KR101199641B1 - Optical laminate and hardcoat film - Google Patents

Abstract

assignment
The present invention provides an optical laminated body having excellent surface hardness while suppressing curl due to cracking and hardening shrinkage, and having good visibility of the screen, and which can be suitably used for LCD and PDP TV applications.
Solution
In an optical laminated body in which an optical functional layer is provided on one or both surfaces of a light transmitting substrate directly or through another layer, the optical functional layer has a thickness of 3 to 50 µm, contains a translucent resin and translucent fine particles, and the translucent resin It is formed by irradiating ionizing radiation with respect to the resin composition containing an ionizing radiation hardening-type polyfunctional acrylate and 5-50 weight% of ionizing radiation hardening-type fluorinated acrylate with respect to the total weight of the solid component in the said optical function layer. Optical laminates.

Description

Optical laminated body and hard coat film {OPTICAL LAMINATE AND HARDCOAT FILM}

The present invention (α) relates to an optical laminate provided on a display surface such as a liquid crystal display (LCD) or a plasma display (PDP), and in particular, to improve scratch resistance, chemical resistance, and visibility of a screen. It relates to an optical laminate.

The present invention (β) relates to a hard coat film, and more particularly to a hard coat film that can be suitably used for display surfaces such as liquid crystal displays (LCDs) and plasma displays (PDPs).

Although LCDs are one of various image display devices, applications using LCDs are changing from notebook PCs or monitors to TVs with technological innovations such as high viewing angle, high definition, high-speed response, and color reproducibility of LCDs. In the basic configuration of the LCD, a gap of a predetermined interval is set by a spacer between flat glass having two transparent electrodes, and a liquid crystal material is injected and encapsulated therein, so that the front and rear surfaces of the flat glass are The polarizing plate is affixed on it. Since the polarizing plate is easily damaged, conventionally, a cover plate made of glass or plastic is attached to the LCD surface to prevent damage to the polarizing plate attached to the LCD surface. However, attaching the cover plate is disadvantageous in terms of cost and weight, so that a polarizing plate having an optical functional layer treatment gradually applied to the surface thereof has been used. The hard coat treatment is usually performed by providing a hard coat film having a hard coat layer on a transparent plastic film base on the surface of the polarizing plate.

The optical functional layer is usually formed on a transparent plastic film by a thin coating film on the transparent plastic film using an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. However, if the thickness of the optical functional layer is not sufficient, the surface of the optical functional layer will be damaged by the underlying transparent plastic film base. In the case of LCD, triacetyl cellulose (TAC) film is mainly used as a transparent plastic film base, but in the above case, about 2 to 3H was generally used as a pencil hardness (JIS K5600), a representative measurement method for evaluating the scratch resistance of the hard coat surface. .

The spread of LCD and PDP TV market is remarkable, but general consumers of home TV are expected to treat these displays with strict handling (load due to physical, mechanical and chemical stimulus) as with conventional CRT TV. For example, wipe off dirt or fingerprints on the surface of the display with a rag that infiltrated with glass cleaners (surfactants, organic solvents, etc.), or rub or tap the surface with toys, etc. Etc. CRT's CRT is made of glass excellent in chemical resistance, and since the surface hardness is about 9H in pencil hardness, durability against such a load was sufficient. However, the surface of the hard coat film mounted on the display has a low pencil hardness, not enough chemical resistance, and improvement is required.

In addition, when a hard coat film is stuck to various image display apparatuses, the interference unevenness of the light which arises from the fall of contrast by the reflection of the light of a display surface, ie, the surface of a hard coat film, and the slight film thickness variation of a hard coat layer (details) It also had a problem that visibility is reduced by the following). Therefore, the hard coat film is also required to improve the visibility in addition to the surface hardness.

As a method of improving the surface hardness of the hard coat layer, a method of simply increasing the thickness of the hard coat layer is considered. However, although the hardness becomes hard by the said method, since wrinkles and curls become large by hardening shrinkage of a hard-coat layer, cracking and peeling of a hard-coat layer tend to occur, it was not usable practically. Thus, several methods have been proposed in recent years to realize high hardness of the hard coat film and to solve the problem of curl due to cracking and curing shrinkage of the hard coat layer (Patent Documents 1 to 4).

In patent document 1, the protective film for polarizing plates which formed the cured coating film layer (optical functional layer) which consists of a composition containing an ultraviolet curable polyol acrylate-type resin in at least one surface of a transparent plastic film base is proposed. As the ultraviolet curing polyol acrylate resin, dipentaerythritol hexaacrylate is mainly exemplified. When coating this resin on a plastic film base material, it is possible to ensure the hardness of 4H or more by pencil hardness by making thickness of a cured coating layer 10 micrometers or more, but it is difficult to simultaneously suppress curl by hardening shrinkage.

Patent Literature 2 provides a hard coat film having a hard coat layer having a thickness of 3 to 15 µm on a buffer layer provided with a buffer layer composed of one layer or a multilayer having a thickness of 3 to 50 µm on at least one surface of the transparent plastic film base. Is proposed. The pencil hardness of each of the transparent plastic film base, the buffer layer, and the optical functional layer has a value increased in this order, whereby the hard coat film is designed to have a pencil hardness of 4H to 8H as a whole. However, Patent Literature 2 requires a buffer layer in addition to the optical functional layer, and at least a two-layer structure is required, so that the production process is complicated and the production cost is high.

Patent Literature 3 provides a hardened optical functional layer containing inorganic or organic internal crosslinked ultrafine particles in at least one surface of a transparent plastic film or sheet base material, and thereafter, an inorganic or What provided the thin film of clear cured resin which does not contain organic internal crosslinked particle | grains is proposed. However, similarly to patent document 2, patent document 3 also has a drawback that the production process becomes complicated and the production cost becomes high by having a two-layer structure.

Patent Document 4 is a hard coat film having at least one hard coat layer formed on at least one surface of a transparent plastic film base, wherein the hard coat layer forming material contains 20 to 80 parts by weight of inorganic fine particles per 100 parts by weight of resin. Moreover, it is proposed that the thickness of the whole hard-coat layer is 10 micrometers-50 micrometers, and surface pencil hardness is 4H or more. However, a hard coat layer having a thickness of 10 μm or more on a transparent plastic film base by a hard coat layer-forming material containing inorganic fine particles in the above ratio with respect to a resin such as polyester acrylate or polyurethane acrylate used in Patent Document 4 When the layer is formed, it is difficult to balance securing of sufficient hardness and suppression of curl by curing shrinkage.

As a method of improving the visibility of a hard coat film, the hard coat film which has a hard coat layer containing a urethane acrylate, an isocyanuric acid acrylate, and inorganic translucent microparticles on a transparent plastic film base is proposed (patent document 5). This is a content of preventing the reflection of a hard coat film and the interference fringe of light by combining the difference of the refractive index of a transparent plastic base material and a hard-coat layer by inorganic light-transmitting microparticles | fine-particles. Certainly, the reflection of the hard coat film is reduced by adjusting the refractive index of the hard coat layer by the inorganic light-transmitting fine particles. However, due to insufficient compatibility and dispersibility of the hard coat layer constituent material, film formation is poor, and the thickness of the hard coat layer is poor. It was difficult to overcome the interference fringe because it was slightly scattered. Moreover, since the film forming property was bad, it was not said that workability was enough.

In order to improve the pencil hardness of the surface, the hard coat layer had to be thickened. However, when the hard coat layer was thickened, the adhesiveness between the hard coat layer and the transparent plastic film base deteriorated. This problem was one factor that the ionizing radiation curable resin cured and shrinked when the ionizing radiation curable resin, which is a constituent material of the hard coat layer, was cured to form a hard coat layer. As a countermeasure against said curl and wrinkles, the proposal which fills in a hard-coat layer with inorganic fine particles, such as a silica, is made (patent document 6). When using as a polarizing gas, saponification process must be performed beforehand at the time of polarizing plate. However, there has been a problem that silica is eluted in the saponification liquid by the saponification treatment, and the effect of silica is lost.

