TWI498212B - Optical laminate and hardcoat film - Google Patents

Description

Optical laminate and hard coating

The present invention (α) relates to an optical laminate disposed on the surface of a display such as a liquid crystal display (LCD) or a plasma display (PDP), and more particularly to an optical for improving scratch resistance, chemical resistance, and screen visibility. Laminated body.

The present invention (β) relates to a hard coat film, and more particularly to a hard coat film which can be applied to the surface of a display such as a liquid crystal display (LCD) or a plasma display (PDP).

LCD is one type of various image display devices. However, with the improvement of related technologies such as high viewing angle, high definition, high-speed response, and color reproducibility of LCDs, the use of LCDs has also changed from notebook computers or monitors to televisions. on. The basic composition of the LCD is between the flat glass having two transparent electrodes, and the spacers are arranged at intervals of a gap to inject the liquid crystal material therein and seal it, and in the flat glass. A polarizing plate is attached to the inside of the watch. Since the polarizing plate is easily scratched, a cover plate formed of glass or plastic is attached to the surface of the LCD to prevent the polarizing plate attached to the surface of the LCD from being scratched. However, since the attachment of the cover plate is disadvantageous to cost and weight, the polarizing plate which has been subjected to the treatment of the optical functional layer on the surface is gradually used. The hard coating treatment is carried out usually on a transparent plastic film substrate, and a hard coating film on which a hard coat layer is provided is provided on the surface of the polarizing plate.

The optical functional layer is usually formed on a transparent plastic film by using a radiation-curable resin such as a thermosetting resin or an ultraviolet curable resin to form a thin coating film of about several μm. However, if the thickness of the optical functional layer is insufficient, the surface of the optical functional layer may be damaged by the influence of the substrate of the underlying transparent plastic film. In the use of the LCD, although a cellulose triacetate (TAC) film is mainly used as the transparent plastic film substrate, in the above case, the pencil hardness of a representative measurement method for evaluating the rub resistance of the surface of the hard coat layer (JIS K5600) When it is, it is generally about 2 to 3H.

Although LCDs or PDPs have become more and more popular in the TV market, it is conceivable that the average consumer of home TVs is also treated with the same strictness as the past CRT TVs (from physical, mechanical, chemical, etc.). load). For example, a rag that is impregnated with a glass cleaner (various surfactants, organic solvents, etc.) wipes dirt such as dust or fingerprints adhering to the surface of the display, or a child wipes the surface with a toy or the like, or taps. Since the cathode tube of the CRT is made of glass excellent in chemical resistance and has a surface hardness of about 9H of pencil hardness, it has sufficient durability for such loads. However, the surface of the hard coating film mounted on the above display has a low pencil hardness and is insufficient in chemical resistance, so there is a need for improvement.

At the same time, when a hard coating film is attached to various image display devices, the surface of the display device, that is, the light on the surface of the hard coating film is reflected, the contrast is reduced, and the film thickness of the hard coating layer is scattered. Light interference spots (details described later), etc., have problems of reducing the visibility. Therefore, in addition to the above surface hardness, there is a need to improve the visibility of the hard coating film.

As for the method of increasing the surface hardness of the hard coat layer, a method of simply increasing the thickness of the hard coat layer or the like can be considered. However, the above method hardens the hardness, and not only makes the wrinkles or curls caused by the hardening shrinkage of the hard coat layer large, but also easily breaks or peels off the hard coat layer, and thus is not a practical method. Therefore, in recent years, several proposed methods have been proposed, in addition to the high hardness of the hard coating film, and the problem of curling due to cracking or hardening shrinkage of the hard coating layer (Patent Documents 1 to 4).

Patent Document 1 discloses a protective film for a polarizing plate in which a cured coating film layer (optical functional layer) is formed of a composition containing an ultraviolet curable polyol acrylate-based resin on at least one surface of a transparent plastic film substrate. As the ultraviolet curable polyol acrylate resin, diisopentyl alcohol hexaacrylate is mainly exemplified. When the resin coating is applied to the plastic film substrate, the thickness of the cured coating layer is 10 μm or more, and the hardness can be 4H or more of the pencil hardness. However, if the curl due to hardening shrinkage is to be suppressed at the same time, difficult.

Patent Document 2 discloses a hard coating film in which a buffer layer formed of one or more layers having a thickness of 3 to 50 μm is provided on at least one surface of a transparent plastic film substrate, and a hard coating layer having a thickness of 3 to 15 μm is formed on the buffer layer. . The pencil hardness of each of the transparent plastic film substrate, the buffer layer, and the optical functional layer has a value that increases in this order. Therefore, the entire hard coating film can be designed to have a pencil hardness of 4H to 8H. However, in Patent Document 2, in addition to the optical functional layer, a buffer layer is required, and since at least a two-layer structure is required, the production steps are complicated, and there is a disadvantage that the production cost becomes high.

Patent Document 3 discloses that a hard optical functional layer containing inorganic or organic internal crosslinked ultrafine particles is provided as a first hard coat layer on at least one surface of a transparent plastic film or a sheet substrate, and then no inorganic or organic substance is contained. A film of a transparent hardening resin of internal crosslinked fine particles is used as the second hard coat layer. However, Patent Document 3 is also a two-layer structure as in Patent Document 2, so that the production steps become complicated and the production cost becomes high.

Patent Document 4 proposes forming a hard coating film of at least one hard coat layer on at least one surface of a transparent plastic film substrate, the hard coat layer forming material containing 20 to 80 parts by weight of the inorganic fine particles with respect to 100 parts by weight of the resin, and being hard. The thickness of the entire coating layer is from 10 μm to 50 μm, and the pencil hardness of the surface is 4H or more. However, the hard coat forming material used in Patent Document 4 contains inorganic fine particles in the above ratio with respect to a resin such as polyester acrylate or polyurethane acrylate, and is formed on a transparent plastic film substrate. When a hard coat layer having a thickness of 10 μm or more is used, it is difficult to obtain a balance between ensuring sufficient hardness and suppressing curl due to hardening shrinkage.

As for a method for improving the visibility of a hard coating film, there is a proposal of a hard coating film having a hard coating layer on a transparent plastic film substrate, and the hard coating layer contains polyurethane acrylate and isocyanuric acid acrylate. And inorganic light-transmitting fine particles (Patent Document 5). The content of this proposal is to prevent the reflection of the hard coating film and the interference pattern of light by adjusting the difference in refractive index between the transparent plastic film substrate and the hard coating layer by the inorganic light-transmitting fine particles. Although it is indeed possible to reduce the refractive index of the hard coating layer by adjusting the refractive index of the hard coating layer by the inorganic light-transmitting fine particles, the film formation property is poor due to insufficient compatibility or dispersibility of the hard coating material. The thickness of the hard coating is subtly distributed and it is difficult to overcome the interference pattern. At the same time, it is difficult to achieve sufficient processability due to poor film forming properties.

In terms of increasing the hardness of the pencil on the surface, although it is necessary to make the hard coating thicker, when the hard coating is thickened, the adhesion between the hard coating and the transparent plastic film substrate is deteriorated, and there is a hard coating film. Produces curling or wrinkling problems. One of the causes of this problem is that when the ionizing radiation-curable resin of the constituent material of the hard coat layer is cured to form a hard coat layer, the ionizing radiation-curable resin hardens and shrinks. As for the countermeasure against curling and wrinkles, it has been proposed to fill the hard coat with inorganic fine particles such as ruthenium oxide (Patent Document 6). When used as a polarizing substrate, it is necessary to carry out a saponification treatment before the polarizing plate. However, due to this saponification treatment, cerium oxide is eluted into the saponification liquid, and there is a problem that the effect of cerium oxide is lost.

The hard coating film is provided on the surface of the casing or the surface of the display or the like, and the damage of each constituent member can be prevented by the improvement of the surface hardness. The hard coat film is one in which one or more layers of a hard coat layer are laminated on the resin film, or another layer is provided between the resin film and the hard coat layer.

After coating the ionizing radiation-curable resin such as a thermosetting resin or an ultraviolet curable resin as a hard coat layer on the resin film, it is possible to form a hard coat film by curing. The thickness of the hard coat layer is about several μm, and the surface hardness of the hard coat layer is generally H to 3H of pencil hardness (JIS K5400).

Further, from the viewpoint of effective use of the resin film, a hard coat layer is generally formed by completely covering one or both sides of the resin film.

As a method of increasing the surface hardness of the hard coat layer, a method of increasing the thickness of the hard coat layer can be cited. However, although this method can improve the surface hardness of the hard coating layer, it is easy to cause cracking or peeling of the hard coating layer, and also causes wrinkles or curls in the process of the hard coating film or various secondary processing processes using the same. Waiting for an accident, but not providing practicality. The above problems such as wrinkles or curls are more likely to occur when the surface hardness of the hard coat layer is higher. When used for optical applications, the above-mentioned problems such as wrinkles or curls are more important problems. For example, when a hard coating film is used as a protective film for a polarizing plate, saponification (acid, alkali) treatment is generally performed on the hard coating film. The surface of the hard coating film can be modified by saponification treatment to improve the applicability of the adhesive or the adhesive. Therefore, an adhesive or an adhesive can be interposed to improve the adhesion between the polarizing substrate and the hard coating film. However, due to the saponification treatment, it is also easy to cause cracking or hardening shrinkage on the hard coating film to cause wrinkles or curling.

At the same time, productivity can be improved by making a hard coating film by Roll-to-Roll. However, when the step of producing a hard coating film by Roll-to-Roll or the secondary processing process (for example, saponification treatment) is applied, there is a problem that the hard coating film is broken and wrinkles or curls are caused by hardening shrinkage.

Further, for example, Patent Document 1 discloses that a protective film for a polarizing plate is formed by forming a cured coating film layer containing a composition of diisopentaerythritol hexaacrylate and cerium oxide fine particles on at least one surface of a transparent resin film. When the resin is applied onto the transparent resin film substrate, the thickness of the cured coating film layer can be made 10 μm or more to ensure a pencil hardness of 4H or more. However, when the thickness of the cured coating layer is made 10 μm or more, it is difficult to suppress curl due to hardening shrinkage. The generation of this curl is more likely to occur due to the saponification treatment.

