically functional layer-forming material, wherein such difference in refractive index and the optical functional layer of the light-transparent substrate is reduced, to adjust the amount of the inorganic light-transparent fine particles suitably have preferable. If the refractive index difference is large, a phenomenon occurs in which reflected light of external light incident to the optical stack called interference unevenness exhibiting a hue of iridescent, will drop the display quality. In particular, the high frequency of the image display device having an optical stack is used office, as fluorescent lamps, three band fluorescent lamp has been greatly increased. Three band fluorescent lamp, stronger emission intensity of a specific wavelength, but has a feature that an object can be seen clearly, further interference unevenness in the three-wavelength fluorescent lamp is found that remarkable.

In the present invention, the transparent substrate on the surface opposite to the optical functional layer may be laminated polarization substrate. Here, the polarization substrate is used the polarizing film and the light-absorbing absorbing other light transmits only specific polarized light, the polarizing film transmitting only specific polarized light reflection type for reflecting the other light to it can be. The polarizing film of light-absorbing, polyvinyl alcohol, films obtained by stretching a polyvinylene etc. are possible using, for example, a polyvinyl alcohol having adsorbed iodine or a dye as a dichroic element obtained by uniaxially stretching polyvinyl alcohol (PVA) film and the like was. The polarizing film of the light reflection type, for example, the stretched two in which the refractive index in the stretching direction is different when the polyester resin (PEN and PEN copolymers) were laminated and stretched to several hundred layers alternately by extrusion techniques 3M Co. "DBEF" or configuration, by laminating the cholesteric liquid crystal polymer layer and a quarter-wave plate, separated into two circularly polarized light opposite directions the light incident from the cholesteric liquid crystal polymer layer side, whereas transmits and reflects the other, manufactured by Nitto Denko Corporation configuration for converting the circularly polarized light transmitted through the cholesteric liquid crystal polymer layer into linearly polarized light by the quarter-wave plate "Nipokkusu" and Merck "trans Max" and the like .

The light-transparent substrate, an antistatic layer may be provided in order to prevent contamination such as dust adhering electrostatically to the display surface. However, the antistatic layer is disposed in addition to the outermost surface. Antistatic layer, aluminum, metals such as tin, depositing a metal oxide film such as ITO, a method of providing an extremely thin by sputtering or the like, aluminum, metal particles or whiskers, such as tin, antimony or the like to a metal oxide such as tin oxide doped particles and whiskers, 7,7,8,8-tetracyanoquinodimethane and the metal ion and an electron donor organic cations such as polyesters what was a charge-transfer complex made between (donor) and a filler, etc. resin, acrylic resin, dispersed in an epoxy resin or the like, provided by a method such as a method, polypyrrole, provided by polyaniline in camphorsulfonic acid and solvent coating or the like doped with providing by a solvent coating, and the like. Transmittance of the antistatic layer in the case of optical applications, preferably 80% or more.

Furthermore, in order to improve the contrast, it is possible to use an optically functional layer as a low-reflection layer. In this case, it is preferable to further provide a hard coat layer having a thickness of 3 ~ 50 [mu] m in the lower layer. In this case, it is preferable to increase the wettability of the surface of the hard coat layer. By increasing the wettability, improved affinity with the hard coat layer and the optical functional layer, it is possible to improve the adhesion between the layers. Corona treatment surface of the hard coat layer, by performing plasma treatment or the like, it is possible to enhance the wettability. As the wettability of the hard coat layer surface, the contact angle of water of the surface of the hard coat layer can be used as an index. Preferably the contact angle is less than 80 degrees, more preferably not more than 65 degrees. In this case, it is necessary that the refractive index of the low reflective layer is lower than the refractive index of the lower layer is preferably 1.45 or less. As the material having these especially fine, in addition to the fluorinated acrylate mentioned above, for example, LiF (refractive index n = 1.4), MgF 2 ( n = 1.4), 3NaF · AlF 3 (n = 1. 4), AlF 3 (n = 1.4), Na 3 AlF 6 (n = 1.33), the inorganic material into fine particles and the like, inorganic low-reflection material containing the acrylic resin or epoxy resin, etc. it can be combined organic compound of a silicone-based, thermoplastic resin, thermosetting resin, and organic low-reflection material such as a radiation curable resin. Further, the low reflective layer preferably has a critical surface tension is less than 20 dyne / cm, more preferably not more than 18dyne / cm, more preferably not more than 15 dyne / cm. If the critical surface tension is greater than 20 dyne / cm is hardly 0.00 dirt adhering to the low reflection layer.

Furthermore, it is also possible to use a 5 ~ 30 nm of the ultrafine silica particles low reflection material obtained by mixing a sol with a fluorine-based film-forming agent dispersed in water or an organic solvent. The 5 ~ 30 nm silica ultrafine particles dispersed in water or an organic solvent sol, a method of neutralizing the alkali metal ions in the alkali silicate and a method of de-alkali ion exchange or the like, the alkali silicate with a mineral acid known sol obtained by condensing an active silicic acid known in such known silica sol obtained by hydrolysis and condensation in the presence of a basic catalyst to the alkoxysilane in an organic solvent, more above aqueous the organic solvent-based silica sol obtained by substituting the organic solvent by distillation or the like of water in the silica sol (organosilica sol) are used. These silica sols can be employed in either an aqueous or organic solvent-based. In the production of the organic solvent-based silica sol is not necessary to replace the organic solvent completely water. The silica sol, a solid content of 0.5 to 50% strength by weight as SiO 2. Structure of ultrafine silica particles in the silica sol are spherical, needle-shaped, are various plate or the like can be used.