The hard coat film is provided on the surface of the case, the display surface, or the like, and the surface hardness can be improved to prevent damage to each structural member. The hard coat film has a hard coat layer laminated one or more layers on the resin film or has a separate layer between the resin film and the hard coat layer.

A hard coat film is formed by apply | coating an ionizing radiation curable resin, such as a thermosetting resin or an ultraviolet curable resin, and hardening | curing as a hard coat layer on a resin film. The hard coat layer has a thickness of about several micrometers, and the surface hardness of the hard coat layer is generally pencil hardness (JIS K5400) of about H to 3H.

In addition, from the viewpoint of effectively utilizing the resin film, it is common to form a hard coat layer by covering both one side or both sides of the resin film.

As a method of improving the surface hardness of a hard coat layer, the method of increasing the thickness of a hard coat layer is mentioned. However, in this method, although the surface hardness of the hard coat layer is improved, cracks and peeling of the hard coat layer are likely to occur, and troubles such as wrinkles and curls in the manufacturing process of the hard coat film or various secondary processing processes using the same are possible. Since this occurred, it was not practically usable. The above problems such as wrinkles and curls tend to occur as the surface hardness of the hard coat layer increases. The above problems, such as wrinkles and curls, are particularly problematic when used for optical applications. For example, when using a hard coat film as a protective film for polarizing plates, it is common to perform a saponification (acid alkali) treatment to the said hard coat film. The saponification process causes surface modification of the hard coat film to improve the coating property of the adhesive or the adhesive. Thereby, adhesiveness of a polarizing substrate and a hard-coat film improves through an adhesive agent and an adhesive. However, the saponification process had a problem that the hard coat film was easily cracked and curled due to cracking and curing shrinkage.

Moreover, productivity is improved by creating a hard coat film by Roll-to-Roll. However, in the case where the hard coat film is produced by Roll-to-Roll or when the secondary processing process (for example, saponification treatment) is performed, the hard coat film is wrinkled or curled due to cracking or curing shrinkage. This had a problem of becoming easy to happen.

For example, Patent Document 1 proposes a protective film for polarizing plates in which a cured coating film layer formed of a composition containing dipentaerythritol hexaacrylate and silica fine particles is formed on at least one surface of a transparent resin film. When coating the said resin on a transparent resin film base material, hardness whose pencil hardness is 4H or more can be ensured by making thickness of a cured coating layer into 10 micrometers or more. However, when the thickness of the cured coating layer was set to 10 µm or more, it was difficult to suppress the generation of curl due to curing shrinkage. The occurrence of this curl was more likely to occur by the saponification treatment.

Patent Literature 2 provides a hard coat film having a hard coat layer having a thickness of 3 to 15 μm on one side or a multilayer having a thickness of 3 to 50 μm on at least one surface of a plastic substrate film, and further forming a hard coat layer having a thickness of 3 to 15 μm on the buffer layer. Proposed. The pencil hardness of each of the transparent plastic film base, the buffer layer, and the hard coat layer has a value increased in this order, thereby designing the entire hard coat film to have a pencil hardness of 4H to 8H. However, in the invention disclosed in Patent Literature 2, a buffer layer is required in addition to the hard coat layer, and thus there is a drawback that a load is applied to the production process.

Japanese Patent Laid-Open No. 9-113728 Japanese Patent Laid-Open No. 11-300873 Japanese Patent Application Laid-Open No. 2000-52472 Japanese Patent Application Laid-Open No. 2000-112379 Japanese Patent Application Laid-Open No. 2006-106427 Japanese Patent Laid-Open No. 2003-248101

This invention ((alpha)) provides the optical laminated body which has the outstanding surface hardness, suppresses the curl by a crack and hardening shrinkage, and also has good visibility of the screen, and can be used suitably also for TV use of LCD or PDP. It aims to do it.

Conventionally, the optical laminated body which has high surface hardness, is hard to generate | occur | produce curl and wrinkles, and was excellent in chemical resistance (for example, alkali treatment in a saponification process) did not exist. Accordingly, the present invention (α) has an excellent scratch resistance, high surface hardness (pencil hardness), excellent chemical resistance, less curling, and an anti-fouling optical functional layer (for example, a hard coat layer). Another object is to provide an optical laminate having an antiglare layer. Moreover, also when a saponification process is given to an optical laminated body, it is an object to provide the optical laminated body which does not dissipate translucent microparticles | fine-particles (for example, silica) in a saponification liquid, and the effect of a translucent microparticle is not lost.

This invention ((beta)) aims at providing the hard-coat film which curl is hard to produce even when the pencil hardness of the said hard-coat layer is 4H or more in the laminated constitution which laminated | stacked one hard coat layer on the resin film.

Moreover, this invention ((beta)) uses the hard coat film which hardly produces a curl in the case of performing a process which manufactures a hard coat film by Roll-to-Roll, or the secondary processing process (for example, saponification process). It is also intended to provide.

This invention ((alpha)) is the following inventions (1)-(4).

The present invention (1) is an optical laminated body in which an optical functional layer is provided on one side or both sides of a translucent base directly or through another layer.

The optical functional layer is 3-50 μm in thickness,

It contains a light transmitting resin and light transmitting fine particles,

The light transmitting resin is formed by irradiating ionizing radiation to a resin composition containing 0.05 to 50% by weight of ionizing radiation curable fluorinated acrylate relative to the total weight of the ionizing radiation curable polyfunctional acrylate and the solid component in the optical functional layer. It is an optical laminated body characterized by the above-mentioned.

This invention (2) is the optical laminated body of the said invention (1) in which the fluorinated acrylate is unevenly distributed on the surface side rather than the said translucent base side of an optical function layer.

This invention (3) is the optical laminated body of said invention (1) or (2) which further has a polarizing gas.

This invention (4) is an anti-glare film characterized by including the surface asperity structure of the optical function layer as described in said invention (1) or (2).

This invention ((beta)) solved the said subject by the technical structure of following invention (5)-(9).

(5) A hard coat layer is laminated on a resin film, wherein the thickness of the hard coat layer is set to A (mm), and the width from the edge of the resin film to the edge of the hard coat layer (odor width ( When A) is set to B (mm), it is A * 1,500 <B (but 0.003 mm <= A <0.020mm), The hard-coat film characterized by the above-mentioned.

(6) The hard coat film as described in (5) characterized by the elasticity modulus of the said resin film being 2 GPa-8 GPa.

(7) The hard coat film as described in (5) characterized by the thickness of the said resin film being 5-100 micrometers.

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

(9) The antiglare film comprising the hard coat layer according to any one of the inventions (5) to (8) having a surface uneven structure.

In addition, in this specification, an "optical laminated body" and a "hard coat film" mean the same thing.

According to this invention (1), as a result of the resin composition of an optical function layer containing a polyfunctional acrylate and a fluorinated acrylate, surface hardness improves and it can provide activity to the surface of an optical function layer. Therefore, the scratch resistance is improved. Moreover, since the resin composition of an optical function layer contains fluorinated acrylate, the chemical resistance and antifouling property are improved by the water repellent effect of the said component. Moreover, when light-transmitting microparticles | fine-particles disperse | distribute among the molecules of a resin matrix, cured shrinkage | contraction of UV resins, such as a polyfunctional acrylate, can be reduced and curl can be prevented.