Patent Document 2 discloses that a hard coat film having a hard coat layer having a thickness of 3 to 15 μm is formed on at least one surface of a plastic substrate film by providing a buffer layer formed of one or more layers having a thickness of 3 to 50 μm. . The respective pencil hardnesses of the transparent plastic film substrate, the buffer layer, and the hard coat layer have values increased in this order, so that the entire cured film can be designed to have a pencil hardness of 4H to 8H. However, in the invention disclosed in Patent Document 2, in addition to the hard coat layer, a buffer layer is required, and there is a disadvantage that the production step increases the load.

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-113728

Patent Document 2: Japanese Patent Laid-Open No. Hei 11-300873

Patent Document 3: Japanese Patent Laid-Open Publication No. 2000-52472

Patent Document 4: Japanese Laid-Open Patent Publication No. 2000-112379

Patent Document 5: Japanese Laid-Open Patent Publication No. 2006-106427

Patent Document 6: Japanese Patent Laid-Open Publication No. 2003-248101

The object of the present invention (α) is to provide an optical laminate which is excellent in surface hardness and which can suppress cracking or curling due to hardening shrinkage, and is also applicable to an LCD or a PDP because of good screen visibility. TV use.

In the past, there has been no optical laminate having excellent surface hardness, being less likely to cause curling or wrinkles, and chemical resistance (for example, alkali treatment in saponification treatment). Therefore, the object of the present invention (α) is to provide an optical functional layer (for example, a hard coat layer or an excellent optical layer having excellent scratch resistance, high surface hardness (pencil hardness), excellent chemical resistance, and low curling and antifouling properties. Optical layer of anti-glare layer). At the same time, it is an object of the present invention to provide an optical layered body in which the light-transmitting fine particles (for example, cerium oxide) are eluted into the saponified liquid and the effect of the light-transmitting fine particles is not lost.

The object of the present invention (β) is to provide a hard coating film in which a layer of a hard coat layer is laminated on a resin film, and even if the pencil hardness of the hard coat layer is 4H or more, curling is less likely to occur.

Meanwhile, the object of the present invention (β) is to provide a hard coating film which is not easily produced even when a hard coating film is produced by a Roll-to-Roll step or subjected to a secondary processing (for example, saponification treatment). curly.

The invention (α) includes the following inventions (1) to (4).

The present invention (1) is an optical layered body characterized in that the optical layer is provided on an optical layered body in which an optical functional layer is provided directly or on another side of a light-transmitting substrate, via another layer. The thickness is 3 to 50 μm, and the light-transmitting resin and the light-transmitting fine particles are contained, and the light-transmitting resin is opposed to the ion-containing radiation-curable polyfunctional acrylate and the solid component in the optical functional layer. A resin composition of 0.05 to 50% by weight of ionizing radiation-curable fluorinated acrylate having a total weight is formed by irradiating ionized radiation.

The optical layered body according to the invention (1), wherein the fluorinated acrylate is present on the surface side of the side of the light-transmitting substrate of the optical functional layer.

The invention (3) is the optical layered body of the invention (1) or (2), which further has a polarizing substrate.

The invention (4) is an anti-foaming film which is formed by providing the optical functional layer of the invention (1) or (2) with a surface uneven structure.

The present invention (β) is an invention which solves the above problems by applying the technical compositions of the following inventions (5) to (9).

(5) A hard coating film comprising: laminating a hard coat layer on a resin film, such as a thickness of the hard coat layer of A (mm), from an edge portion of the resin film to the hard coat layer When the width of the edge portion (the width of both edges) is B (mm), A × 1500 < B (however, 0.003 mm ≦ A ≦ 0.020 mm).

(6) The hard coat film according to (5), wherein the resin film has an elastic modulus of from 2 GPa to 8 GPa.

(7) The hard coating film according to (5), wherein the resin film has a thickness of 5 to 100 μm.

(8) The hard coat film according to (5), wherein the hard coat layer contains a radiation curable resin, and the radiation curable resin has a volume shrinkage ratio of 5 to 25%.

(9) An anti-foaming film comprising the surface uneven structure of the hard coat layer according to any one of the aspects (5) to (8).

In addition, the "optical laminated body" and the "hard coating film" in this specification are the same thing.

According to the invention (1), the resin composition of the optical functional layer contains a polyfunctional acrylate and a fluorinated acrylate, and the surface hardness can be improved, and the scratch resistance of the surface of the optical functional layer can be enhanced to improve the scratch resistance. The effect of injury. At the same time, since the resin composition of the optical functional layer contains a fluorinated acrylate, the effect of improving the chemical resistance and the antifouling property can be exhibited in the water repellency effect of the component. Further, since the light-transmitting fine particles are dispersed between the molecules of the resin matrix, the curing shrinkage of the UV resin such as the polyfunctional acrylate can be reduced, and the effect of preventing curling can be exhibited.

According to the invention (2), since the fluorinated acrylate is biased on the side of the surface, the fluorinated acrylate component is easily exposed to the surface, and the scratch resistance is improved as the surface lubricity is improved, or the water repellency is improved. The effect of improving the chemical resistance and the antifouling property is more remarkable. At the same time, since the material having fluorine is usually a high-priced material, the addition amount of the fluorine-containing material can be reduced by biasing the fluorine on the surface of the optical functional layer (present near the surface layer portion), which is advantageous for the economical surface.

According to the invention (3), when the polarizing substrate is provided, even if the saponification treatment which must be performed is performed, since the light-transmitting fine particles (for example, cerium oxide) dispersed in the optical functional layer are hardly eluted into the saponification treatment liquid, Continue to prevent curling.

According to the present invention (β), the hard coating film of the present invention is made to have a thickness A of the hard coat layer when compared with a hard coat film which forms a hard coat layer on the one side or both sides of the resin film in the past. (mm) and the width B (mm) from the edge of the resin film to the edge of the hard coat layer, forming a relationship of A × 1500 < B (however, 0.003 mm ≦ A ≦ 0.020 mm), but on the resin film Since the layer structure of the hard coat layer is laminated, even if the pencil hardness of the hard coat layer is 4H or more, a hard coat film which is less likely to be curled can be provided.

Meanwhile, the present invention (β) can provide a hard coating film which is less likely to cause curling even when a hard coating film is produced by a Roll-to-Roll step or subjected to a secondary processing (for example, saponification treatment).

According to the inventions (6) and (7), it is possible to provide a hard coating film which is not easily broken and which is less likely to cause wrinkles due to hardening shrinkage.

Hereinafter, an optical laminate relating to (α) of the present invention will be described.

The optical layered body of the present preferred embodiment has a basic composition in which an optical functional layer is laminated on a light-transmitting substrate. Further, the optical functional layer of the present preferred embodiment is suitably used as a hard coat layer or a low refractive index layer on the outermost surface of the optical layered body. In this case, the optical functional layer may be laminated on one surface of the light-transmitting substrate, or may be laminated on both surfaces of the light-transmitting substrate. Further, the optical laminate may have other layers. As for the other layers herein, a polarizing substrate, a hard coat layer (for example, an optical functional layer is used as a low refractive index layer), and a layer having other functional properties (for example, an antistatic layer, near infrared rays (for example, an antistatic layer, a near infrared ray (for example, an optical functional layer) is used. NIR) absorption layer, neon cut layer, electromagnetic wave shielding layer, optical functional layer). Meanwhile, the position of the other layer may be provided on the light-transmitting substrate opposite to the optical function layer in the case of a polarizing substrate, and may be the optical functional layer when a functional layer is imparted. The bottom layer. Further, the optical function layer can also function as a low reflection layer. Hereinafter, each component (translucent substrate, optical functional layer, and the like) of the optical layered body according to the present preferred embodiment will be described in detail.

First, as the light-transmitting substrate of the present preferred embodiment, the light transmittance is not particularly limited, and although glass such as quartz glass or alkali glass may be used, polyethylene terephthalate (PET) may be used. Cellulose triacetate (TAC), polyethylene terephthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimine (PI), polyethylene (PE) , polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene resin, polyether oxime, cellophane, aromatic polyamide and other resins The membrane is ideal. These films may use a film that is not stretched, or a film that has been stretched. In particular, the biaxially stretched polyethylene terephthalate film is preferred in terms of its mechanical strength or dimensional stability, and the unstretched cellulose triacetate (TAC) is in-plane position. The difference is very small. Further, when used in a PDP or an LCD, a PET or TAC film such as this is preferable.

Although the transparency of these light-transmitting substrates is preferably as high as possible, it is preferably 80% or more at a total light transmittance (JIS K7105) and preferably 90%. Meanwhile, the thickness of the light-transmitting substrate is preferably thinner from the viewpoint of weight reduction, but it is preferably used in the range of 1 to 700 μm and preferably 20 to 250 μm in consideration of productivity or handleability. . When the optical laminate of the present invention is used for LCD applications, TAC of 20 to 80 μm is preferably used as the light-transmitting substrate. As for the optical laminate of the present invention, in particular, when TAC of 20 to 80 μm is used as the light-transmitting substrate, since it can prevent curling, it can be suitably used for LCD applications requiring thinness and light weight.

Further, on the light-transmitting substrate, surface treatment such as alkali treatment, corona treatment, plasma treatment, sputtering treatment, saponification treatment, or application of a surfactant, a decane coupling agent, or the like, or a surface such as Si vapor deposition. The modification treatment can improve the adhesion between the light-transmitting substrate and the optical functional layer. The adhesion between the light-transmitting substrate and the optical functional layer can be improved by the progress of the treatment, and the scratch resistance, surface hardness, and chemical resistance in the optical functional layer can be improved.