The thickness for the low reflective layer to exhibit good antireflection function can be calculated by known formulas. If the incident light is perpendicularly incident on the low reflective layer, the conditions for the low reflective layer is not reflects and transmits light 100% is a should satisfy the following relation. The refractive index of wherein N o is the low reflective layer, N s is lower refractive index, h is the thickness of the low reflective layer, lambda o represents the wavelength of light.

Figure JPOXMLDOC01-appb-M000008

According to the above (1), the reflection of light in order to prevent 100%, the refractive index of the low reflective layer is understood that the material may be selected such that the square root of the refractive index of the lower layer. However, in practice, the material that satisfies this equation completely is difficult heading will select the material as close as possible. Equation (2) In (1) in the refractive index of the selected low-reflection layer, the optimum thickness of the wavelength of light as the reflection preventing film of the low reflective layer is calculated. For example, the lower layer, respectively the refractive index of the low reflective layer 1.50,1.38, the wavelength of light and 550 nm (reference luminosity) Substituting these values ​​into equation (2) above, the low reflective layer thickness 0.1μm before and after the optical film thickness is calculated preferably to be optimal in the range of 0.1 ± 0.01 [mu] m.

Method of producing an optical laminate of the present invention, for example, on a light-transparent substrate, a multi-functional acrylate, fluorinated acrylate, coating a radiation-curable resin coating material containing a light-transmitting particles, after drying, radiation cured It carried out by creating. Since fluorine-containing material is expensive, it is preferable to unevenly distributed on the surface of the optical function layer. In the present invention, in particular the drying process is important. It is preferable to perform slow drying at low temperatures in the drying process. By performing slow drying, collection fluorinated acrylate is the optical functional layer surface, which by radiation curing, it is possible to obtain an optical functional layer fluorinated acrylate is unevenly distributed on the surface side. Here, the drying temperature is preferably 50 ~ 130 ° C., and more preferably 60 ~ 100 ° C.. Drying time is preferably 1-10 minutes, 2-5 minutes is more preferable. Further, by applying a radiation-curable resin coating material immediately after having formed a coating film, while entering the drying step, it is preferable to provide a pre-drying step. Thus, it is possible to further perform slow drying of the coating film, the fluorinated acrylate is easily localized on the surface side of the optical functional layer. The pre-drying step, from the coating film flat, substantially vertical, refers to a uniform spraying process weak airflow with respect to the coating film. Air volume of weak air flow is preferably in the range of 0.01 ~ 1.0m / sec. The air volume, a wind speed detection hole anemometer (KANOMAX CLIMOMASTER (TM)) may be measured in a state where away 1cm from the coating film. The temperature of the air flow in the pre-drying step may be set to 20 ~ 60 ° C..

As a method for applying a coating material on a light-transparent substrate, it is applied usual coating method or printing method. More specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating slot orifice coating, calendar coating, dam coating, dip coating, coating or such as die coating, intaglio printing of gravure printing, printing of stencil printing such as screen printing or the like can be used.

Hereinafter, after the present invention (beta) has been described with reference to the drawings, the materials and manufacturing methods constituting the present invention will be described in order.

2 on the resin film 10 is a plan view of the hard coat layer 20 showed a hard coat film 1 formed by laminating the first layer. As shown in FIG. 2, the hard coat layer 20 can be laminated from the end face 11a of the resin film 10 to the end face 11b, but is not limited thereto. That is, the hard coat layer 20 is a than only to be stacked on the resin film 10, and the end faces 21a, 21b of the hard coat layer 20, the end face 11a of the resin film 10, 11b do not have to match.

Figure 3 is a cross-sectional view of the hard coat film 1 by a straight line L in FIG. 2. 3, the thickness of the hard coat layer 20 A, and from the edge 12a of the resin film 10 length to the edge 22a of the hard coat layer 20 (Ear-up width) is B, the resin film 10 edge 12b up to a length of the edge 22b of the hard coat layer 20 is set to B 'from. The length of the B and B 'may be the same, may have separate lengths.

Hard coat film of the present invention is required to be A × 1500 <B. With A × 1500 <B, it is possible to suppress the curling of the hard coat film 1. For example, if the thickness of the hard coat layer is 0.003mm which is the lower limit of the present invention, the above relation becomes 4.5 <B. Further, if the thickness of the hard coat layer is 0.020mm which is the upper limit of the present invention, the above relation becomes 30 <B. Here, the upper limit of B in the above equation is not particularly limited, for example, is 100, preferably 50. Divided by all values ​​if the value below the lower limit of B, wrinkles, it is possible to provide a hard coat film curling hardly occurs. From the viewpoint of effective use of resin film, the ear up width B in relation of A × 1500 <B be brought close to the lower limit of the B preferred.

If it is A × 1500 ≧ B, when the pencil hardness of the hard coat layer constituting the hard coat film (JIS K5400) is not less than 4H, because curling is likely to occur, it is used as a hard coat film of the present invention can not. In the above equation, the value of B is the value of either the smaller values ​​of the B 'and B shown in FIG. 3 is applied.

Next, the material constituting the present invention (beta).