According to the present invention (2), since the fluorinated acrylate is unevenly distributed on the surface side, the fluorinated acrylate component is easily exposed to the surface, and the chemical resistance and antifouling property due to the improvement of scratch resistance and the water repellent effect accompanied by the improvement of the surface activity The effect of the improvement of becomes more remarkable. Moreover, since the material which has a fluorine is generally expensive, it is economically advantageous from being able to reduce the addition amount of the material which has a fluorine by ubiquitous on the surface of an optical function layer.

According to the present invention (3), even if the saponification treatment which is essentially performed in the installation of the polarizing gas is performed, it is almost impossible for the light-transmitting fine particles (for example, silica) to be dispersed in the saponification treatment liquid. Since no curling effect lasts.

According to the present invention (β), the hard coat film of the present invention has a thickness A (mm) and a thickness of the hard coat layer in comparison with the conventional hard coat film in which the hard coat layer is formed by covering both one side or both sides of the resin film. Since the relation of the width B (mm) from the edge of the resin film to the edge of the hard coat layer was set to A x 1,500 <B (where 0.003 mm? A? 0.020 mm), the hard coat layer was formed on the resin film by 1 In the layer structure laminated | stacked, even if the pencil hardness of the said hard-coat layer is 4H or more, the hard-coat film which curl is hard to produce can be provided.

Moreover, this invention ((beta)) hard-film which hardly produces curl also in the case of performing the process of manufacturing a hard-coat film by Roll-to-Roll, or the secondary processing process (for example, saponification process). Can be provided.

According to this invention (6), (7), the hard-coat film which is hard to produce the wrinkle by a crack and hardening shrinkage can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the measuring method of the curl which concerns on this invention ((alpha)).
2 is a plan view of the hard coat film of the present invention (β).
3 is a cross-sectional view of the hard coat film of the present invention (β).
It is a figure which shows the measuring method of the curl which concerns on this invention ((beta)), and is a partial enlarged view of (a) top view and (b) side view.

Hereinafter, the optical laminated body which concerns on this invention ((alpha)) is demonstrated.

The optical laminated body which concerns on this preferable aspect has a basic structure by which the optical function layer was laminated | stacked on the translucent base. Moreover, it is preferable that the optical function layer which concerns on this preferable aspect is located in the outermost surface of an optical laminated body, and is used as a hard-coat layer or as a low refractive index layer. Here, the optical function layer may be laminated on one surface of the light-transmissive substrate or may be laminated on both surfaces. Furthermore, the said optical laminated body may have another layer. Here, as another layer, for example, a polarizing gas, a hard coat layer (e.g., provided when the optical function layer is used as the low refractive index layer), another function imparting layer (e.g., antistatic layer, near infrared ray (NIR) ), An absorbing layer, a neon cut layer, an electromagnetic shielding layer, and an optical function layer). The position of the other layer is, for example, in the case of a polarizing substrate, above the light-transmissive substrate on the opposite side to the optical functional layer, and in the case of another functional provision layer, the lower layer of the optical functional layer. Moreover, you may make the said optical function layer function as a low reflection layer. Hereinafter, each component (translucent base, optical function layer, etc.) of the optical laminated body which concerns on this preferable aspect is explained in full detail.

First, the light-transmissive gas according to the present preferred embodiment is not particularly limited as long as it is light-transmissive, and glass such as quartz glass or soda glass can also be used, but polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polyethylene naphthalate (PEN) can be used. ), Polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin Various resin films, such as a copolymer (COC), a norbornene-containing resin, a polyether sulfone, a cellophane, and an aromatic polyamide, can be used preferably. These films can also be unstretched or those which have been subjected to stretching. In particular, a biaxially stretched polyethylene terephthalate film is preferable in terms of excellent mechanical strength and dimensional stability, and unstretched triacetyl cellulose (TAC) is preferable in that the phase difference in the film plane is very small. Moreover, when using for PDP and LCD, these PET and TAC films are more preferable.

The higher the transparency of these light-transmissive substrates, the better. However, the total light transmittance (JIS K7105) is preferably 80% or more, more preferably 90% or more. The thickness of the light-transmissive substrate is preferably thin in terms of weight reduction, but considering its productivity and handleability, it is preferably in the range of 1 to 700 µm, preferably 20 to 250 µm. When using the optical laminated body of this invention for LCD uses, it is preferable to use TAC of 20-80 micrometers as a translucent base. In the optical laminated body of this invention, since curling can be prevented especially when 20-80 micrometers TAC is used as a translucent base, it can be used suitably for the LCD use which requires thin weight reduction.

The light-transmissive substrate is subjected to surface treatment such as alkali treatment, corona treatment, plasma treatment, sputter treatment, saponification treatment, coating with surfactant, silane coupling agent or the like, or surface modification treatment such as Si deposition. The adhesion between the base and the optical functional layer can be improved. Since the adhesiveness of a translucent base and an optical functional layer improves by performing such a process, the scratch resistance, surface hardness, and chemical-resistance in the said optical functional layer improve.

Next, the optical function layer which concerns on this preferable aspect is explained in full detail. The translucent resin contained in the optical function layer which concerns on this preferable aspect is formed by irradiating ionizing radiation with respect to the resin composition containing an ionizing radiation hardening type polyfunctional acrylate and an ionizing radiation hardening type fluorinated acrylate. 20-80 weight% is preferable with respect to the total weight of the solid component in an optical function layer, and, as for the compounding quantity of an ionizing radiation hardening type polyfunctional acrylate, 30-60 weight% is more preferable. As for the compounding quantity of an ionizing radiation curable fluorinated acrylate, 0.05-50 weight% is contained essentially with respect to the total weight of the solid component in an optical function layer, 0.2-50 weight% is preferable, 5-50 weight% is more preferable, 10-40 weight% is more preferable. When the compounding quantity of an ionizing radiation hardening type polyfunctional acrylate is less than 20 weight%, the crosslinking density of an optical functional layer falls, and pencil hardness worsens. Moreover, when more than 80 weight%, curling becomes easy to generate | occur | produce. When the amount of the ionizing radiation curable fluorinated acrylate is less than 0.05% by weight, the water repellent effect and activity decrease, and the scratch resistance, antifouling property and chemical resistance deteriorate.

Here, it is preferable that the fluorinated acrylate is ubiquitous on the surface side rather than the translucent base side. By having the said structure, the effects of scratch resistance, chemical resistance, and antifouling property become more remarkable. In particular, the fluorinated acrylate is more preferably present gradually from the light transmissive base side of the optical functional layer to the surface side. In the present specification and the claims, the fluorinated acrylate-derived component (component in which the fluorinated acrylate is cured by ionizing radiation) and the polyfunctional acrylate-derived component (polyfunctional acrylate are cured by ionizing radiation) in the optical functional layer. One component) is simply referred to as "fluorinated acrylate" and "polyfunctional acrylate". In the present invention, the fact that the fluorinated acrylate is unevenly distributed on the surface side of the light transmissive gas side means that the proportion of fluorine elements present in the range from the surface of the optical functional layer containing fluorinated acrylate to 5 nm in depth is 10% or more. It is preferable that the said fluorine element ratio is 20% or more. Although an upper limit is not specifically limited, For example, it is 80% or less. A fluorine element ratio is measured by X-ray photoelectron spectroscopy ("Electron Spectroscopy for Chemical Analysis", hereinafter referred to as "ESCA"). In ESCA, the abundance ratio of fluorine is calculated from peak areas of fluorine, carbon, oxygen, and silicon obtained at a depth of 5 nm.