Next, detail the optical functional layer associated with this best form. The translucent resin which is required to be contained in the optical functional layer according to the present embodiment is irradiated with ionized radiation to a resin composition containing ionizing radiation-curable polyfunctional acrylate and ionizing radiation-curable fluorinated acrylate. And formed. The ionizing radiation-curable polyfunctional acrylate is preferably formulated in an amount of from 20 to 80% by weight, preferably from 30 to 60% by weight, based on the total weight of the solid component in the optical functional layer. The ionizing radiation-curable fluorinated acrylate must be contained in an amount of 0.05 to 50% by weight, preferably 0.2 to 50% by weight, preferably 5 to 50% by weight, based on the total weight of the solid component in the optical functional layer. More preferably from 10 to 40% by weight. When the amount of the ionizing radiation-curable multifunctional acrylate is less than 20% by weight, the crosslinking density of the optical functional layer is lowered, and the pencil hardness is deteriorated. Further, when it is more than 80% by weight, curling tends to occur. When the amount of the ionizing radiation-curable fluorinated acrylate is less than 0.05% by weight, the water repellency and the slip property are lowered, so that scratch resistance, antifouling property, and chemical resistance are deteriorated.

At this time, it is preferred that the fluorinated acrylate is biased from the side of the light-transmitting substrate to the surface side. By having such a structure, the effect of scratch resistance, chemical resistance, and antifouling property can be made more remarkable. In particular, it is more preferred to have the fluorinated acrylate gradually present on the surface side from the side of the light transmissive substrate of the optical functional layer. Further, in the present specification and the scope of the present patent application, a component derived from a fluorinated acrylate (a component which hardens a fluorinated acrylate by ionizing radiation energy) and a component derived from a polyfunctional acrylate in an optical functional layer ( The component which hardens a polyfunctional acrylate by ionizing radiation energy can be simply referred to as "fluorinated acrylate" and "multifunctional acrylate". In the present invention, the fluorinated acrylate is biased on the surface side from the side of the light-transmitting substrate, and the ratio of the fluorine element present in the range from the surface of the optical functional layer containing the fluorinated acrylate to the depth of 5 nm is 10% or more. meaning. It is preferred that the fluorine element ratio is 20% or more. The upper limit is not particularly limited, and is, for example, 80% or less. The fluorine element ratio is measured by Electron Spectroscopy for Chemical Analysis (hereinafter referred to as "ESCA"). As for the ESCA, the existence ratio of fluorine can be calculated from the peak areas of fluorine, carbon, oxygen, and helium obtained in a depth of 5 nm.

Meanwhile, when the surface of the optical functional layer was measured by the ESCA on a scale of 5 nm to a depth of 200 nm, the ratio of fluorine elements present at a depth of 5 nm from the surface of the optical functional layer to a depth of 5 nm was measured at a scale of 5 nm. The value of the average value of the fluorine element ratio which is present from the depth of 5 nm to the depth of 200 nm of the surface of the optical function layer is preferably 10 or more, more preferably 20 or more. The upper limit is not particularly limited, and is, for example, 1,000 or less. When the value is 10 or more, since the fluorine atom can be effectively present on the surface of the optical function layer, an optical layered body excellent in economical efficiency can be provided even when an expensive fluorine material is used.

In this case, the polyfunctional acrylate is not particularly limited as long as the number of (meth)acryloxy groups in one molecule is two or more, and for example, an EO addendum of bisphenol A can be used. Methyl) acrylate, ethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, trimethylolpropane II (Meth) acrylate, glycerol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diisopentaerythritol tri (methyl) Acrylate, diisopentaerythritol tetra(meth)acrylate, diisopentyltetraolpenta(meth)acrylate, diisopentyltetraol hexa(meth)acrylate, trimethylolpropane tris(A) Acrylate, pentaerythritol tris(meth)acrylate hexamethylene diisocyanate urethane ethyl ester polymer, isopentanol tris(meth) acrylate hexamethylene diisocyanate urethane Prepolymer, pentaerythritol tri(meth)acrylate toluene diisocyanate urethane ethyl ester prepolymer, pentaerythritol tris(meth)acrylate isophorone diisocyanate Ethyl urethane prepolymer, diisopentaerythritol hexaacrylate, and the like. These monomers may be used alone or in combination of two or more. The above polyfunctional acrylate is preferably a trifunctional or higher functional group, and more preferably a tetrafunctional or higher functional group.

As the fluorinated acrylate, there is no particular limitation, and for example, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate can be used. Ester, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-9-methylindenyl)ethyl methacrylate, 3-(all Fluoro-8-methylindenyl)-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(all Fluorin-9-methylindenyl)ethyl acrylate, pentafluorooctyl (meth) acrylate, undecafluorohexyl (meth) acrylate, nonafluoropentyl (meth) acrylate, heptafluoro Butyl (meth) acrylate, octafluoropentyl (meth) acrylate, pentafluoropropyl (meth) acrylate, trifluoro (meth) acrylate, triisofluoroisopropyl (methyl) Acrylate, trifluoroethyl (meth) acrylate, the following compounds (i) to (xxx), and the like. Further, the following compounds are all examples of acrylates, and the propyl group in the formula may be changed to a methyl propyl group.

The above compounds (i) to (xxx) are only a compound in which a hydrogen atom is R in the following formula (1), and one of the methylene groups bonded to the carbonyl carbon may be changed to a methyl group.

These compounds may be used singly or in combination of plural kinds. Among the above fluorinated acrylates, polyfunctional fluorinated acrylates are preferred. Further, the polyfunctional fluorinated acrylate herein means two or more (preferably three or more, more preferably four or more) (meth) acryloyloxy groups.

The translucent resin according to the preferred embodiment preferably contains at least one isocyanurate modified by ε-caprolactone formed by the following formula 7 as an optional component. Since the link portion of the ε-caprolactone has good affinity with the miscible resin, the inorganic pigment, and the additive thereof, it contributes to, for example, productivity in the coating process of the optical functional layer, and in the film forming step. Film formation stability (reducing the dispersion of film thickness) and the like. At the same time, it is effective (suppressing curl) in order to impart flexibility to the entire optical function layer, to relieve internal stress, and the like.

In the optical functional layer, in addition to the ε-caprolactone-modified isocyanurate, the thermosetting resin or the radiation-curable resin may be mixed and used, but it is advantageous in terms of production efficiency and energy cost. In other words, a series of radiation-curable resins in which the optical functional layer can be cured by radiation can be suitably used. As an example of the radiation curable resin, a radical polymerizable functional group such as an acryl fluorenyl group, a methacryl fluorenyl group, an acryl fluorenyloxy group or a methacryl fluorenyloxy group, or an epoxy group or an ethylene group can be used alone. A monomer, an oligomer, a prepolymer, or a composition obtained by appropriately mixing a cationically polymerizable functional group such as an ether group or an oxetane. Examples of the monomer include methyl acrylate, methyl methacrylate, methoxypolyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, and the like. Examples of the oligomer and the prepolymer include polyester acrylate, polyurethane acrylate, phenyl dehydroglyceryl ether hexamethylene diisocyanate urethane prepolymer, and phenyl group. Glycidyl ether toluene diisocyanate urethane prepolymer, epoxy acrylate, polyether acrylate, acid alcohol acrylate, melamine acrylate, polyoxy acrylate acrylate compound, unsaturated polyester, tetra Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether or various epoxy compounds such as alicyclic epoxy groups, 3-B 3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl An oxetane compound such as (3-oxetanyl)methyl ether.

The amount of the ε-caprolactone-modified isocyanurate is not particularly limited, but the ratio of the total solid content of the constituent material forming the optical functional layer is preferably in the range of 5 to 50%, and 10 to 30. The range of % is better. When the amount of the ε-caprolactone-modified isocyanurate is small, the adhesion between the light-transmitting substrate and the optical functional layer may be lowered, or the curl may become severe. At the same time, interference spots (disturbing spots caused by subtle thickness spots of the optical functional layer) are generated due to deterioration of film formability, and the visibility is deteriorated. Further, wrinkles or cracks occur in the optical functional layer due to the thickening of the optical functional layer. On the other hand, if the amount of the compound is too large, the scratch resistance of the optical functional layer may be lowered.

The radiation of the series which can harden the above-mentioned radiation hardening type resin can be any of ultraviolet rays, visible rays, infrared rays, and electron beams. At the same time, these radiations may be polarized or non-polarized. In particular, from the viewpoints of equipment cost, safety, and operating cost, it is preferably ultraviolet light. As for the ultraviolet energy source, for example, high pressure mercury lamp, halogen lamp, xenon lamp, halogen metal lamp, nitrogen laser, electron beam acceleration device, radioactive element, and the like. The irradiation amount of energy radiation source, accumulated exposure amount of ultraviolet wavelengths of 365nm, should range from 100 to 5,000mJ / cm ² at 300 to 3,000mJ / cm ² irradiation amount preferred, such as irradiation amount less than 100mJ / cm ² when The hardness of the optical functional layer may be lowered due to insufficient hardening. Further, when it exceeds 5,000 mJ/cm ² , the optical functional layer is colored to lower the transparency. When performing ultraviolet irradiation hardening, it is necessary to add a photopolymerization initiator. As the photopolymerization initiator, a compound which has never been known can be used. For example, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4'-diaminodi Benzene and other alkyl ethers such as benzophenone and benzyl methyl acetal; acetophenone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxy Acetophenones such as benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone; methyl hydrazine, 2-ethyl hydrazine, 2-pentyl Equivalent steroids; xanthone; thioxanthone, 2,4-diethylthiaxanthone, 2,4-diisopropylthiaxanthone, etc. Xanthone ketones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-dimethylaminobenzophenone Others such as 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one and the like. These initiators may be used singly or in combination of two or more. The photopolymerization initiator is used in an amount of about 5% or less, and preferably from 1 to 4%, based on the total amount of the radiation-curable resin composition.

In the filament of the radiation curable resin composition, a polymer resin may be added and used in a range that does not inhibit the polymerization hardening. The polymer resin is a thermoplastic resin which can be dissolved in an organic solvent used in an optical functional layer coating to be described later, and specifically, for example, an acrylic resin, an acid alcohol resin, a polyester resin, a cellulose derivative or the like. Among these resins, a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group or a sulfonic acid group is preferred.

At the same time, additives such as a leveling agent, an adhesion promoter, an antistatic agent, a filler, and a body pigment can be used. The leveling agent can trim the defect before the formation of the coating film, and the tension on the surface of the coating film can be made uniform, and the material having the interface tension and the surface tension lower than the radiation-curable resin composition can be used.