<Resin Film>
Material of the resin film constituting the present invention is not particularly limited.
When using the hard coat film of the present invention for optical applications, such as LCD or PDP, a resin film is good as has high transparency. Specifically, the total light transmittance of the resin film (JIS K7105) of 80% or more, more preferably 90% or more.
As the resin film that can be preferably used in optical applications, in particular, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene-containing resins, polyether sulfone, cellophane, and aromatic polyamide it can be suitably used various resin films. These films also those of non-oriented, it is also possible to use those having been subjected to stretching. PET films, in particular biaxially stretched, preferably from the viewpoint of excellent mechanical strength and dimensional stability, the film comprising a non-stretched TAC film and norbornene-containing resins, in that the phase difference in the plane is very small preferable. Incidentally, PDP, when used in optical applications such as an LCD, these PET films, TAC films, norbornene-containing resin film is more preferable.

Preferably the elastic modulus of the resin film is 2 GPa ~ 8 GPa, more preferably 3 GPa ~ 7 GPa.
By using a resin film having an elastic modulus in the above range as a component of a hard coat film, when using the hard coat film in processed liquid crystal display device on the polarizing plate, a environment of high humidity and low humidity also light leakage is preferable because troubles such as reduction of the polarization degree is hard to occur.
When the elastic modulus of the resin film is less than 2 GPa, when applying the hard coat layer-forming coating material with Roll-to Roll, there is a possibility that the resin film is cut.
Note that the elastic modulus in the present invention means a value measured according to JIS P8113. Specifically, tensile tester (A & D Co., Ltd. Product Name: RTG1210) using the resin film can be obtained by measuring by pulling at 1 mm / min.

Thickness and weight and thinner display of the resin film, from the viewpoint of production suitability of the hard coat film is preferably in the 5 ~ 100 [mu] m, more preferably from 20 ~ 100 [mu] m, is 40 ~ 80 [mu] m it is particularly preferred.
By the thickness of the resin film to the range, the shrinkage stress generated when the hard coat layer is cured, it is possible to resin film is absorbed or alleviated, it is possible to suppress wrinkles and curling of the hard coat film .
Is less than 5μm thickness of the resin film, it becomes difficult to suppress the shrinkage stress caused when curing the hard coat layer, shrinkage in the hard coat layer is generated, wrinkles and curling occurs in the hard coat film, a hard coat film productivity is poor. If the thickness of the resin film is 100μm greater, wrinkles and curling of the hard coat film can be suppressed, but are not preferred because the weight and thickness is difficult. In particular, when a hard coat film of the present invention for optical applications, the thickness of the resin film is 100μm greater it is not preferable.

The resin film, alkali treatment, corona treatment, plasma treatment, sputtering treatment, performing and surface treatment of the saponification process and the like, surfactants, coating such as a silane coupling agent, or a surface modification treatment such as Si deposition can. This can improve the adhesion between the resin film and the hard coat layer.

<Hard coat layer>
The hard coat layer of the present invention may be used after heat-curable resin, a radiation-curable resin or a thermosetting resin and a radiation-curable resin mixed. Volumetric shrinkage of the thermosetting resin or a radiation-curable resin is preferably 5 to 25%. Preferably 7 to 15%.
If it is less than 5%, there is a possibility that abrasion resistance of the hard coat layer decreases.
When it is over 25%, since the shrinkage of the hard coat layer is likely to occur, undesirably curling of the hard coat film is likely to occur.

In the present invention, it is preferable to use a radiation curable resin which can be cured hard coat layer with a radiation as a hard coat layer. Thus, production efficiency is increased, energy costs have advantages such as reducing.
Examples of the radiation curable resin, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy or Le radically polymerizable functional group such as oxy group, an epoxy group, vinyl ether group, a monomer having a cationic polymerizable functional group such as oxetane group, oligomer composition the prepolymer alone or appropriately mixed is used. Examples of monomers are methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate it can. Oligomers, as a prepolymer, polyester acrylate, polyurethane acrylate, polyphenylene glycidyl ether hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether triene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, a polyfunctional urethane acrylate and pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, epoxy acrylate, polyether acrylate, alkyd acrylate, melamine acrylate, acrylate compounds and silicone acrylate, unsaturated Sum polyester, tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxy compounds such as epoxy, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and di [1-ethyl (3-oxetanyl)] oxetane compounds such as methyl ether.

Although radiation curable resins may be employed alone or in combination, a multifunctional acrylate, such as curing speed, dipentaerythritol hexaacrylate with excellent scratch resistance of the hard coat layer, the resin film and the hard coat layer adhesion to the flexibility of the hard coat layer, a mixed system of a multifunctional urethane acrylate having excellent flexibility is more preferable. The mixing ratio of the polyfunctional urethane acrylate for multifunctional acrylates is preferably in the range of 0.1 to 1.5. Range of 0.2 to 0.7 is more preferred. When the ratio of the multifunctional urethane acrylate for multifunctional acrylate is too low, easily wrinkle or crack occurs in the hard coat layer, curling of the hard coat film is likely to occur. And an excessively multi scratch resistance of the hard coat layer is lowered, which is undesirable.