Moreover, when ESCA measures the range from the optical functional layer surface to 200 nm in depth at 5 nm intervals, it exists every 5 nm of depth obtained by measuring at 5 nm intervals from the said optical functional layer surface to 5 nm in depth. The value obtained by dividing the fluorine element ratio by the average value of the fluorine element ratio present from the depth of 5 nm to the depth of 200 nm on the surface of the optical functional layer is preferably 10 or more, more preferably 20 or more. Although an upper limit is not specifically limited, For example, it is 1,000 or less. Since the fluorine atom can be efficiently existed on the surface of an optical functional layer by setting this value to 10 or more, even if expensive fluorine material is used, the optical laminated body excellent in economic efficiency can be provided.

The polyfunctional acrylate is not particularly limited as long as the number of (meth) acryloyloxy groups in one molecule is two or more, and for example, EO adduct di (meth) acrylate of bisphenol A and ethylene glycol di (Meth) acrylate, polyethyleneglycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate hexanemethylene diisocyanate urethane polymer, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol tri (meth) acrylate toluene diisocyanate urethane prepolymer, pentaerythritol tri (meth) acrylate Isophorone diisocyanate urethane prepolymer, dipentaerythritol hexaacrylate, etc. can be used. These monomers can be used 1 type or in mixture of 2 or more types. Trifunctional or more than trifunctional acrylate is preferable, and tetrafunctional or more is more preferable.

Although it does not specifically limit as fluorinated acrylate, For example, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro -7-methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-9-methyldecyl) ethyl methacrylate, 3- (perfluoro-8-methyldecyl) -2-hydroxy Propylmethacrylate, 3-perfluorooctyl-2-hydroxypropylacrylate, 2- (perfluorodecyl) ethylacrylate, 2- (perfluoro-9-methyldecyl) ethylacrylate, pentadeca Fluorooctyl (meth) acrylate, undecafluorohexyl (meth) acrylate, nonafluoropentyl (meth) acrylate, heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, Pentafluoropropyl (meth) acrylate, trifluoro (meth) acrylate, triisofluoro Isopropyl (meth) acrylate, can be used (meth) acrylate, the following compounds (ⅰ) ~ (ⅹⅹⅹ) such as trifluoromethyl. In addition, the following compounds show the case where all are acrylates, and all the acryloyl groups in a formula can be changed into a methacryloyl group.

The compounds (i) to (iii) describe only those which are hydrogen atoms as R in the following general formula (1), and one of the hydrogen atoms in the methylene group bonded to carbonyl carbon can be changed to a methyl group.

These can also be used individually or in mixture of multiple types. Among the above-mentioned fluorinated acrylates, polyfunctional fluorinated acrylates are preferable. In addition, the polyfunctional fluorinated acrylate here means having two or more (preferably three or more, more preferably four or more) (meth) acryloyloxy groups.

It is preferable that the translucent resin which concerns on this preferable aspect contains at least 1 type of (epsilon) -caprolactone modified isocyanurate which consists of an arbitrary component by the following formula. Since the segment part of the said epsilon caprolactone has good affinity with the resin to mix, an inorganic pigment, and the additive, for example, in the coating manufacturing process of an optical function layer, in production efficiency and a film-forming process, It contributes to film-forming stability (reduction of film thickness imbalance). In addition, flexibility is generated in the entire optical functional layer, and is effective in relieving internal stress and the like (curl suppression).

Although thermosetting resins and radiation curable resins can be used in addition to the isocyanurate of ε-caprolactone modified to the optical functional layer, a system using a radiation curable resin capable of curing the optical functional layer with radiation can be used for production efficiency, It is advantageous in terms of energy cost and the like. Examples of the radiation curable resins include radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group and methacryloyloxy group, and cationically polymerizable functional groups such as epoxy group, vinyl ether group and oxetane group. The composition which used the monomer, oligomer, and prepolymer individually or mixed suitably is used. Examples of the monomer include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate and the like. As oligomers and prepolymers, polyester acrylates, polyurethane acrylates, phenylene glycidyl ether hexamethylene diisocyanate urethane prepolymers, phenyl glycidyl ether triene diisocyanate urethane prepolymers, epoxy acrylates, polyether acrylates , Acrylate compounds such as alkyd acrylate, melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, bisphenol A Epoxy compounds such as diglycidyl ether and various alicyclic epoxy compounds, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl } Oxetane compounds, such as a benzene and di [1-ethyl (3-oxetanyl)] methyl ether, are mentioned.

Although the compounding quantity of the epsilon caprolactone modified isocyanurate is not specifically limited, The range of 5-50% is preferable at the total solid content ratio of the structural material which forms an optical function layer, and the range of 10-30% is more preferable. Do. When the compounding quantity of the isocyanurate of (epsilon) -caprolactone modified | denatured is small, the adhesiveness of a translucent base and an optical function layer will fall or a curl will become strong. Moreover, film-forming property deteriorates, interference spots (interference spots by subtle thickness spots of an optical function layer) generate | occur | produce, and visibility is worse. In addition, the optical functional layer may be thickened, and wrinkles or cracks may occur in the optical functional layer. On the other hand, when there is too much compounding quantity, the scratch resistance of an optical function layer falls.

As radiation which hardens the system using said radiation curable resin, any of an ultraviolet-ray, a visible ray, an infrared ray, and an electron beam may be sufficient. Moreover, these radiations may be polarized or unpolarized light. In particular, ultraviolet rays are preferable from the viewpoint of equipment cost, safety, operation cost and the like. As an energy source of an ultraviolet-ray, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, etc. are preferable, for example. The irradiation dose of the energy source is preferably in the range of 100 to 5,000 mJ / cm 2, and more preferably 300 to 3,000 mJ / cm 2, in terms of integrated exposure at an ultraviolet wavelength of 365 nm. When it is less than 100 mJ / cm <2>, since hardening becomes inadequate, the hardness of an optical functional layer may fall. Moreover, when it exceeds 5,000 mJ / cm <2>, an optical function layer will color and transparency will fall. In the case of performing curing by ultraviolet irradiation, the addition of a photopolymerization initiator is required. As a photoinitiator, a conventionally well-known thing can be used. For example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4'-diaminobenzophenone, benzylmethyl ketal Phosphorus and its alkyl ethers; Acetophenes such as acetophenone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl ketone Rice field; Anthraquinones such as methyl anthraquinone, 2-ethyl anthraquinone and 2-amyl anthraquinone; Xanthones; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone and 2,4-diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; In addition, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one etc. can be illustrated. These can be used individually or in mixture of 2 or more types. As for the usage-amount of a photoinitiator, about 5% or less in total solid content ratio with respect to a radiation curable resin composition, Furthermore, 1 to 4% is preferable.

A polymer resin can be added and used to the system of the said radiation curable resin composition in the range which does not prevent the polymerization hardening. This polymer resin is a thermoplastic resin soluble in the organic solvent used for the optical function layer paint mentioned later, and an acrylic resin, an alkyd resin, a polyester resin, a cellulose derivative etc. are mentioned specifically, In these resin, a carboxyl group, a phosphate group, It is preferable to have acidic functional groups, such as a sulfonic acid group.

Moreover, additives, such as a leveling agent, a thickener, an antistatic agent, a filler, a extender pigment, can be used. The leveling agent has a function of correcting defects prior to coating film formation by promoting uniformity of the surface of the coating film, and a material having both lower interfacial tension and surface tension than the radiation curable resin composition is used.

Although the optical function layer is mainly comprised by hardened | cured material, such as the resin composition mentioned above, the formation method coats the coating material which consists of a resin composition and an organic solvent, and after evaporating an organic solvent, radiation (for example, electron beam or ultraviolet irradiation) Or hardening by heat. As the organic solvent used here, it is necessary to select a suitable one for dissolving the resin composition. Specifically, single or mixed solvents selected from alcohols, esters, ketones, ethers, and aromatic hydrocarbons can be used in consideration of coating aptitudes such as wettability, viscosity, and drying rate for the light-transmissive gas.