Although the optical functional layer is mainly composed of a cured product such as the above-mentioned resin composition, it is formed by coating a coating material formed of a resin composition and an organic solvent, and then volatilizing the organic solvent, and then radiating (for example, an electron beam or UV irradiation) or heat to harden it. At the organic solvent which can be used at this time, it is necessary to select a solvent suitable for dissolving the resin composition. Specifically, after considering the coating workability such as wettability, viscosity, and drying speed of the light-transmitting substrate, a single one or a mixed solvent selected from the group consisting of alcohols, esters, ketones, ethers, and aromatic hydrocarbons may be used. .

The thickness of the optical functional layer must be in the range of 3 to 50 μm, preferably in the range of 5 to 30 μm, and more preferably in the range of 7 to 20 μm. If the optical functional layer is thinner than 3 μm, the scratch resistance will be deteriorated, and the interference spots will not appear well. When it is thicker than 50 μm, curling occurs due to curing shrinkage of the optical functional layer, or microcracking occurs on the surface of the optical functional layer, or adhesion to the light-transmitting substrate is lowered, and light transmittance is further lowered. Moreover, increasing the amount of coating material required as the film thickness increases is also a cause of cost increase.

As the light-transmitting fine particles contained in the optical functional layer, for example, an acrylic resin, a polystyrene resin, a styrene-acrylic acid copolymer, a polyethylene resin, an epoxy resin, a polyoxymethylene resin, a polydisperse film can be used. Organic light-transmitting fine particles formed of vinyl fluoride, polyvinyl fluoride resin, or titanium oxide, cerium oxide (cerium oxide), aluminum oxide, zinc oxide, cerium oxide, zirconium oxide, calcium oxide, indium oxide, antimony oxide, Or inorganic light-transmitting fine particles (inorganic ultrafine particles) such as these composites. Further, these fine particles may be used alone or in combination of two or more. As the light-transmitting fine particles, it is preferred to use the crosslinked organic light-transmitting fine particles and the inorganic light-transmitting fine particles. Thereby, the pencil hardness of the hard coating film after hardening can be improved, and curling can also be prevented. Further, when the light-transmitting fine particles are used, for example, when the refractive index of the optical functional layer is lowered, the interference which affects the image quality of the display is preferably reduced. Further, when the cerium oxide is treated with a phthalic acid-based material (for example, a decane coupling agent such as an alkoxy decane having a functional group such as a vinyl group, a methacryl group, an amine group or an epoxy group), the saponification treatment is carried out. It can prevent the dissolution of cerium oxide. The particle diameter of the light-transmitting fine particles is preferably from 1 to 100 nm, and preferably from 10 to 50 nm. When the particle diameter is less than 1 nm, the chemical resistance is lowered, and the production cost of the particles is increased. When it is larger than 100 nm, the transmittance which affects optical characteristics is lowered, or the haze value is increased, or the contrast is lowered. "Particle size" means an average value of the diameters of 100 particles measured by an electron microscope. Further, within the total number, the fine powder and the coarse powder in the process of mixing the fine particles are less than 5% (preferably less than 1%). The amount of the light-transmitting fine particles is preferably from 5 to 70% by weight, preferably from 10 to 50% by weight. If the amount is less than 5% by weight, the effect of preventing curling and the hardness of the pencil are lowered. When the amount is more than 70% by weight, the scratch resistance is deteriorated. The light-transmitting fine particles are preferably used as a melt-bonding material, and in addition to being easy to form a coating, the dispersibility of the light-transmitting fine particles in the coating material can be improved at the same time. As the melted light-transmitting fine particles, for example, an alumina melt or a cerium oxide melt can be used. The method of forming the melt rubber will be described later.

Further, when the light-transmitting fine particles having an average particle diameter of 0.3 to 10 μm are contained in the optical functional layer or the like and the uneven structure is formed on the surface of the optical functional layer, it can be used as an anti-glare layer. Therefore, it can also be used as an anti-glare film. The refractive index of the light-transmitting fine particles having an average particle diameter of 0.3 to 10 μm is preferably 1.40 to 1.75. If the refractive index is less than 1.40 or greater than 1.75, the refractive index difference with the light-transmitting substrate or the resin matrix is excessive. Reduce the total light transmission rate. At the same time, the difference in refractive index between the light-transmitting fine particles and the resin component is preferably 0.2 or less. The average particle diameter of the light-transmitting fine particles is preferably in the range of 0.3 to 10 μm, and preferably 1 to 8 μm. When the particle diameter is less than 0.3 μm, the anti-glare property is lowered, and when it is more than 10 μm, in addition to the occurrence of glare, the degree of surface unevenness is also excessively increased, resulting in whitening of the surface, which is not preferable. The ratio of the light-transmitting fine particles contained in the above-mentioned resin is not particularly limited, but it is preferably from 1 to 20 parts by mass based on 100 parts by mass of the resin composition, because it can satisfy characteristics such as anti-glare function and flashing. It is also easy to control the fine concavo-convex shape and haze value of the surface of the optical functional layer. Here, the "refractive index" means a measured value in accordance with JIS K-7142. Meanwhile, the "average particle diameter" means an average value of diameters of 100 particles measured by an electron microscope.

In other words, since an optical functional layer (anti-glare layer) containing light-transmitting fine particles having a particle diameter of 1 to 100 nm and light-transmitting fine particles having a particle diameter of 0.3 to 10 μm can be formed, it is possible to provide an increase in pencil hardness and prevention of curling. And anti-glare optical laminate (anti-glare film).

In the optical layered body of the present invention, the difference between the refractive index of the light-transmitting substrate and the refractive index of the optical functional layer ([the refractive index of the light-transmitting substrate] - [the refractive index of the optical functional layer]) is preferably 0.10 or less. It is preferable that the refractive index of the optical functional layer is equal to or less than the refractive index of the light-transmitting substrate. By controlling the refractive index difference to the above range, it is possible to suppress the light reflection on the surface from becoming low.

The refractive index can be controlled by appropriately including the inorganic light-transmitting fine particles in the optical functional layer. The inorganic light-transmitting fine particles have a function of adjusting the apparent refractive index of the optical functional layer in accordance with the blending amount thereof. The refractive index of the light-transmitting substrate and the refractive index of the optical functional layer are as described above, and are preferably approximated. Therefore, when the optical functional layer forming material is prepared, it is preferable to appropriately adjust the blending amount of the inorganic light-transmitting fine particles so that the refractive index difference between the refractive index of the light-transmitting substrate and the optical functional layer becomes small. When the refractive index difference is large, the reflected light of the external light incident on the optical layered body is caused to appear in an iridescent phase, and when a so-called interference spot phenomenon occurs, the display quality is lowered. Especially in offices with high frequency of image display devices having optical laminates, a large number of three-wavelength fluorescent lamps have been added as fluorescent lamps, and three-wavelength fluorescent lamps have enhanced luminous intensity at specific wavelengths, and the objects are clearly visible. The characteristics, but under this three-wavelength fluorescent lamp, the determination of interference spots is more apparent.

In the present invention, the optical functional layer may have a polarizing substrate laminated on the opposite light transmissive substrate. In this case, the polarizing substrate can be a light-absorbing polarizing film that absorbs other light by transmitting only specific polarized light, or a light-reflecting polarizing film that reflects other light only by transmitting specific polarized light. As the light absorbing polarizing film, a film obtained by stretching polyvinyl alcohol, polyethylene or the like can be used, and for example, a polyvinyl alcohol (PVA) film obtained by uniaxially stretching a polyvinyl alcohol having adsorbed iodine or a dye can be used. As a dichroic element. For the light-reflective polarizing film, for example, "DBEF" manufactured by 3M Company, which is a type of polyester resin (PEN and PEN copolymer) having different refractive indices in the extending direction during stretching, is extruded. A composition in which a plurality of layers are formed by alternately forming a plurality of layers, or "NIPOCS" manufactured by Nitto Denko Corporation, which is formed by laminating a cholesteric liquid crystal polymer layer and a quarter-wavelength plate, and is incident on the side of the cholesteric liquid crystal polymer layer. The light is separated into two circularly polarized lights which are opposite to each other, one of which is transmitted and the other of which is reflected, and the circularly polarized light that has passed through the cholesteric liquid crystal polymer layer is converted into linearly polarized light by a quarter-wave plate, or manufactured by MERCK Corporation. "Trans Max" and so on.

In the light-transmitting substrate, an antistatic layer may be provided to prevent dirt such as dust from adhering electrostatically to the surface of the display. However, the antistatic layer is disposed outside the outermost surface. The method of providing an antistatic layer may be a method in which a metal oxide film such as alumina or tin or a metal oxide film such as ITO is provided to be extremely thin by vapor deposition or sputtering, or a metal such as alumina or tin or metal fine particles such as ITO or Metal oxide fine particles or whiskers such as whiskers, tin oxide doped with antimony, etc., formed between 7,7,8,8-tetracyanoquinodimethane and an electron donor such as a metal ion or an organic cation. a charge-moving bulk filler or the like, which is dispersed in a polyester resin, an acrylic resin, an epoxy resin, or the like, and a method of providing a polypyrrole such as camphorsulfonic acid or the like by a solvent coating method or the like, or a solvent coating method. A method in which polyaniline or the like is provided. The transmittance of the antistatic layer is preferably 80% or more for optical use.

Further, an optical functional layer can be used as a low reflection layer to improve contrast. At this time, it is preferable to provide a hard coat layer having a thickness of 3 to 50 μm on the bottom layer. At this time, it is preferable to increase the wettability of the surface of the hard coat layer. Since the wettability is increased, the affinity between the hard coat layer and the optical functional layer is improved, and the adhesion between the layers can be improved. The wettability can be increased by performing corona treatment, plasma treatment, or the like on the surface of the hard coat layer. On the wettability of the surface of the hard coat layer, the contact angle of water on the surface of the hard coat layer can be used as an index. The contact angle is preferably 80 degrees or less, and more preferably 65 degrees or less. At this time, it is necessary to make the refractive index of the low reflection layer lower than the refractive index of the underlayer, and preferably 1.45 or less. As the material having such characteristics, in addition to the above-mentioned fluorinated acrylate, there are, for example, LiF (refractive index n = 1.4), MgF ₂ (n = 1.4), 3NaF‧ AlF ₃ (n = 1.4), AlF. Microparticles of inorganic materials such as ₃ (n=1.4) and Na ₃ AlF ₆ (n=1.33), inorganic low-reflection materials contained in acrylic resins or epoxy resins, organic compounds of antimony oxides, and thermoplastic resins A combination of an organic low-reflection material such as a thermosetting resin or a radiation curable resin. Meanwhile, the critical surface tension of the low reflection layer is preferably 20 dyne/cm or less, preferably 18 dyne/cm or less, more preferably 15 dyne/cm or less. If the critical surface tension is greater than 20 dyne/cm, it is difficult to remove the dirt adhering to the low reflection layer.