The radiation of curing the system using the above radiation-curable resin, ultraviolet, visible, infrared, may be any of the electron beam. These radiation, even the polarization may be a non-polarized light. In particular, equipment cost, safety, ultraviolet from the viewpoint of running cost are preferred. As the energy ray source of the ultraviolet, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, nitrogen laser, an electron beam accelerator, such as a radioactive element is preferred. The amount of irradiation with the energy radiation source of accumulative exposure at an ultraviolet wavelength of 365 nm, preferably in the range of 100 ~ 5,000mJ / cm 2, 300 ~ 3,000mJ / cm 2 irradiation amount, of less than 100 mJ / cm 2 since the curing becomes insufficient, there is a case where the hardness of the hard coat layer is lowered. If it exceeds 5,000 mJ / cm 2, the hard coat layer is transparent and colored to decrease. When performing curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. As the photopolymerization initiator, there can be used those known in the art. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4'-diamino benzophenone, benzoin and its alkyl ethers such as benzyl methyl ketal; acetophenone, 3 - methylacetophenone, 4-chloro benzophenone, 4,4'-dimethoxy benzophenone, 2,2-dimethoxy-acetophenone such as 1-hydroxycyclohexyl phenyl ketone; methyl anthraquinone, 2-ethylanthraquinone, 2-amyl anthraquinones, such as anthraquinone; thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone; xanthone a DOO acetophenone dimethyl ketal, ketals such as benzyl dimethyl ketal; benzophenone, benzophenones such as 4,4-bis-methylamino-benzophenone and the like; 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1 the on-the like. These may be used alone, or two or more thereof. The amount of the photopolymerization initiator, relative to the radiation curable resin composition, degree 5% in total solids ratio, more preferably 1-4%.

The system of the radiation curable resin composition, may be added using a polymer resin in a range that does not interfere with the polymerization curing. The polymeric resin is a soluble thermoplastic resin in an organic solvent used in the hard coat layer coating to be described later, specifically, acrylic resins, alkyd resins, polyester resins, and the like, in these resins a carboxyl group or a phosphoric acid group preferably has an acidic functional group such as sulfonic acid groups.

Further, a leveling agent, a thickener, an antistatic agent, may be used fillers, additives such as extender pigment. Leveling agent, there is work to fix the defect before film formation achieving tension uniformity of the coating film surface, interfacial tension than the radiation curable resin composition, the surface tension are both less material is used.

The hard coat layer is mainly composed of a cured product of such aforementioned resin composition, a method of forming the radiation after coating a coating material comprising a resin composition and an organic solvent, to evaporate the organic solvent ( for example, those of curing by electron beam or ultraviolet radiation) or heat. The organic solvent used here, it is necessary to select those suitable for dissolving the resin composition. Specifically, the wettability of the resin film, the viscosity, in view of the coatability such drying rate, alcohol, ester, ketone, ether, alone or mixed solvent selected from aromatic hydrocarbons it can be used.

The thickness of the hard coat layer is in the range of 3.0 ~ 20.0 .mu.m, more preferably in the range of 5.0 ~ 15.0 .mu.m, even more preferably in the range of 7.0 ~ 13.0.
If the hard coat layer is less than 3.0μm surface hardness is lowered.
If the hard coat layer is thicker than 20.0μm, since the stress during cure shrinkage of the hard coat layer is a resin film hardly absorbed and relaxed, curling may occur in the hard coat film, microcracks in the hard coat layer surface There or generated, or reduced adhesion to the resin film, further optical transparency or decreased. Then, also causes a cost increase due to an increase in required coating amount with an increase in film thickness.

During the hard coat layer may be appropriately be contained organic and inorganic fine particles. Organic and inorganic fine particles alone may be contained in the hard coat layer, may contain a combination of organic and inorganic fine particles.
As the organic fine particles, acrylic resin, polystyrene resin, styrene - can be used acrylic copolymer, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluoride, a polyethylene fluoride resin or the like.
As the inorganic fine particles, for example, titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, calcium oxide, indium oxide, antimony oxide and the like. Also it can be used these composites. Titanium oxide Among these, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, zirconium oxide is preferred.
The organic and inorganic fine particles may be used alone or in combination of two or more thereof.

Incidentally, in such contain an average particle diameter of 0.3 ~ 10 [mu] m translucent fine particles in the hard coat layer, when forming the uneven structure on the surface of the hard coat layer, it is possible to use as the antiglare layer preferable. Thus, it is possible to use a hard coat film as an antiglare film. Refractive index of the average particle diameter of 0.3 ~ 10 [mu] m translucent fine particles is 1.40 preferably to 1.75, the refractive index is greater than 1.40 or less than 1.75, the light-transmitting substrate Alternatively the difference in refractive index between the resin matrix becomes too large, the total light transmittance decreases. The difference in refractive index between the translucent particles and the resin component is preferably 0.2 or less. The average particle size of the translucent particles is preferably in the range of 0.3 ~ 10μm, 1 ~ 8μm and more preferably. Since the particle size is in the case 0.3μm less than the antiglare property is degraded, and if 10μm greater, as well generates a glare is not preferable because the surface degree of surface irregularity becomes too large becomes whitish. The proportion of the light-transmitting particle contained in the resin is not particularly limited, the resin composition 100 parts by weight, antiglare function to 1 to 20 parts by weight, preferably in order to satisfy the characteristics such as glare , easy to control the fine irregularities and haze value of the hard coat layer surface. Here, "refractive index" refers to the measurements in accordance with JIS K-7142. Further, the "average particle size" refers to the average value of the diameters of 100 particles were measured by electron microscopy.