The thickness of the optical functional layer needs to be in the range of 3 to 50 µm, more preferably in the range of 5 to 30 µm, still more preferably in the range of 7 to 20 µm. When the optical functional layer is thinner than 3 mu m, it is not preferable because the scratch resistance deteriorates and the interference spots appear remarkably. When it is thicker than 50 µm, curling occurs due to curing shrinkage of the optical functional layer, microcracks occur on the surface of the optical functional layer, adhesiveness with the light-transmissive substrate is lowered, or light transmittance is lowered. And it may become a cause of the cost increase by the increase of the required coating amount accompanying an increase of a film thickness.

As light-transmitting microparticles | fine-particles contained in an optical function layer, organic substance which consists of an acrylic resin, a polystyrene resin, a styrene-acryl copolymer, a polyethylene resin, an epoxy resin, a silicone resin, polyvinylidene fluoride, a polyfluoroethylene resin etc., for example is used. Light-transmitting fine particles or inorganic light-transmitting fine particles (inorganic ultrafine particles) such as titanium oxide, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, zirconium oxide, calcium oxide, indium oxide, antimony oxide, or a combination thereof can be used. have. Moreover, these microparticles may be used individually by 1 type, and may use 2 or more types together. It is preferable to use crosslinked organic light transmitting fine particles and inorganic light transmitting fine particles as the light transmitting fine particles. Thereby, the pencil hardness of the hard coat film after hardening can be improved and curl can be prevented. In addition, the use of silica as the light-transmitting fine particles is preferable because the refractive index of the optical functional layer is reduced to reduce interference spots that affect the image quality of the display. In addition, when silica is treated with a silicate-based material (for example, a silane coupling agent such as an alkoxysilane having functional groups such as vinyl group, methacryl group, amino group, epoxy group, etc.), elution of silica during saponification can be prevented. have. 1-100 nm is preferable and, as for the particle diameter of a translucent microparticle, 10-50 nm is more preferable. If the particle diameter is smaller than 1 nm, the chemical resistance is lowered or the production cost of the particles is increased. When larger than 100 nm, an influence arises on the optical characteristic that a transmittance | permeability falls, haze rises, or contrast falls. "Particle diameter" points out the average value of the diameter of 100 particle | grains measured with the electron microscope. Moreover, the fine powder and coarse powder mixed in the manufacturing process of the said microparticles | fine-particles in all the numbers are less than 5% (more preferably, less than 1%). 5-70 weight% is preferable and, as for the compounding quantity of a light-transmitting microparticle, 10-50 weight% is more preferable. When the amount is less than 5% by weight, the curl prevention effect and pencil hardness are lowered. If the blending amount is more than 70% by weight, scratch resistance is poor. The light-transmitting fine particles are preferably solized and used, and coating is easily performed, and the dispersibility of the light-transmitting fine particles in the coating is improved. As the light-transmitting fine particles solvated, for example, alumina sol, silica sol and the like can be used. The formation method of a sol is mentioned later.

Moreover, since the translucent microparticles | fine-particles which have an average particle diameter of 0.3-10 micrometers are made to contain in an optical function layer, and an uneven structure is formed in the optical function layer surface, since it can use as an anti-glare layer, it is preferable. This can be used as an antiglare 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, and when the refractive index is less than 1.40 or larger than 1.75, the difference in refractive index with the light-transmissive substrate or the resin matrix becomes too large, and the total light transmittance is lowered. . Moreover, as for the difference of the refractive index of a translucent microparticle and a resin component, 0.2 or less are preferable. It is preferable that it is the range of 0.3-10 micrometers, and, as for the average particle diameter of translucent microparticles | fine-particles, 1-8 micrometers is more preferable. If the particle size is smaller than 0.3 mu m, the anti-glare property is lowered. If the particle diameter is larger than 10 mu m, it is not preferable because the glare occurs and the degree of the surface irregularities becomes too large and the surface becomes cloudy. Although the ratio of the translucent microparticles contained in the said resin is not specifically limited, It is preferable to set it as 1-20 weight part with respect to 100 weight part of resin compositions, in order to satisfy characteristics, such as an anti-glare function and glare, and the fine unevenness | corrugation of the surface of an optical function layer is It is easy to adjust shape and haze value. Here, "refractive index" points out the measured value according to JISK-7142. In addition, an "average particle diameter" points out the average value of the diameter of 100 particle | grains measured with the electron microscope.

That is, the optical laminated body which improved pencil hardness, prevented curl, and provided anti-glare property by setting it as the optical functional layer (antiglare layer) containing the translucent microparticles | fine-particles whose particle diameters are 1-100 nm, and the translucent microparticles | fine-particles whose particle diameters are 0.3-10 micrometers (Anti-glare film) can be provided.

In the optical laminated body of this invention, it is preferable that the difference (refractive index of a translucent base-refractive index of an optical functional layer) of the refractive index of a translucent base and an optical functional layer is 0.10 or less, and the refractive index of an optical functional layer is It is more preferable that it is below the refractive index of a translucent base. By controlling the refractive index difference to be within the above range, the reflection of light on the surface can be suppressed low.

The said refractive index can be controlled by containing an inorganic translucent fine particle in an optical function layer suitably. Inorganic translucent microparticles | fine-particles have a function which adjusts the refractive index of the external appearance of an optical function layer according to the compounding quantity. It is preferable that the refractive index of the translucent substrate and the refractive index of the optical functional layer are approximated as described above. For this reason, in preparation of an optical functional layer formation material, it is preferable to adjust suitably the compounding quantity of an inorganic light-transmitting microparticle so that the difference of the refractive index of the said translucent base and the refractive index of an optical functional layer may become small. When the difference in refractive index is large, a phenomenon called interference spots in which reflected light of external light incident on the optical laminate is iridescent color occurs, resulting in deterioration of display quality. In particular, in offices where an image display device having an optical stack is used, the number of fluorescent lamps having three wavelengths has increased very much. Although the three-wavelength fluorescent lamp has a characteristic of strong emission intensity at a specific wavelength and clearly visible objects, it is known that interference spots are more remarkable under this three-wavelength fluorescent lamp.

In this invention, you may laminate | stack a polarizing base on the translucent base of the surface opposite to an optical function layer. Here, the said polarizing gas can use the light absorption type polarizing film which transmits only specific polarization and absorbs other light, and the light reflection type polarizing film which transmits only specific polarization and reflects other light can be used. As a light absorption type polarizing film, the film obtained by extending | stretching polyvinyl alcohol, polyvinylene, etc. can be used, For example, the polyvinyl obtained by uniaxially stretching the polyvinyl alcohol which adsorbed oxo or dye as a dichroic element. Vinyl alcohol (PVA) film is mentioned. As a light reflection type polarizing film, when extending | stretching, for example, the structure which laminated | stacked and extended | stretched several types of polyester resins (PEN and PEN copolymer) from which the refractive index of an extending | stretching direction differs by extrusion molding technique, and extended | stretched several hundred layers. DBEF manufactured by 3M Corporation, a cholesteric liquid crystal polymer layer and a quarter wave plate are laminated, and two circularly polarized light in which light incident from the cholesteric liquid crystal polymer layer side is reversed from each other Nitto Corporation and Merck, manufactured by Nitto Electric Engineering Co., Ltd., are configured to separate light into a polarized light, reflect one side and reflect the other, and convert the circularly polarized light transmitted through the cholesteric liquid crystal polymer layer into linearly polarized light by a quarter wave plate. "Transmax", etc. are made.