Further, a low-reflection material obtained by mixing a sol formed by dispersing 5 to 30 nm of cerium oxide ultrafine particles in water or an organic solvent with a fluorine-based film forming agent may also be used. The 5 to 30 nm cerium oxide ultrafine particles are dispersed in water or an organic solvent to form a sol, and a method of de-alkaliating an alkali metal ion in an alkali citrate salt by ion exchange or the like, or neutralizing a citric acid base with a mineral acid may be used. A salt method, etc., a known cerium oxide sol is obtained by condensing a known active citric acid, and a known aerated cerium oxide is obtained by subjecting an alkoxy decane to hydrolysis and condensation in an organic solvent in the presence of a salt-based catalyst. In the sol, an organic solvent-based cerium oxide sol (organic cerium oxide sol) obtained by substituting water in the above aqueous cerium oxide sol into an organic solvent by a distillation method or the like is further used. As the cerium oxide sol, any of an aqueous system and an organic solvent may be used. In the production of an organic solvent-based cerium oxide sol, it is not necessary to completely replace water into an organic solvent. The solid content of 0.5 to 50% by weight of the above cerium oxide sol is SiO ₂ . The structure of the cerium oxide microparticles of the cerium oxide sol can be various shapes such as a spherical shape, a needle shape, and a plate shape.

The low-reflection layer is used to calculate the thickness of the anti-reflection function well by a well-known calculation formula. When the incident light is incident perpendicularly to the low reflection layer, the low reflection layer can be made to reflect light and be 100% transmitted as long as the condition of the following relationship is satisfied. Meanwhile, in the formula, N ₀ represents the refractive index of the low reflection layer, N _S represents the refractive index of the underlayer, h represents the thickness of the low reflection layer, and λ ₀ represents the wavelength of light.

[Number 1]

N ₀ =N _s ^1/2 (1)

N ₀ h=λ ₀ /4 (2)

According to the above formula (1), it is known that the reflection of light can be prevented 100% by selecting a material which allows the refractive index of the reflective layer to be the square root of the refractive index of the underlayer. However, it is actually difficult to have a material that fully satisfies this number, so it is only possible to choose a material that is close to the limit. In the above formula (2), the refractive index of the low-reflection layer selected by the formula (1) and the wavelength of light can be used to calculate the optimum thickness of the low-reflection layer as the anti-reflection film. For example, when the refractive indices of the underlying layer and the low-reflection layer are set to 1.50 and 1.38, respectively, and the wavelength of light is 550 nm (the basis of the sensitivity), the values of the low-reflection layer can be calculated by substituting these values into the above formula (2). The optical film thickness of about 0.1 μm is optimal in the range of 0.1 ± 0.01 μm.

In the method for producing an optical layered body of the present invention, for example, a radiation-curable resin coating material containing a polyfunctional acrylate, a fluorinated acrylate, or a translucent fine particle is applied onto a light-transmitting substrate, and after being dried, it is cured by radiation. Can be made. Since the price of the fluorine-containing material is high, it is preferable to make it biased on the surface of the optical functional layer. The drying step is particularly important in the present invention. It is preferred to carry out the drying slowly at a low temperature in the drying step. By slowly drying, the fluorinated acrylate can be accumulated on the surface of the optical functional layer and hardened by radiation to obtain an optical functional layer having a fluorinated acrylate biased on the surface side. At this time, the drying temperature is preferably from 50 to 130 ° C, and preferably from 60 to 100 ° C. The drying time is preferably from 1 to 10 minutes, and preferably from 2 to 5 minutes. At the same time, when the radiation-curable resin coating is applied to form a coating film and immediately enters the drying step, it is preferable to design a preliminary drying step. Thereby, the fluorinated acrylate is easily biased on the surface side of the optical functional layer because the drying of the coating film can be performed more slowly. The preliminary drying step is a step of uniformly blowing a weak gas stream against the coating film from a direction slightly perpendicular to the plane of the coating film. The air volume of the weak airflow is preferably from 0.01 to 1.0 m/sec. The air flow rate may be measured in a state where the wind speed detecting hole of the anemometer (KANOMAX CLIMOMASTER (trademark)) is 1 cm away from the coating film. At the same time, the temperature of the gas stream in the preliminary drying step may be set at 20 to 60 °C.

As for the method of applying the coating on the light-transmitting substrate, a usual coating method or printing method can be applied. Specifically, air doctor coating, strip coating, blade coating, knife coating, trans coating, transfer roller coating, gravure coating, and pressure can be used. Coatings such as kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating, die coating, or gravure printing Printing such as printing and screen printing, etc.

Hereinafter, the constituent materials and production methods of the present invention will be described in order after explaining the drawings of the present invention (β).

Fig. 2 is a plan view showing a hard coat film 1 in which a hard coat layer 20 is laminated on a resin film 10. As shown in Fig. 2, although the hard coat layer 20 can be laminated to the end surface 11b from the end surface 11a of the resin film 10, it is not limited thereto. That is, as long as the hard coat layer 20 is laminated on the resin film 10, it is not necessary to make the end faces 21a and 21b of the hard coat layer 20 coincide with the end faces 11a and 11b of the resin film 10.

Fig. 3 is a cross-sectional view showing the hard coating film 1 cut by a straight line L in Fig. 2 . In the third drawing, the thickness of the hard coat layer 20 is set to A, the length from the edge portion 12a of the resin film 10 to the edge portion 22a of the hard coat layer 20 (both edge widths) is B, and the edge of the resin film 10 is obtained. The length from the portion 12b to the edge portion 22b of the hard coat layer 20 is set to B'. B and B' may be of the same length or may have respective lengths.

The hard coat film of the present invention must be A × 1500 < B. Since A × 1500 < B is made, curling of the hard coating film 1 can be suppressed. For example, when the thickness of the hard coat layer is 0.003 mm which is the lower limit of the invention, the above relationship can be made to be 4.5 < B. Meanwhile, if the thickness of the hard coat layer is 0.020 mm of the upper limit of the invention, the above relationship becomes 30 < B. At this time, the upper limit of B in the above relation is not particularly limited, and may be, for example, 100, and preferably 50. As long as it exceeds the lower limit of B, it is possible to provide a hard coating film which is less likely to cause wrinkles and curl. From the viewpoint of effective use of the resin film, the relationship between the two edges in the relationship of A × 1500 < B is preferably close to the lower limit of the B.

When the pencil hardness (JIS K5400) of the hard coat layer constituting the hard coat film is 4 or more, when it is A × 1500 ≧ B, since it is easy to curl, it cannot be used as the hard coat film of this invention. Further, in the above relation, the B value can be applied to any smaller value of the B value and the B' value shown in Fig. 3.

Next, a material which can constitute the present invention (β) will be described.

<Resin film>

The material which can constitute the resin film of the present invention is not particularly limited.

When the hard coat film of the present invention is used for optical applications such as LCD or PDP, the transparency of the resin film is preferably as high as possible. Specifically, the total light transmittance (JIS K7105) of the resin film is 80% or more, and preferably 90% or more.

As for a resin film suitable for optical use, specifically, polyethylene terephthalate (PET), cellulose triacetate (TAC) polyethylene naphthalate (PEN), polymethyl group are used. Methyl acrylate (PMMA), polycarbonate (PC), polyimine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cyclic olefin Various resin films such as a copolymer (COC), a norbornene resin, a polyether oxime, a cellophane, and an aromatic polyamine are preferable. These films may use a film that is not stretched, or a film that has been stretched. In particular, the PET film which has been biaxially stretched is excellent in mechanical strength or dimensional stability, and the film formed from the unstretched TAC film and the norbornene-containing resin has very little in-plane phase difference. And good. Further, in the case of use in optical applications such as PDP and LCD, it is preferred that the PET film, the TAC film, and the norbornene-containing resin film are used.

The elastic modulus of the resin film is preferably from 2 GPa to 8 GPa, and preferably from 3 GPa to 7 GPa.

Since a resin film having an elastic modulus in the above range is used as a constituent material of the hard coating film, when the hard coating film is processed into a polarizing plate and used in a liquid crystal display device, even in a high-humidity and low-temperature environment, Defects such as light leakage and a decrease in the degree of polarization are therefore preferable.

When the elastic modulus of the resin film is less than 2 GPa, there is a fear that the resin film is broken when the coating for forming a hard coat layer is applied by Roll to Roll.

Further, the modulus of elasticity in the present invention means a value measured in accordance with JIS P8113. Specifically, it can be obtained by measuring a tensile strength of a resin film at a speed of 1 mm/min using a tensile tester (trade name: RTG1210, manufactured by A&D Co., Ltd.).

The thickness of the resin film is preferably from 5 to 100 μm, more preferably from 20 to 100 μm, even more preferably from 40 to 80 μm, in terms of weight reduction, thinning of the display or production suitability of the hard coating film.

When the thickness of the resin film is within this range, the resin film can absorb or alleviate the shrinkage stress generated when the hard coat layer is cured, so that wrinkles or curling of the hard coat film can be suppressed.

When the thickness of the resin film is less than 5 μm, shrinkage stress generated during hardening of the hard coat layer is not easily suppressed, so that shrinkage occurs on the hard coat layer, and wrinkles or curls are formed on the hard coat film, so that the hard coat film is formed. Productivity deteriorates. When the thickness of the resin film exceeds 100 μm, wrinkles or curling of the hard coating film can be suppressed, but it is difficult to achieve weight reduction and thinning. In particular, when the hard coat film of the present invention is used for optical use, it is not preferable to make the thickness of the resin film exceed 100 μm.