In the present invention, on the resin film (on the surface hard coat layer is not stacked) may be stacked polarizing substrate. Here, the polarization substrate is used the polarizing film and the light-absorbing absorbing other light transmits only specific polarized light, the polarizing film transmitting only specific polarized light reflection type for reflecting the other light to it can be. The polarizing film of light-absorbing, polyvinyl alcohol, films obtained by stretching a polyvinylene etc. are possible using, for example, a polyvinyl alcohol having adsorbed iodine or a dye as a dichroic element obtained by uniaxially stretching polyvinyl alcohol (PVA) film and the like was. The polarizing film of the light reflection type, for example, the stretched two in which the refractive index in the stretching direction is different when the polyester resin (PEN and PEN copolymers) were laminated and stretched to several hundred layers alternately by extrusion techniques 3M Co. "DBEF" or configuration, by laminating the cholesteric liquid crystal polymer layer and a quarter-wave plate, separated into two circularly polarized light opposite directions the light incident from the cholesteric liquid crystal polymer layer side, whereas transmits and reflects the other, manufactured by Nitto Denko Corporation configuration for converting the circularly polarized light transmitted through the cholesteric liquid crystal polymer layer into linearly polarized light by the quarter-wave plate "Nipokkusu" and Merck "trans Max" and the like .
On the resin film constituting the hard coat film, before stacking the polarization substrate described above, by performing the saponification process to the hard coat film, the adhesion between the hard coat layer and the polarization substrate which constitutes the hard coat film it can be improved (adhesive strength). In a conventional hard coat film, by the saponification treatment, the occurrence of curling and cracking in the hard coat film were those observed significantly, according to the present invention, even curling or cracking in the hard coat film after saponification it is possible to reduce the occurrence.

<Other layers>
The hard coat layer may be laminated on one surface of the resin film is laminated on both sides.
Furthermore, the hard coat film may have other layers. Other layers, where, for example, polarization substrate, the low reflective layer, other functionalization layer (e.g., an antistatic layer, the near infrared (NIR) absorbing layer, a neon-cut layer, an electromagnetic wave shielding layer, a hard coat layer), it can be mentioned. The position of the other layers, for example, in the case of the polarization substrate is a on the resin film on the opposite surface to the hard coat layer, in the case of the low reflective layer and the hard coat layer on the other functions in the case of sex-imparting layer and a lower layer of the hard coat layer.

<Manufacturing Method>
Method for producing a hard coat film of the present invention, for example, by coating the radiation curable resin coating on the resin film, carried out by drying, radiation cured created. During coating, it is sufficient to satisfy the relation of A × 1500 <B. As a method for applying a coating material on a resin film, it is applied normal coating method or printing method. More specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating , and coating such as die coating, intaglio printing of gravure printing, printing of stencil printing such as screen printing or the like can be used.
Further, the hard coat film of the present invention is to satisfy the relation of A × 1500 <B, be produced by Roll-to-Roll, cracks, since it is difficult wrinkles and curling occurs due to curing shrinkage, increase the yield be able to.

Hereinafter, an embodiment of the invention (alpha).

<Examples 1-4, Comparative Examples 1-3>
Methacryloxypropyl 2.8 parts acryloyloxy propyl trimethoxy silane, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST-L, the number average particle diameter of 45 nm, silica concentration 30%) 95.6 parts (solid content 27.4 parts) and a mixture of ion-exchange water 0.1 parts, present by 80 ° C., after stirring for 3 hours, was added 1.4 parts of methyl orthoformate and stirred another 1 hour heating at the same temperature dispersion of light-transmitting fine particles of the invention the (a solution) was obtained. 32% was determined total solids concentration, the average particle diameter of the light transmissive fine particles was 45 nm. Here, the average particle diameter was measured by a transmission electron microscope.
The paint for the obtained optical functional layer by a mixture of ingredients listed in Table 1 to disperse for 30 minutes with a disper, thickness 40 [mu] m, the total light transmittance consisting of 92% light-transmitting substrate TAC ( Konica Minolta Opto, Inc.; one surface on the coating with a roll coating method KC4UYW) (line speed; and 20 m / min), after a preliminary drying 20 seconds at flow rate 0.5m / sec, 30 ~ 50 ℃, 100 ℃ in drying for 1 minute, UV irradiation in a nitrogen atmosphere (nitrogen gas replacement) (lamp; condensing type high pressure mercury lamp, lamp output; 120 W / cm, lamp: 2 lamp, irradiation distance; 20 cm) coating by performing to cure the film. There was thus obtained optical laminates of Examples 1, 2, 4 Comparative Examples 1 to 3 having an optical function layer having a thickness of 10.0 [mu] m. Further, the film thickness of the light-transparent substrate 80 [mu] m, and the thickness of the optical functional layer to 12.0 .mu.m, to obtain an optical laminate of Example 3.

<Comparative Example 4>
Except that the thickness of the optical functional layer is 2μm, the same procedure as in Example 1 to obtain an optical laminate of Comparative Example 4 of the present invention.

Using the obtained optical laminate in Examples 1-4 and Comparative Examples 1-4, adhesion, total light transmittance, haze, contact angle of water, curl, scratch resistance, pencil hardness, chemical resistance, anti stain resistance, interference unevenness, and the element ratio of fluorine were measured and evaluated by the following methods.