The translucent base may be provided with an antistatic layer in order to prevent contamination such as dust that adheres electrostatically to the display surface. However, the antistatic layer is disposed at the outermost surface. The antistatic layer is formed by thinly depositing a metal oxide film such as aluminum or tin, or a metal oxide film such as ITO by sputtering or the like, or by applying antimony to metal fine particles such as aluminum or tin, or metal oxide such as whisker or tin oxide. Fillers of doped fine particles, whiskers, and charge transfer complexes formed between 7,7,8,8-tetracyanoquinomethane and an electron donor (donor) such as metal ions or organic cations It may be provided by a method of dispersing in a polyester resin, an acrylic resin, an epoxy resin or the like and installing it by solvent coating or the like, or a method in which polypyrrole or polyaniline is doped with camphorsulfonic acid or the like by solvent coating or the like. The transmittance of the antistatic layer is preferably 80% or more for optical applications.

Moreover, in order to improve contrast, it is possible to use an optical function layer as a low reflection layer. In this case, it is preferable to further provide a hard coat layer having a thickness of 3 to 50 m in the lower layer. In that case, it is preferable to improve the wettability of the surface of the hard coat layer. By increasing the wettability, the affinity between the hard coat layer and the optical functional layer can be improved, and the adhesion between the layers can be improved. By performing a corona treatment, a plasma treatment, etc. on the hard-coat layer surface, wettability can be improved. As 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. It is preferable that it is 80 degrees or less, and, as for the said contact angle, it is more preferable that it is 65 degrees or less. In this case, it is necessary that the refractive index of the low reflection layer is lower than the refractive index of the lower layer, and preferably 1.45 or less. As a material having such a characteristic, in addition to the above-mentioned fluorinated acrylate, for example, LiF (refractive index n = 1.4), MgF ₂ (n = 1.4), 3NaF-AlF ₃ (n = 1.4), AlF Inorganic low-reflective material in which inorganic materials such as ₃ (n = 1.4) and Na ₃ AlF ₆ (n = 1.33) are granulated and contained in acrylic resins or epoxy resins, silicon-based organic compounds, thermoplastic resins, thermosetting resins, It can be combined with organic low reflection materials, such as radiation curable resin. The low reflection layer preferably has a critical surface tension of 20 dyne / cm or less, more preferably 18 dyne / cm or less, and even more preferably 15 dyne / cm or less. If the critical surface tension is greater than 20 dyne / cm, it becomes difficult to erase the contamination attached to the low reflection layer.

Moreover, the low reflection material which mixed the sol which disperse | distributed the ultrafine silica particle of 5-30 nm in water or the organic solvent, and the fluorine-type film forming agent can also be used. Sols obtained by dispersing ultrafine silica particles of 5 to 30 nm in water or an organic solvent may be de-alkali alkali metal ions in an alkali silicate salt by ion exchange, or neutralized alkali silicate salt in a mine. Known silica sol and alkoxy silane obtained by condensation of known active silicic acid in the organic solvent in the presence of a basic catalyst hydrolysis and condensation, known silica sol, and furthermore, the water in the aqueous silica sol is distilled or the like into the organic solvent. Organic solvent-based silica sol (organosilica sol) obtained by substitution is used. These silica sol can be used either in an aqueous system or an organic solvent system. In the preparation of the organic solvent-based silica sol, it is not necessary to completely substitute water with the organic solvent. The silica sol contains a solid content of 0.5 to 50% by weight as SiO ₂ . As the structure of the ultrafine silica particles in the silica sol, various ones such as spherical shape, needle shape, and plate shape can be used.

The thickness for showing the low reflection layer having a good antireflection function can be calculated by a known calculation formula. In the case where incident light enters the low reflection layer perpendicularly, it is considered that the condition for transmitting the low reflection layer without reflecting the light and transmitting 100% may satisfy the following relational expression. In the formula, N _O represents the refractive index of the low reflection layer, N _S represents the refractive index of the lower layer, h represents the thickness of the low reflection layer, and λ _O represents the wavelength of light.

According to Equation (1), in order to prevent the reflection of light by 100%, it is understood that the material may be selected so that the refractive index of the low reflection layer is the square root of the refractive flow of the lower layer. In practice, however, it is difficult to find a material that completely satisfies this formula, and the material is selected as close as possible. In the above formula (2), the optimum thickness as the antireflection film of the low reflection layer is calculated from the refractive index of the low reflection layer selected from the expression (1) and the wavelength of light. For example, if the refractive index of the lower layer and the low reflection layer is 1.50, 1.38, and the wavelength of the light is 550 nm (a standard of visibility), and these values are substituted in the above formula (2), the thickness of the low reflection layer is It is calculated that the optical film thickness of about 0.1 mu m and preferably a range of 0.1 ± 0.01 mu m is optimal.

The manufacturing method of the optical laminated body of this invention is performed by coating the radiation curable resin coating containing polyfunctional acrylate, fluorinated acrylate, and translucent microparticles | fine-particles on a translucent base, drying, and then radiation-curing and creating it, for example. . Since fluorine material is expensive, it is preferable to localize on the surface of an optical function layer. Especially in this invention, a drying process is important. In a drying process, it is preferable to perform drying loosely at low temperature. By carrying out drying slowly, the fluorinated acrylate is collected on the surface of the optical functional layer, and by radiation curing, the optical functional layer in which the fluorinated acrylate is unevenly distributed on the surface side can be obtained. Here, 50-130 degreeC is preferable and 60-100 degreeC of drying temperature is more preferable. 1 to 10 minutes are preferable and, as for drying time, 2 to 5 minutes are more preferable. Moreover, it is preferable to set a preliminary drying process, after entering a drying process from immediately after coating a radiation curable resin coating and forming a coating film. Thereby, since drying of a coating film can be performed more relaxed, fluorinated acrylate is easy to be localized on the surface side of an optical function layer. The preliminary drying step refers to a step of uniformly blowing out the weak air flow with respect to the coating film from the direction perpendicular to the coating film plane. It is preferable that the air volume of the weak airflow is 0.01-1.0 m / sec. What is necessary is just to measure the said air volume in the state which made the wind speed detection hole of the anemometer (KANOMAX CLIMOMASTER (trademark)) 1 cm away from a coating film. Moreover, what is necessary is just to set the temperature of airflow in a predrying process to 20-60 degreeC.

As a method of coating the coating on the light-transmissive substrate, a conventional coating method or a printing method is applied. Specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calender coating, dam coating, dip coating, Coating such as die coating, intaglio printing such as gravure printing, printing such as stencil printing such as screen printing, and the like can be used.

EMBODIMENT OF THE INVENTION Hereinafter, after this invention ((beta)) is demonstrated using drawing, the material and manufacturing method which comprise this invention are demonstrated one by one.

FIG. 2: is a top view which shows the hard coat film 1 by which one hard coat layer 20 is laminated | stacked on the resin film 10. As shown in FIG. As shown in FIG. 2, although the hard-coat layer 20 can be laminated | stacked from the end surface 11a to the end surface 11b of the resin film 10, it is not limited to this. That is, the hard coat layer 20 should just be laminated | stacked on the resin film 10, and the end surface 21a, 21b of the hard coat layer 20 and the end surface 11a, 11b of the resin film 10 may correspond. There is no need.

3 is a cross-sectional view of the hard coat film 1 cut along the straight line L of FIG. 2. In FIG. 3, the thickness of the hard coat layer 20 is A, and the length (odor width) from the edge portion 12a of the resin film 10 to the edge portion 22a of the hard coat layer 20 is B. FIG. And the length from the edge part 12b of the resin film 10 to the edge part 22b of the hard coat layer 20 is set to B '. The length of B and B 'may be the same, and they may have different length, respectively.