On the resin film, surface treatment such as alkali treatment, corona treatment, plasma treatment, sputtering treatment, or saponification treatment, or application of a surfactant, a decane coupling agent, or the like, or surface modification treatment such as Si vapor deposition may be performed. Thereby, the adhesion between the resin film and the hard coat layer can be improved.

<hard coating>

In the hard coat layer of the present invention, a thermosetting resin, a radiation curable resin, or a resin obtained by mixing a thermosetting resin and a radiation curable resin can be used. The volume shrinkage ratio of the thermosetting resin or the radiation curable resin is preferably from 5 to 25%, and preferably from 7 to 15%. If it is less than 5%, there may be a reduction in the scratch resistance of the hard coating. When it exceeds 25%, it is easy to cause the shrinkage of the hard coat layer, and it is easy to cause the hard coat film to curl, which is not preferable.

In the hard coat layer of the present invention, a radiation curable resin which can harden a hard coat layer by radiation is preferably used. Thereby, advantages such as improved production efficiency and reduced energy costs can be obtained.

As an example of the radiation curable resin, a radical polymerizable functional group such as an acrylonitrile group, a methacryl fluorenyl group, an acryloyloxy group, or a methacryloxy group may be used, or an epoxy group or a vinyl ether group may be used. A monomer, an oligomer, or a prepolymer of a cationically polymerizable functional group such as an oxethone group is used alone or in an appropriate mixture. Examples of the monomer include methyl acrylate, methyl methacrylate, methoxypolyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, and ethylene. Alcohol dimethacrylate, diisopentyl alcohol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. Examples of the oligomer and the prepolymer include polyester acrylate, polyurethane acrylate, benzene dehydroglyceryl ether hexamethylene diisocyanate urethane prepolymer, and phenyl group. Glycidyl ether toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane pre Polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, acid alcohol acrylate, melamine acrylic acid, such as a polymer, isopentanol triacrylate, isophorone diisocyanate urethane prepolymer Acrylates such as esters, polyoxy acrylates, unsaturated polyesters, tetramethyl glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A Ethylene oxide such as glyceryl ether or various alicyclic epoxy groups, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxocyclic) Oxygen heterocycles such as butanyl)methoxy]methyl}benzene and bis[1-ethyl(3-oxetanyl)methyl ether Butane compound.

Although the radiation curable resin may be used singly or in combination of several kinds, a polyfunctional acrylate such as diisalitol hexaacrylate which is excellent in curing rate and scratch resistance of a hard coat layer, and a resin film and a hard coat layer are used. The adhesion of the adhesiveness, the flexibility of the hard coat layer, and the polyfunctional urethane acrylate excellent in flexibility are preferable. The mixing ratio of the polyfunctional urethane acrylate relative to the polyfunctional acrylate is preferably in the range of 0.1 to 1.5, and preferably in the range of 0.2 to 0.7. When the mixing ratio of the polyfunctional urethane acrylate relative to the polyfunctional acrylate is too low, wrinkles or cracks are likely to occur on the hard coat layer, and the hard coat film is easily curled. On the other hand, if there is too much, the scratch resistance of the hard coat layer is lowered, which is not preferable.

The radiation of the wire which can harden the above-mentioned radiation hardening type resin can be any of ultraviolet rays, visible rays, infrared rays, and electron beams. At the same time, these radiations may be polarized or non-polarized. In particular, ultraviolet rays are preferred from the viewpoints of equipment cost, safety, and operating cost. As for the ultraviolet energy source, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a halogenated metal lamp, a nitrogen gas injection, an electron beam acceleration device, a radioactive element, and the like are preferable. The amount of exposure of the energy source, the cumulative exposure amount of the ultraviolet light wavelength of 365 nm is preferably in the range of 100 to 5,000 mJ/cm ² , and preferably 300 to 3,000 mJ/cm ² , and if the irradiation amount is less than 100 mJ/cm ² , The hardness of the hard coat layer may be lowered due to insufficient hardening, and if it exceeds 5,000 mJ/cm ² , the hard coat layer may be colored to lower the transparency. When hardening by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. As the photopolymerization initiator, a starter known in the past can be used. For example, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, N,N,N,N-tetramethyl-4,4'-diaminobenzophenone, benzene Benzene and other alkyl ethers such as methyl methyl acetal; acetophenone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 2, Acetophenones such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone; methylhydrazine, 2-ethylhydrazine, 2-pentylfluorenone, etc. Class; xanthone; thiazinone, 2,4-diethylthiaxanthone, 2,4-diisopropylthiaxanthone, etc.; acetophenone dimethyl condensate Ketones such as ketones and benzyl dimethyl ketals; benzophenones such as benzophenone and 4,4-dimethylaminobenzophenone; others such as 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one and the like. These initiators may be used singly or in combination of two or more. The photopolymerization initiator is used in an amount of about 5% or less in terms of total solid content, and preferably from 1 to 4%, relative to the radiation-curable resin composition.

In the series of the radiation curable resin composition described above, a polymer resin may be added and used in a range that does not inhibit the polymerization hardening. The polymer resin is a thermoplastic resin which can be dissolved in an organic solvent used in a hard coat coating material to be described later, and specific examples thereof include an acrylic resin, an acid alcohol resin, and a polyester resin. Among these resins, a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group or a sulfonic acid group is preferred.

At the same time, additives such as a leveling agent, an adhesion promoter, an antistatic agent, a filler, and a body pigment can be used. The leveling agent can trim the defect before the formation of the coating film, and the tension on the surface of the coating film can be made uniform, and a material having a lower interfacial tension and a surface tension than the above-mentioned radiation-curable resin composition can be used.

Although the hard coat layer is mainly composed of a hardened material such as the above resin composition, it is formed by coating a coating material formed of a resin composition and an organic solvent, volatilizing the organic solvent, and then irradiating with radiation (for example, electron beam or ultraviolet light). Or heat to harden it. In the organic solvent to be used at this time, it is necessary to select a solvent suitable for dissolving the resin composition. Specifically, in consideration of coating properties such as wettability, viscosity, and drying speed of the resin film, a single one or a mixed solvent selected from the group consisting of alcohols, esters, ketones, ethers, and aromatic hydrocarbons can be used.

The thickness of the hard coat layer is in the range of 3.0 to 20.0 μm, preferably in the range of 5.0 to 15.0 μm, and more preferably in the range of 7.0 to 13.0 μm.

When the hard coat layer is thinner than 3.0 μm, the surface hardness is lowered.

If the hard coat layer is thicker than 20.0 μm, the resin film may not absorb or moderate the stress at the time of hardening and shrinking of the hard coat layer, and the hardened coat film may be curled, or microcracks may occur on the surface of the hard coat layer, or the resin may be lowered. The adhesion between the films further reduces the light transmittance. Therefore, increasing the amount of necessary coating as the film thickness increases is also a cause of an increase in cost.

Organic and inorganic fine particles can also be moderately contained in the hard coat layer. The organic and inorganic fine particles may be contained alone in the hard coat layer, or the organic and inorganic fine particles may be combined and contained therein.

As the organic fine particles, for example, an acrylic resin, a polystyrene resin, a styrene-acrylic acid copolymer, a polyethylene resin, an epoxy resin, a polyoxynoxy resin, a polyvinylidene fluoride, a polyvinyl fluoride resin, or the like can be used. .

As the inorganic fine particles, for example, titanium oxide, cerium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, calcium oxide, indium oxide, cerium oxide or the like can be used. Composites of such oxides can also be used. Among these fine particles, titanium oxide, cerium oxide (cerium oxide), aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferred.

The above-mentioned organic and inorganic fine particles may be used singly or in combination of two or more kinds.

Further, when the light-transmitting fine particles having an average particle diameter of 0.3 to 10 μm are contained in the hard coat layer, and the uneven structure is formed on the surface of the hard coat layer, it is preferably used as an anti-glare layer. Therefore, a hard coat film can also be used as the anti-glare film. The light-transmitting fine particles having an average particle diameter of 0.3 to 10 μm preferably have a refractive index of 1.40 to 1.75. If the refractive index is less than 1.40 or greater than 1.75, the refractive index difference from the light-transmitting substrate or the resin matrix is too large, resulting in total light. The transmission rate will decrease. At the same time, the difference in refractive index between the light-transmitting fine particles and the resin component is preferably 0.2 or less. The average particle diameter of the light-transmitting fine particles is preferably in the range of 0.3 to 10 μm, and preferably 1 to 8 μm. Since the particle size is less than 0.3 μm, the anti-glare property is lowered, and when it is more than 10 μm, in addition to the occurrence of glare, the degree of surface unevenness is also excessively increased, so that the surface becomes white, which is not preferable. The ratio of the light-transmitting fine particles to the above-mentioned resin is not particularly limited. However, when it is 1 to 20 parts by mass based on 100 parts by mass of the resin composition, it is preferable because it can satisfy characteristics such as anti-glare function and flashing. It is easy to control the fine uneven shape and haze value of the surface of the hard coat layer. Here, the "refractive index" means a measured value in accordance with JIS K-7142. Meanwhile, the "average particle diameter" means an average value of diameters of 100 particles measured by an electron microscope.

In the present invention, a polarizing substrate may be laminated on the resin film (the surface on which the hard coat layer is not laminated). In this case, the polarizing substrate may be a light-absorbing polarizing film that absorbs other light by transmitting only a specific polarized light, or a light-reflecting polarizing film that transmits only other light by transmitting a specific polarized light. As the light absorbing polarizing film, a film obtained by stretching polyvinyl alcohol, polyethylene or the like can be used, and for example, polyvinyl alcohol (PVA) obtained by uniaxially stretching polyvinyl alcohol having adsorbed iodine or a dye can be used. The film acts as a dichroic element. As a light-reflective polarizing film, for example, "DBEF" manufactured by 3M Company, which is a polyester resin (PEN and PEN copolymer) having different refractive indices in the extending direction during stretching, is applied by extrusion molding. "NIPOCS" manufactured by Nitto Denko Co., Ltd., which is a combination of a liquid crystal polymer layer and a quarter-wave plate, and which is incident on the side of the cholesteric liquid crystal polymer layer. Separation into two circularly polarized lights that are opposite to each other, one of which is transmitted and the other of which is reflected, and the circularly polarized light that has passed through the cholesteric liquid crystal polymer layer is converted into linearly polarized light by a quarter-wave plate, or manufactured by MERCK Corporation. "Trans Max" and so on.