Adhesiveness
In accordance with cross-cut method of JIS K5600, it was carried out.
The distance of the cut is set to 1 mm, the number of cuts is eleven. Evaluation of the ratio of the number which is not peeled off the gratings crosscut, displayed in%. For example, if five peeling, indicated as 95/100.
Total light transmittance
In accordance with JIS K7105, a haze meter (trade name: NDH2000, Japan electricity made Irosha) was measured using a.
Hayes
In accordance with JIS K7105, a haze meter (trade name: NDH2000, Japan electricity made Irosha) was measured using a.
The contact angle of water (θ / 2 method)
First, the contact angle of water was measured in the optical functional layer surface. Then the contact angle of water was measured saponification treated optical functional layer surface. The contact angle of water conforms to JIS R3257 (wettability test method for a substrate glass surface), the contact angle meter (trade name: Elma G-1 type contact angle meter, manufactured by Erma Inc.) was used to measure.
Saponification of the optical stack according to the following procedure.
(1) 55 ℃, immersed for 2 minutes in a 6% aqueous sodium hydroxide.
(2) washing with water for 30 seconds.
(3) 35 ℃, 30 seconds immersed in 0.1 N sulfuric acid.
(4) washing with water for 30 seconds.
(5) 120 ℃, 1 minute, hot air drying.
If the value of the contact angle is greater raise the water repellency, chemical resistance, abrasion resistance, antifouling property is improved. Before saponification contact angle 90 ° or more, preferably at 100 ° or more, the contact angle after saponification 70 ° or more, preferably more than 80 °.
curl
First, an optical laminate prepared JIS K5600-1-6 environment shown in (temperature and humidity of the curing and test) (temperature 23 ± 2 ° C., humidity 50 ± 5 RH%) to stand for 16 hours. Next, cut out measurement sample 10 cm × 10 cm in the same environment, placed on a flat plate so that the optical functional layer is on top, was determined to "measurement unit" shown in FIG. Measurements, × a of less than 0 ~ 10 mm, those of less than 10 ~ 30 mm △, was ○ a of less than 30 ~ 50 mm, 50 mm or more of the ◎.
Antifouling
Fabricated optical laminate permanent marker the optical function layer (trade name: Mackie, ZEBRA Co.) Draw a line of 3cm lengths in, after standing for 1 minute, clean wiper (part number; FF-390C KURARAYKURAFLEX Ltd. was evaluated in a way that wiping by). After rubbing back and forth 20 times with 500 g / cm 2 load, a case of completely wiped off ○, a case where there is a portion not wiped △, and as × when no wiped off at all.
chemical resistance
Ligroin, toluene, sulfuric acid (10%), NaOH (6%), ethanol, neutral detergent (Family Pure), hand cream (Nivea), hair liquid: each reagent (Success morning hair water) the optical function layer surface after the dropwise addition, 10 hours allowed to clean the wiper from; with (part number FF-390C Kuraray class manufactured by flex Inc.), was evaluated in 500 g / cm 2 load, a method of wiping with rubbing 20 times. After wiping off, it was visually assess the presence or absence of a change of appearance. For all of the chemicals, the case change defunct ○, was a case where a change is observed even in one of the chemicals any whitening, etc. and ×.
Scratch resistance
Nippon Steel Wool Co., Ltd. # 0000 steel wool abrasion tester (Fu Chien Co. Abrasion Tester, Model; 339) attached to, was reciprocated 10 times optical functional layer surface under a load 250 g / cm 2. Then, it was confirmed scratches of wear parts under a fluorescent lamp. When the number of scratches is 0 this ◎, when the number of scratches of 1 to less than ten ○, when the number of scratches of less than 10 to 30 this △, the number of scratches was × when more than 30 lines.
Surface hardness (pencil hardness)
Using pencil hardness meter (Yoshimitsu Seiki Co., Ltd.), in compliance with JIS 5400, it was measured. The number of measurements is set to 5 times, and count the number of bad hair scratches. For example, a pencil of 3H, Without three wounds were so on 3/5 (3H). Pencil hardness was good 4/5 (3H) above.
Interference unevenness
As the optical functional layer is on the front side polarizing plate surface of the crossed Nicols, the adhesive layer having a refractive index of 1.5 stuck through the (thickness 20 [mu] m), three band fluorescent lamp (manufactured by Matsushita Electric Industrial Co., Ltd.: FLR40S · EX-N / M-X, by the reflection of illumination about 500 lux), was visually evaluated. A case where the interference unevenness can not be confirmed ○, a case can be confirmed slightly thinner △, was × a case that clearly can be confirmed.
The element ratio of fluorine
The amount of fluorine element in the optical functional layer surface was evaluated by ESCA.
As the measurement conditions below.
Measuring device; ULVAC-PHI, Inc. Quantera SXM
Load angle of photoelectrons; 45 ° X-ray output; 25.0W
Measurement X diameter; 100 [mu] m
Pass Energy; 112.0eV
Measurement element; C1s, O1s, F1s, Si2p
By ESCA, the optical functional layer surface, C1s present in depth 5nm, O1s, F1s, the Si2p was measured. From the resulting element peak area was calculated element ratio.