The hard coat film of this invention needs to be Ax1,500 <B. By setting it as A * 1,500 <B, the curl of the hard coat film 1 can be suppressed. For example, in the case where the thickness of the hard coat layer is 0.003 mm, which is the lower limit of the present invention, the above relation is 4.5 <B. In addition, when the thickness of the hard coat layer is 0.020 mm, which is the upper limit of the present invention, the above relational expression is 30 < B. Here, in the relational expression, the upper limit value of B is not particularly limited, but is, for example, 100, preferably 50. If the value exceeds the lower limit of B, it is possible to provide a hard coat film in which cracks, wrinkles, and curls are less likely to occur at all values. From the viewpoint of effectively utilizing the resin film, it is preferable that the off-odor width B is close to the lower limit of the B in the relational formula of A × 1,500 <B.

When A x 1500, B, curling tends to occur when the pencil hardness (JIS K5400) of the hard coat layer constituting the hard coat film is 4H or more, and thus it cannot be used as the hard coat film of the present invention. In addition, in the said relational formula, as for B value, the smaller one of the B value and B 'value shown in FIG. 3 is applied.

Next, the material which comprises this invention ((beta)) is demonstrated.

<Resin film>

The material of the resin film constituting the present invention is not particularly limited.

When using the hard coat film of this invention for optical uses, such as LCD and a PDP, the higher the transparency, the better. Specifically, the total light transmittance (JIS K7105) of the resin film is 80% or more, more preferably 90% or more.

As a resin film which can be used suitably for optical use, Specifically, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC) , Polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene resin, polyether sulfone, cellophane And various resin films such as aromatic polyamide can be preferably used. These films can be either undrawn or stretched. In particular, a biaxially stretched PET film is preferable in terms of excellent mechanical strength and dimensional stability, and a film made of an unstretched TAC film and a norbornene resin is preferable in that the in-plane retardation is very small. Moreover, when using for optical uses, such as a PDP and LCD, these PET films, TAC film, and a norbornene resin film are more preferable.

It is preferable that the elasticity modulus of a resin film is 2 GPa-8 GPa, More preferably, it is 3 GPa-7 GPa.

By using a resin film having an elastic modulus within the above range as a constituent material of the hard coat film, problems such as light leakage and a decrease in polarization degree even when the hard coat film is processed to a polarizing plate and used in a liquid crystal display device even in a high humidity and low humidity environment. It is preferable because is less likely to occur.

When the elasticity modulus of a resin film is less than 2 GPa, when a coating material for hard-coat layer formation is applied by Roll to Roll, there exists a possibility that a resin film may be cut off.

In addition, the elasticity modulus in this invention means the value measured based on JISP8113. Specifically, it can measure and obtain | require by tensioning a resin film at a speed | rate of 1 mm / min using a tensile tester (product name: RTG1210 by A & D company).

It is preferable that it is 5-100 micrometers, It is more preferable that it is 20-100 micrometers, It is especially preferable that it is 40-80 micrometers from the viewpoint of the weight reduction and thinning of a display, or the product suitability of the said hard coat film. .

By setting the thickness of the resin film in the above range, since the resin film can absorb or relieve the shrinkage stress generated when the hard coat layer is cured, wrinkles and curls of the hard coat film can be suppressed. When the thickness of the resin film is less than 5 µm, shrinkage stress caused when curing the hard coat layer becomes difficult to be suppressed, so that shrinkage occurs in the hard coat layer, wrinkles and curls occur in the hard coat film, Productivity worsens. When the thickness of a resin film exceeds 100 micrometers, wrinkles and curls of a hard coat film can be suppressed, but since weight reduction and thinning become difficult, it is unpreferable. In particular, when using the hard coat film of this invention for an optical use, it is not preferable that the thickness of a resin film exceeds 100 micrometers.

The resin film can be subjected to surface treatment such as alkali treatment, corona treatment, plasma treatment, sputter treatment, saponification treatment, coating with a surfactant or silane coupling agent, or surface modification treatment such as Si deposition. Thereby, adhesiveness of a resin film and a hard-coat layer can be improved.

<Hard coat layer>

The hard coat layer which comprises this invention can use what mixed thermosetting resin, radiation curable resin, or thermosetting resin and radiation curable resin. It is preferable that the volume shrinkage rate of thermosetting resin or radiation curable resin is 5 to 25%. Preferably it is 7-15%.

If it is less than 5%, the scratch resistance of the hard coat layer may be reduced.

If it exceeds 25%, since the shrinkage of the hard coat layer is likely to occur, curling of the hard coat film is likely to occur, which is not preferable.

In this invention, it is preferable to use the radiation hardening type resin which can harden a hard coat layer by radiation as a hard coat layer. Thereby, there exists an advantage that a production efficiency raises and energy cost decreases. Examples of the radiation curable resin include monomers having radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group and methacryloyloxy group, and cationically polymerizable functional groups such as epoxy group, vinyl ether group and oxetane group. The composition which mixed an oligomer and a prepolymer individually or appropriately is used. Examples of the monomer include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, etc. are mentioned. As oligomers and prepolymers, polyester acrylates, polyurethane acrylates, phenylene glycidyl ether hexamethylene diisocyanate urethane prepolymers, phenyl glycidyl ether triene diisocyanate urethane prepolymers, pentaerythritol triacrylate hexamethylene Polyisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, such as polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, alkyd Acrylate compounds such as acrylate, melamine acrylate, silicone acrylate, unsaturated polyesters, tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Epoxy compounds, such as neopentylglycol diglycidyl ether, bisphenol A diglycidyl ether, and various alicyclic epoxy, 3-ethyl-3-hydroxymethyl oxetane, 1, 4-bis {[(3-ethyl Oxetane compounds, such as -3- oxetanyl) methoxy] methyl} benzene and di [1-ethyl (3-oxetanyl)] methyl ether, are mentioned.

Although the radiation curable resin can be used alone or in combination, a polyfunctional acrylate such as dipentaerythritol hexaacrylate having excellent hardening speed and scratch resistance of the hard coat layer, adhesiveness between the resin film and the hard coat layer, and hard coat More preferred is a mixed system with a polyfunctional urethane acrylate excellent in flexibility and flexibility of the layer. The range of 0.1-1.5 is preferable and, as for the mixing ratio of polyfunctional urethane acrylate with respect to polyfunctional acrylate, the range of 0.2-0.7 is more preferable. When the ratio of the polyfunctional urethane acrylate to the polyfunctional acrylate is too low, wrinkles and cracks are likely to occur in the hard coat layer, and curling of the hard coat film is likely to occur. On the contrary, too much is not preferable because the scratch resistance of the hard coat layer is lowered.

As radiation which makes the system which uses said radiation curable resin harden | cure, any of an ultraviolet-ray, a visible ray, an infrared ray, and an electron beam may be sufficient. Moreover, these radiations may be polarized or unpolarized light. In particular, ultraviolet rays are preferable from the viewpoint of equipment cost, safety, operation cost and the like. As an energy source of an ultraviolet-ray, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, etc. are preferable, for example. The irradiation amount of the energy source is preferably in the range of 100 to 5,000 mJ / cm 2 as the integrated exposure amount at the ultraviolet wavelength of 365 nm, and more preferably in the range of 300 to 3,000 mJ / cm 2. When it is less than 100 mJ / cm <2>, since hardening becomes inadequate, the hardness of a hard-coat layer may fall. Moreover, when it exceeds 5,000 mJ / cm <2>, a hard coat layer will color and transparency will fall. In the case of performing curing by ultraviolet irradiation, the addition of a photopolymerization initiator is required. As a photoinitiator, a conventionally well-known thing can be used. For example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4'-diaminobenzophenone, benzylmethyl ketal Phosphorus and its alkyl ethers; Acetophenes such as acetophenone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl ketone Rice field; Anthraquinones such as methyl anthraquinone, 2-ethyl anthraquinone and 2-amyl anthraquinone; Xanthones; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone and 2,4-diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; In addition, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one etc. can be illustrated. These can be used individually or in mixture of 2 or more types. As for the usage-amount of a photoinitiator, about 5% or less in total solid content ratio with respect to a radiation curable resin composition, Furthermore, 1 to 4% is preferable.