On the resin film constituting the hard coating film, the saponification treatment on the hard coating film can improve the adhesion between the hard coating layer constituting the hard coating film and the polarizing substrate before laminating the polarizing substrate ( Then force). In the past hard coating film, although curling or cracking can be clearly observed on the hard coating film by the saponification treatment, according to the present invention, curling can be reduced even on the hard coating film after saponification. Or the occurrence of a rupture.

<other layers>

The hard coat layer may be laminated on one side of the resin film or may be laminated on both sides. Further, the hard coat film may have other layers. As for the other layers herein, for example, a polarizing substrate, a low reflection layer, and a layer imparted with other functions (for example, an antistatic layer, a near-infrared (NIR) adsorption layer, a filtered twilight layer, an electromagnetic wave shielding layer, and a hard layer) coating). At the same time, the position of the other layer is, for example, in the case of the polarizing substrate, on the resin film opposite to the hard coating layer, and in the case of the low reflection layer, above the hard coating layer, in imparting other functions The layer of the layer is at the bottom layer of the aforementioned hard coat layer.

<Manufacturing method>

In the method for producing a hard coat film of the present invention, for example, a radiation curable resin paint is applied onto a resin film, dried, and then radiation-cured. When coating is performed, it is sufficient to satisfy the relationship of A × 1500 < B. As a method of coating the resin film, a usual coating method or printing method can be applied. Specifically, air doctor coating, strip coating, blade coating, knife coating, trans coating, transfer roller coating, gravure coating, and pressure can be used. Coatings such as kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating, die coating, or gravure printing Printing such as printing and screen printing, etc.

At the same time, in order to satisfy the relationship of A × 1500 < B, the hard coating film of the present invention is less likely to be cracked or wrinkled or curled due to hardening shrinkage even when it is manufactured by Roll-to-Roll, so that the yield can be improved.

[Examples]

Hereinafter, an embodiment of the invention (α) will be described.

<Examples 1 to 4, Comparative Examples 1 to 3>

2.8 parts of methacryl methoxy propyl trimethoxy decane and methyl ethyl ketone cerium oxide sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST-L, number average particle diameter: 45 nm, dioxide a mixture of 95.6 parts (27.4 parts of solid content) and 0.1 part of ion-exchanged water was stirred at 80 ° C for 3 hours, then 1.4 parts of methyl orthoformate was added, and the mixture was heated and stirred at the same temperature for 1 hour. The dispersion of the light-transmitting fine particles of the present invention (liquid A) can be obtained. The total solid content concentration was found to be 32%, and the average particle diameter of the light-transmitting fine particles was 45 nm. At this time, the average particle diameter was measured by a penetration electron microscope.

The coating for the optical functional layer obtained by dispersing the mixture of the components described in Table 1 in a disperser for 30 minutes was applied by a roll coating method (linear rate; 20 m/min) at a film thickness of 40 μm and a total light transmittance of 92. % of the TAC (Konica Minolta Opt Co., Ltd.; KC4UYW) which forms a light-transmitting substrate is subjected to preliminary drying for 20 seconds at a flow rate of 0.5 m/sec and 30 to 50 ° C, and then dried at 100 ° C for 1 minute. Ultraviolet irradiation was carried out in a nitrogen atmosphere (instead of nitrogen gas) (lamp: concentrating high-pressure mercury lamp, lamp output: 120 W/cm, number of lamps: 2 lamps, irradiation distance: 20 cm), and the coating film was cured. Thus, the optical laminates of Examples 1, 2, and 4 and Comparative Examples 1 to 3 having an optical functional layer having a thickness of 10.0 μm were obtained. At the same time, an optical layered body of Example 3 in which the film thickness of the light-transmitting substrate was 80 μm and the thickness of the optical function layer was 12.0 μm was obtained.

<Comparative Example 4>

The optical laminate of Comparative Example 4 of the present invention was obtained in the same manner as in Example 1 except that the thickness of the optical functional layer was 2 μm.

Using the optical laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 4, adhesion, total light transmittance, haze value, contact angle of water, curl, scratch resistance, and the like were performed by the following methods. Determination and evaluation of the ratio of pencil hardness, chemical resistance, antifouling, interference spots and fluorine.

Adhesion

This was carried out in accordance with the cross cut method of JIS K5600.

Further, the interval between the cuts was 1 mm, and the number of cuts was 11. The ratio of the number of uncut cross-cut grids is evaluated in %. For example, if there are 5 peels, it is expressed as 95/100.

Total light transmittance

The haze meter (trade name: NDH2000, manufactured by Nippon Denshoku Co., Ltd.) was used in accordance with JIS K7105.

Haze

The haze meter (trade name: NDH2000, manufactured by Nippon Denshoku Co., Ltd.) was used in accordance with JIS K7105.

Contact angle of water (θ/2 method)

First, the contact angle of water on the surface of the optical functional layer was measured. Next, the contact angle of water on the surface of the saponified optical functional layer was measured. The contact angle of the water was measured in accordance with JIS R3257 (Test method for wettability of the surface of the substrate glass) using a contact angle meter (trade name: Elma G-1 contact angle meter, manufactured by Elma Co., Ltd.).

The saponification treatment of the optical laminate is in the following order.

(1) Immersed in a 6% aqueous sodium hydroxide solution at 55 ° C for 2 minutes.

(2) Washed for 30 seconds.

(3) Immersed in sulfuric acid at 35 ° C, 0.1 N for 30 seconds.

(4) Wash for 30 seconds.

(5) Drying at 120 ° C for 1 minute with hot air.

As long as the value of the contact angle is made large, the water repellency effect can be improved, and the chemical resistance, abrasion resistance, and antifouling property can be improved. The contact angle before the saponification treatment is 90 or more, preferably 100 or more, and the contact angle after the saponification treatment is 70 or more, preferably 80 or more.

curly

First, the produced optical laminate was placed in an environment shown in JIS K5600-1-6 (temperature and humidity of the test and test) (temperature: 23±2° C., humidity: 50±5 RH%) for 16 hours. Then, a measurement piece of 10 cm × 10 cm was cut out in the same environment, and the optical function layer was placed on top of the flat plate, and the "measurement portion" shown in Fig. 1 was measured. When the measured value is less than 0 to 10 mm, it is represented by ×. If it is less than 10 to 30 mm, it is represented by Δ. If it is less than 30 to 50 mm, it is represented by ○, and when it is 50 mm or more, it is represented by ◎.

Antifouling

On the optical functional layer of the optical laminate produced, a 3 cm-length line was drawn with an oil-based pen (trade name: Mckee, manufactured by ZEBRA), and after 1 minute, a cleaning cloth was used (product number: FF-390C, Kuraray Kuraflex) Company (share) system) method of wiping evaluation. After rubbing back and forth 20 times with a load of 500 g/cm ² , it was ○ when it was completely wiped off, △ when there was no wiped off portion, and × when it was not wiped off.

Chemical resistance

Ligroin, toluene, sulfuric acid (10%), NaOH (6%), ethanol, neutral detergent (Family Pure), hand cream (Nivea), hair liquid (Success:Morning) Each of the reagents of Hair Water was dropped on the surface of the optical functional layer and left for 10 hours. The cleaning cloth (FF-390C, manufactured by Kuraray Kuraflex Co., Ltd.) was wiped 20 times with a load of 500 g/cm ² . Methodological assessment. After wiping, the appearance was visually evaluated for change. For all drugs, when there is no change, it is ○, and any one of the drugs can be seen as × when the whitening changes.

Scratch resistance

Steel Wool #0000 manufactured by Steel Wool Co., Ltd. of Japan was mounted on an abrasion resistance tester (Abrasion Tester, Model: 339, manufactured by Fu Chien Co., Ltd.), and the optical function layer was rotated 10 times at a load of 250 g/cm ² . Then, under the fluorescent light, confirm the abrasion of the worn part. When the number of scars is 0, it is ◎, when the number of scars is less than 1 to 10, it is ○, when the number of scars is less than 10 to 30, it is △, and when the number of scars is 30 or more, it is ×.

Surface hardness (pencil hardness)

It measured by a pencil hardness meter (made by the YOSHIMITSU Seiki Co., Ltd.) in accordance with JIS 5400. The number of measurements was 5, and the number of scratches was counted. For example, a pencil with 3H is 3/5 (3H) as long as there are no three scratches. It is preferable that the pencil hardness is 4/5 (3H) or more.

Interference spot

On the surface of the polarizing plate of the cross Nicol prism, the optical functional layer was used as the front side, and the adhesive layer having a refractive index of 1.5 was interposed and bonded (film thickness: 20 μm) to the three-wavelength fluorescent lamp (Panasonic Electric Apparatus). The industrial company system: FLR40S‧EX-N/MX, illuminance of about 500 lux (lux), was visually evaluated under reflection. When it is not possible to confirm that there is an interference spot, it is ○, and it can be confirmed as △ when it is shallow, and it is × when it can be clearly confirmed.

Fluorine element ratio

The amount of fluorine element on the surface of the optical functional layer was evaluated using ESCA. The measurement conditions are as follows.

Measuring device: Ulvac-phi company (Albakfa)

Quantera SXM

Photoelectron take-in angle: 45 degrees

X-ray output: 25.0W

Determination of X-ray diameter: 100 μm

Pass Energy: 112.0eV

Determination of elements: Cls, Ols, Fls, Si2p

Using ESCA, Cls, Ols, Fls, Si2p present from the surface of the optical functional layer to a depth of 5 nm were measured. The element ratio can be calculated from the peak area of the resulting element.

The components in Table 1 are described in detail herein.