Figure JPOXMLDOC01-appb-T000009

Here will be described each component in Table 1 in detail.
Polyfunctional acrylate Kyoeisha Chemical PE3A: Pentaerythritol triacrylate (trifunctional)
Multifunctional urethane acrylate manufactured by Kyoeisha Chemical UA-306H: Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (hexafunctional)
Polyfunctional acrylic Nippon Kayaku PET-30: pentaerythritol triacrylate (trifunctional)
Polyfunctional acrylic Toagosei M-305: Pentaerythritol triacrylate (trifunctional)
Monofunctional acrylate manufactured by Kyoeisha Chemical HOP-A: 2-hydroxypropyl acrylate (monofunctional)
Fluorinated acrylate Kyoeisha Chemical LINC-3A: tri acryloyl heptadecafluoro root sulfonyl pentaerythritol (tetrafunctional) 65% pentaerythritol tetraacrylate (tetrafunctional) 35% mixture (the following formula 8)
Fluorinated acrylate Kyoeisha Chemical LINK-102A: Compound Represented by Formula 9

Figure JPOXMLDOC01-appb-C000010

Figure JPOXMLDOC01-appb-C000011

The measurement results are summarized in Table 2.

Figure JPOXMLDOC01-appb-T000012

In Examples 1-4, by ESCA, was C1s present in depth 200nm from the optical functional layer surface, O1s, F1s, the Si2p measured at 5nm increments. The fluorine element ratio existing in the optically functional layer surface to 5nm, the average value of the fluorine element ratio that exists for each depth of 5nm obtained measured in the optical functional layer 5nm increments to a depth 200nm from the depth of 5nm on the surface in dividing the value was 20 or more in examples 1-4.

Describing Examples and Comparative Examples of the present invention (beta) below. Incidentally, "part" means "part by weight".

[Example 5]
The coating obtained by stirring 1 hour a mixture of paint components below as a hard coat layer coating with a disper, thickness 40 [mu] m, TAC resin film comprising a total light transmittance of 92% (manufactured by Konica Minolta Holdings, Inc. product name: KC4UYW on one side of), was applied by a die head coating method, dried for 1 minute at 100 ° C., UV irradiation (irradiation distance 10cm at 120 W / cm condensing type high pressure mercury lamp 2 lamps in a nitrogen atmosphere, the irradiation time for 30 seconds) to cure the coating film. The hard coat layer thickness is set to 19μm, ears up width was 30mm. There was thus obtained the hard coating film of Example 5.
And multi-functional acrylate (Kyoeisha Chemical Co., Ltd. Product name: Light Acrylate DPE-6A) 150 parts multifunctional urethane acrylate (Shin-Nakamura Chemical Co., Ltd. Product name: U-6HA) 40 parts light initiator (manufactured by Ciba Specialty Chemicals Inc. Ltd. product name: Irgacure 184) 9 parts leveling agent (Kyoeisha chemical Co., Ltd. product name: Polyflow No. 77 Available) 1 part solvent (MEK) 200 parts

[Example 6]
The thickness of the hard coat layer 10 [mu] m, except for using 20mm ear up width in the same manner as in Example 5, to obtain a hard coat film of Example 6 of the present invention.

[Example 7]
Change to that shown the paint components for the hard coat layer below, the thickness of the hard coat layer 9 .mu.m, except that the ears up width is 15mm in the same manner as in Example 5, the hard of Example 7 of the present invention to obtain a coated film.
And multi-functional acrylate (Shin-Nakamura Chemical Co., Ltd. Product Name: A-DPH) 130 parts multifunctional urethane acrylate (Nippon Synthetic Chemical Industry Co., Ltd. Product name: Shiko UV-1700B) 60 parts light initiator (manufactured by Ciba Specialty Chemicals Inc. Ltd. product name: Irgacure 127) 9 parts leveling agent (Kyoeisha chemical Co., Ltd. product name: Polyflow No. 77 Available) 1 part solvent (MEK) 120 parts solvent (MIBK) 80 parts

[Example 8]
A resin film thickness of 80μm of TAC (FUJIFILM Opto Materials Co., Ltd. Product Name: TD80) was changed to, except that the ears up width is 29mm in the same manner as in Example 5, the hard of Example 8 of the present invention to obtain a coated film.

[Example 9]
PET having a thickness of 75μm resin film (manufactured by Toyobo Co., Ltd. Product Name: A 4300) was changed to the film in the same manner as in Example 5, to obtain a hard coat film of Example 9 of the present invention.

[Comparative Example 5]
Except that the ears up width is 20mm, in the same manner as in Example 5, to obtain a hard coat film of Comparative Example 5.

[Comparative Example 6]
Except that the thickness of the hard coat layer and 28μm is in the same manner as in Example 5, to obtain a hard coat film of Comparative Example 6.

[Comparative Example 7]
The thickness of the hard coat film 10 [mu] m, except for using 5mm ear up width in the same manner as in Example 5, to obtain a hard coat film of Comparative Example 7.

[Comparative Example 8]
Change to that shown the paint components for the hard coat layer below, the thickness of the hard coat layer 15 [mu] m, except that the ears up width is 10mm in the same manner as in Example 5, a hard coat film of Comparative Example 8 Obtained.
And multi-functional acrylate (Kyoeisha Chemical Co., Ltd. Product name: Light Acrylate DPE-6A) 40 parts multifunctional urethane acrylate (Shin-Nakamura Chemical Co., Ltd. Product name: U-6HA) 150 parts photoinitiator (Ciba Specialty Chemicals Inc. Ltd. product name: Irgacure 184) 9 parts leveling agent (Kyoeisha chemical Co., Ltd. product name: Polyflow No. 77 Available) 1 part solvent (MEK) 200 parts

Using the hard coat film obtained in Examples 5-9 and Comparative Examples 5-8, Carl and wrinkle adhesion, the pencil hardness was measured and evaluated by the following methods. The results obtained are shown in Table 3.