Multifunctional acrylates Kyoeisha Chemicals PE3A: Isobaerythritol triacrylate (3 functional)

Multifunctional urethane acrylate Kyoeisha Chemical UA-306H: Isopentanol triacrylate hexamethylene diisocyanate urethane prepolymer (6 functional)

Polyfunctional acrylate-based Japanese medicine PET-30: isopentanol triacrylate (3-functional)

Polyfunctional acrylate-based East Asian synthesis M-305: Isobaerythritol triacrylate (3-functional)

Monofunctional acrylate Coronal Chemical HOP-A: 2-hydroxy propyl acrylate (1-functional)

Fluorinated acrylate Kyoeisha Chemical LINC-3A: a mixture of tripropylene decyl heptafluorononyl isopentaerythritol (4-functional) 65% and isopentaerythritol tetraacrylate (4 functional) 35% (described below) 8)

Fluorinated Acrylate Gongrongshe Chemical LINC-102A: Compound shown in the following Chemical Formula 9

[化8]

[Chemistry 9]

The measurement results are summarized in Table 2.

Cls, Ols, Fls, Si2p present in the examples from 1 to 4 in the surface of the optical functional layer to a depth of 200 nm were measured using an ESCA on a 5 nm scale. The ratio of the fluorine element ratio from the surface of the optical functional layer to 5 nm divided by the depth of the surface of the optical functional layer of 5 nm to 20 nm is measured on a 5 nm scale, and the value of the average value of the fluorine element per 5 nm is measured. It is 20 or more in 1 to 4.

Examples and comparative examples of the present invention (β) will be described below. In addition, "parts" means "parts by mass".

[Example 5]

After the mixture of the following coating components was stirred by a disperser for 1 hour, the obtained coating material was applied as a coating for a hard coating layer by a die head coating method at a film thickness of 40 μm and a total light transmittance of 92%. One side of a resin film-coated TAC (manufactured by Konica Minolta Co., Ltd., trade name: KC4UYW) was dried at 100 ° C for 1 minute, and then irradiated with ultraviolet light at a 120 W/cm condensed high-pressure mercury lamp in a nitrogen atmosphere. The coating film was hardened by a distance of 10 cm and an irradiation time of 30 seconds. The hard coat layer was made to have a thickness of 19 μm and both edge widths of 30 nm. Thereby, the hard coat film of Example 5 was obtained.

‧Multifunctional acrylate (product name: Lightacrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) 150 parts

‧Multifunctional urethane acrylate (product name: U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40 parts

‧Photoinitiator (Ciba Specialty Chemicals, trade name: Irgacure 184) 9 parts

‧Tuping agent (trade name of Gongrongshe Chemical Co., Ltd.: Polyflow-No. 77) 1 copy

‧ Solvent (MEK) 200 parts

[Embodiment 6]

The hard coat film of Example 6 of the present invention was obtained in the same manner as in Example 5 except that the thickness of the hard coat layer was 10 μm and the width of both edges was 20 mm.

[Embodiment 7]

The hard coat film of Example 7 of the present invention was obtained in the same manner as in Example 5 except that the coating composition of the hard coat layer was changed as follows, and the thickness of the hard coat layer was 9 μm and the width of both edges was 15 mm.

‧Multifunctional acrylate (product name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 130 copies

‧Multifunctional urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd. trade name: UV-UV-1700B) 60 parts

‧Photoinitiator (Vobart Chemical Company, trade name: Irgacure 127) 9 parts

‧Tuping agent (manufactured by Kyoeisha Chemical Co., Ltd. Product name: Polyflow-No. 77) 1 copy

‧Solvent (MEK) 120 parts

‧Solvent (MIBK) 80 parts

[Embodiment 8]

The hardening of Example 8 of the present invention was carried out in the same manner as in Example 5 except that the resin film was changed to TAC (trade name: TD80, manufactured by Fujifilm Opt Materials Co., Ltd.) having a thickness of 80 μm and both edge widths were 29 mm. Coating film.

[Embodiment 9]

The hard coating film of Example 9 of the present invention was obtained in the same manner as in Example 5 except that the resin film was changed to PET (manufactured by Toyobo Co., Ltd.: A4300) film having a thickness of 75 μm.

[Comparative Example 5]

A hard coat film of Comparative Example 5 was obtained in the same manner as in Example 5 except that the width of both edges was 20 mm.

[Comparative Example 6]

A hard coat film of Comparative Example 6 was obtained in the same manner as in Example 5 except that the thickness of the hard coat layer was 28 μm.

[Comparative Example 7]

A hard coat film of Comparative Example 7 was obtained in the same manner as in Example 5 except that the thickness of the hard coat layer was 10 μm and the width of both edges was 5 mm.

[Comparative Example 8]

The hard coating of Comparative Example 8 was obtained in the same manner as in Example 5 except that the coating composition for the hard coat layer was changed to the following, and the thickness of the hard coat layer was 15 μm and the width of both edges was 10 mm. membrane.

‧Multifunctional acrylate (manufactured by Kyoeisha Chemical Co., Ltd. trade name: Lightacrylate DPE-6A) 40 parts

‧Multifunctional urethane acrylate (product name: U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 150 parts

‧Photoinitiator (Vobart Chemical Company, trade name: Irgacure 184) 9 parts

‧Tuping agent (manufactured by Kyoeisha Chemical Co., Ltd. Product name: Polyflow-No. 77) 1 copy

‧ Solvent (MEK) 200 parts

Using the hard coating films obtained in Examples 5 to 9 and Comparative Examples 5 to 8, the following methods were used for measurement and evaluation for curling, wrinkles, adhesion, and pencil hardness. The results obtained are shown in Table 3.

(1. Curl)

The hard coating films of Examples 5 to 9 and Comparative Examples 5 to 8 were produced to have a length of 1.5 m. Next, as shown in Fig. 4(a), the hard coating film 1 is placed on the water table seat 30 with the coated surface as the upper side, and the four corners of the hard coating film 1 are fixed by the cellophane tape (registered trademark) 40. Water platform seat 30. Next, the hard coat layer was placed in an environment shown in JIS K5600-1-6 (temperature and humidity of the test and test) (temperature: 23±2° C., humidity: 50±5 RH%) for 16 hours. Next, the respective heights C rising in the opposite direction from the water platform seat 30 were measured from a portion where the side of the hard coating film 1 was fixed by a cellophane tape (registered trademark) 40 at a distance of 0.5 m. As shown in Fig. 4(b), the height C of the reverse rise is the distance from the center of the water platform seat 30 to the hard coating film 1. After the test 5 times, the average value was taken as the measured value of the curl.

At the same time, when the crimp is 20 mm or less, it is ○. If it is more than 20 mm, the production of a hard coating film or various secondary processed products using the same (for example, a polarizing plate protective film subjected to saponification treatment on a hard coating film) is greatly affected. The effect is therefore ×.

(2. wrinkles)

The average interval between the 10 wrinkles and the wrinkles in the application direction is ○ when it is 10 mm or more, Δ when it is 5 mm or more and less than 10 mm, or × when there is crack or crease on the film.

(3. Adhesiveness)

The adhesion was evaluated in accordance with the cross cutting method of JIS K5600. At the same time, the cutting interval is 1 mm and the number of cutting is 11. The ratio of the number of uncut strips is evaluated in %. For example, if there are 5 peels, it is expressed as 95/100.

(4. Pencil hardness)

According to JIS 5400, the test was performed 5 times, and the number of scratch-free pieces was counted to evaluate the pencil hardness. For example, when a pencil of 3H is used, as long as there are three scratches, it is 3/5 (3H).

As described above, the hard coating films of Examples 5 to 9 have a surface hardness (pencil hardness) of 4H or more and can satisfy A × 1500 < B, so that curling is less likely to occur. With such an effect, cracks and wrinkles are less likely to occur.

On the other hand, since the hard coat films of Comparative Examples 5 to 8 cannot satisfy the relationship of A × 1500 < B, cracks, wrinkles, curls, or surface hardness cannot be 4H or more, and thus cannot be used as the hard form of the present invention. The film is used.

As described above, according to the present invention (β), it is possible to provide a hard coating film which is a layer composition in which a hard coat layer is laminated on a resin film, and which not only has excellent surface hardness but also is less likely to be curled.

Meanwhile, since the hard coating film of the present invention (β) can satisfy the relationship of A×1500<B, even if a hard coating film is applied by Roll-to-Roll or a secondary processing process (for example, saponification treatment) is performed. At the same time, a hard coating film which is less likely to cause curling can be provided.

1. . . Hard coating

1a, 1b. . . Hard coating end face

10. . . Resin film

11a, 11b. . . End face of resin film

12a, 12b. . . Edge of resin film

20. . . Hard coating

21a, 21b‧‧‧ Hard coated end faces

22a, 22b‧‧‧ hard coated edges

30‧‧‧Water platform

40‧‧‧Cellotape (cellophane tape) (registered trademark)

Fig. 1 is a view showing a method of measuring the curl of the present invention (α).

Fig. 2 is a plan view showing a hard coat film of (β) of the present invention.

Fig. 3 is a cross-sectional view showing a hard coat film of the present invention (β).

Fig. 4 is a view showing a method of measuring the curl of the present invention (β), wherein (a) is a plan view and (b) is a partial enlarged view of a side view.

1. . . Hard coating

10. . . Resin film

11a, 11b. . . End face of resin film

20. . . Hard coating

21a, 21b. . . Hard coated end face

Claims (5)

A hard coating film comprising a hard coat layer of one layer laminated on a resin film, characterized in that the hard coat layer contains at least a radiation curable resin, and the radiation curable resin is composed of a polyfunctional acrylate and a plurality of a mixed system of functional urethane acrylate, the mixing ratio of the polyfunctional urethane acrylate to the polyfunctional acrylate is 0.2 to 0.7, and the thickness of the hard coating layer is A (mm) When the width (both edge width) of the edge of the resin film to the edge of the hard coat layer is B (mm), A × 1500 < B (where 0.007 mm ≦ A ≦ 0.020 mm). The hard coat film of the first aspect of the invention, wherein the resin film has an elastic modulus of from 2 GPa to 8 GPa. The hard coat film of claim 1, wherein the resin film has a thickness of 5 to 100 μm. The hard coat film of the first aspect of the invention, wherein the hard coat layer contains a radiation curable resin, and the radiation curable resin has a volume shrinkage ratio of 5 to 25%. An anti-foaming film which is provided with a surface uneven structure of the hard coat layer according to any one of claims 1 to 4.