(1. Carl)
Examples 5-9 and Comparative Examples 5-8 Length 1.5m a hard coat film was produced. Next, as shown in FIG. 4 (a), on the hard coat film 1 a horizontal base 30, mounted so coated surface facing upward, cellophane tape the four corners of the hard coat film 1 on a horizontal pedestal 30 ( was fixed in the registered trademark) 40.
Then, an environment showing a hard coat layer to JIS K5600-1-6 (temperature and humidity of the curing and test) (temperature 23 ± 2 ° C., humidity 50 ± 5 RH%) was left for 16 hours.
Subsequently, at the site of 0.5m hard coat film 1 from fixed end with cellophane tape 40, were each measured upward warping height C from the horizontal pedestal 30. Upward warping height C, as shown in FIG. 4 (b), the distance from the center of the horizontal base 30 to the hard coat film 1. We tested 5 times to obtain a measured value of the curl and the average value.
Incidentally, Karl and a 20mm or less good (○), when it exceeds 20mm, the hard coat film or various secondary processing products using it (for example, a polarizing plate protective film subjected to saponification treatment in the hard coat film ) was × of in order to give a significant impact on production.

(2. wrinkles)
Coating direction of ten wrinkles and average interval of wrinkles over 10 mm ○, 5 mm or more, less than 10 mm △, less than 5 mm, or a case where cracks (cracking) or bending entered the film was ×.

(3. adhesion)
Adhesion, in accordance with cross-cut method of JIS K5600, was carried out.
The distance of the cut is set to 1 mm, the number of cuts is eleven. Evaluation of the ratio of the number which is not peeled off the gratings crosscut, displayed in%. For example, if five peeling, indicated as 95/100.

(4. pencil hardness)
Pencil hardness in accordance with JIS 5400, tested five times to count the number of bad hair scratches. For example, a pencil of 3H, Without three wounds were so on 3/5 (3H).

Figure JPOXMLDOC01-appb-T000013

As described above, the hard coat films of Examples 5-9, the surface hardness (pencil hardness) also has a more than 4H, in order to be A × 1500 <B, be those curling hardly occurs It was. In conjunction with such an effect, cracks, wrinkles was also difficult to occur.
On the other hand, in order hard coat film of Comparative Example 5-8 which do not satisfy the relation of A × 1500 <B, cracks, wrinkles, or curls occurred, such as the surface hardness does not satisfy the above 4H, hard invention the coated films were those which can not be used.

As described above, according to the present invention (beta), a layer formed by laminating a hard coat layer 1 layer on a resin film, it is possible to provide excellent while having a surface hardness, hard hard coat film curling occurs .
Further, the hard coat film A × 1500 <to satisfy the relational expression B, step to prepare a hard coat film by Roll-to-Roll and its fabrication process of the present invention (beta) (e.g., saponification treatment) even in the case of performing, it is possible to provide a curl hardly occurs hard coat film.

1 hard coat film 1a, the end face 10 resin film 11a of 1b hard coat film, 11b end face 12a of the resin film, 12b edge 20 hard coat layer 21a of the resin film, the end face 22a of 21b hardcoat layer, the edges of 22b resin film 30 horizontal pedestal 40 scotch tape (registered trademark)

Claims (9)

  1. On one or both sides of the light-transparent substrate, directly or via another layer, the optical laminate having a optical function layer,
    Wherein the optical functional layer is a thickness of 3 ~ 50 [mu] m,
    Contains a translucent resin and the translucent particles,
    The resin translucent resin, containing the ionizing radiation-curable polyfunctional acrylate, and ionizing radiation-curable fluorinated acrylate 0.05 to 50% by weight relative to the total weight of the solid components of the optical functional layer characterized in that it is formed by irradiating the ionizing radiation of the composition, the optical stack.
  2. It said fluorinated acrylate, the more the light-transparent substrate side of the optical functional layer, is unevenly distributed on the surface side, according to claim 1 laminated body for optical purposes according.
  3. Furthermore, having a polarization substrate, according to claim 1 or 2 optical laminate according.
  4. Antiglare film optical functional layer according to claim 1 or 2 is characterized by being provided with a surface irregular structure.
  5. Hard coat layer stacked on the resin film,
    The thickness of the hard coat layer is A (mm),
    When the width of the edge of the resin film to the edge of the hard coat layer (ear up width) and B (mm), A × 1500 <B (where, 0.003mm ≦ A ≦ 0.020mm)
    Hard coat film, characterized in that it.
  6. The hard coat film according to claim 5 in which the elastic modulus of the resin film is characterized in that it is a 2 GPa ~ 8 GPa.
  7. The hard coat film according to claim 5, wherein the thickness of the resin film is 5 ~ 100 [mu] m.
  8. The hard coat film according to claim 5, wherein the hard coat layer contains a radiation-curable resin, wherein the volumetric shrinkage of the radiation curable resin is 5 to 25%.
  9. Antiglare film hard coat layer according to any one of claims 5-8, characterized by comprising comprises a surface relief structure.
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