A polymer resin can be added and used to the system of the said radiation curable resin composition in the range which does not prevent the polymerization hardening. This polymer resin is a thermoplastic resin soluble in the organic solvent used for the hard coat layer coating mentioned later, and an acrylic resin, an alkyd resin, a polyester resin, etc. are mentioned specifically, In these resin, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. are mentioned. It is preferable to have an acidic functional group of.

Moreover, additives, such as a leveling agent, a thickener, an antistatic agent, a filler, a extender pigment, can be used. The leveling agent has a function of correcting defects prior to coating film formation by promoting uniformity of the surface of the coating film, and a material having both lower interfacial tension and surface tension than the radiation curable resin composition is used.

Although the hard-coat layer is mainly comprised by hardened | cured material, such as the resin composition mentioned above, the formation method coats the coating material which consists of a resin composition and an organic solvent, and after evaporating an organic solvent, radiation (for example, electron beam or ultraviolet irradiation) Or hardening by heat. As the organic solvent used here, it is necessary to select a suitable one for dissolving the resin composition. Specifically, single or mixed solvents selected from alcohols, esters, ketones, ethers, and aromatic hydrocarbons can be used in consideration of coating properties such as wettability, viscosity, and drying rate for the resin film.

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

When the hard coat layer is thinner than 3.0 mu m, the surface hardness decreases.

If the hard coat layer is thicker than 20.0 µm, the resin film becomes less likely to absorb or relieve the stress at the time of curing shrinkage of the hard coat layer. Therefore, curling occurs on the hard coat film or microcracks occur on the surface of the hard coat layer. Adhesiveness with a resin film falls, and also light transmittance falls. And it may become a cause of the cost increase by the increase of the required coating amount accompanying an increase of a film thickness.

The hard coat layer may contain organic and inorganic fine particles as appropriate. The organic and inorganic fine particles may be contained alone in the hard coat layer, or may be contained in combination of the organic and inorganic fine particles.

As the organic fine particles, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluorides, polyethylene fluoride resins and the like can be used.

Examples of the inorganic fine particles include titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, calcium oxide, indium oxide, antimony oxide and the like. Moreover, these composites can also be used. Among these, titanium oxide, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable.

Said organic and inorganic fine particles may be used individually by 1 type, and may use 2 or more types together.

In addition, when the uneven structure is formed on the surface of the hard coat layer by including light-transmitting fine particles having an average particle diameter of 0.3 to 10 탆 in the hard coat layer, the anti-glare layer is preferable. This makes it possible to use a hard coat film as an antiglare film. As for the refractive index of the translucent microparticles | fine-particles whose average particle diameter is 0.3-10 micrometers, 1.40-1.75 are preferable, and when refractive index is less than 1.40 or larger than 1.75, the difference in refractive index with a translucent base or resin matrix will become large too much, and total light transmittance will fall. Moreover, as for the difference of the refractive index of a translucent microparticle and a resin component, 0.2 or less are preferable. It is preferable that it is the range of 0.3-10 micrometers, and, as for the average particle diameter of translucent microparticles | fine-particles, 1-8 micrometers is more preferable. If the particle size is smaller than 0.3 mu m, the anti-glare property is deteriorated. If the particle diameter is larger than 10 mu m, it is not preferable because the glare is generated and the degree of the surface irregularities becomes too large and the surface becomes cloudy. Although the ratio of the translucent microparticles contained in the said resin is not specifically limited, It is preferable to set it as 1-20 weight part with respect to 100 weight part of resin compositions, in order to satisfy characteristics, such as an anti-glare function and glare, and the fine unevenness | corrugation of the surface of a hard-coat layer It is easy to adjust shape and haze value. Here, "refractive index" points out the measured value according to JISK-7142. In addition, an "average particle diameter" points out the average value of the diameter of 100 particle | grains measured with the electron microscope.

In this invention, you may laminate | stack a polarizing base on the resin film (on the surface on which the hard coat layer is not laminated | stacked). Here, the said polarizing gas can use the light absorption type polarizing film which transmits only specific polarization and absorbs other light, and the light reflection type polarizing film which transmits only specific polarization and reflects other light can be used. As a light absorption polarizing film, the film obtained by extending | stretching polyvinyl alcohol, polyvinylene, etc. can be used, For example, the polyvinyl obtained by uniaxially stretching the polyvinyl alcohol which adsorbed oxo or dye as a dichroic element. Alcohol (PVA) film is mentioned. As a light reflection type polarizing film, when extending | stretching, the structure which laminated | stacked and extended | stretched several types of polyester resins (PEN and PEN copolymer) from which the refractive index of an extending | stretching direction differs several hundred layers by extrusion molding technique, for example. 3M company "DBEF" and a cholesteric liquid crystal polymer layer and a quarter wave plate are laminated, and the light incident from the cholesteric liquid crystal polymer layer side is separated into two circularly polarized light in opposite directions, , Nitto Electric Co., Ltd. "Nippox" made by Nitto Corporation and Merck Co., Ltd. "Trans Max" of the structure which transmits light, reflects the other, and converts circularly polarized light which permeate | transmitted the cholesteric liquid crystal polymer layer into linearly polarized light by a quarter wave plate Can be mentioned.

The adhesiveness (adhesive force) of the hard coat layer and the polarizing gas constituting the hard coat film can be improved by performing a saponification treatment on the hard coat film before laminating the polarizing gas on the resin film constituting the hard coat film. In the conventional hard coat film, the generation of curls and cracks was remarkably confirmed in the hard coat film by the saponification treatment, but according to the present invention, the occurrence of curls and cracks can be reduced even in the hard coat film after saponification.

<Other floor>

The hard coat layer may be laminated on one side of the resin film or may be laminated on both sides.

Furthermore, the hard coat film may have another layer. As another layer here, a polarizing gas, a low reflection layer, another function provision layer (for example, antistatic layer, a near-infrared (NIR) absorption layer, a neon cut layer, an electromagnetic shield layer, a hard coat layer) is mentioned, for example. . The position of the other layer is, for example, on the resin film on the opposite side to the hard coat layer in the case of a polarizing gas, and on the hard coat layer in the case of a low reflection layer, and of another functional provision layer. In this case, the hard coat layer is the lower layer.

<Manufacturing Method>

The manufacturing method of the hard coat film of this invention is performed by coating a radiation curable resin coating material on a resin film, drying, and then radiation hardening and creating it. What is necessary is just to satisfy | fill the relationship of Ax1,500 <B at the time of coating. As a method of coating a coating on a resin film, a normal coating method or a printing method is applied. Specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calender coating, dam coating, dip coating, Printing such as intaglio printing such as coating such as die coating or gravure printing, or stencil printing such as screen printing can be used.

In addition, since the hard coat film of the present invention satisfies the relation of A × 1,500 < B, even when manufactured with Roll-to-Roll, cracks and curls due to cure shrinkage are less likely to occur, so that the yield can be improved.

Hereinafter, the Example of invention ((alpha)) is shown.

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

95.6 parts of methacryloyloxypropyl trimethoxysilane, methyl ethyl ketone silica sol (made by Nissan Chemical Co., Ltd., brand name: MEK-ST-L, number average particle diameter 45nm, silica concentration 30%) 27.4 parts of solid content) and 0.1 part of ion-exchange water were stirred at 80 degreeC for 3 hours, and then 1.4 parts of ortho formic acid methyl esters were added, and it stirred again at the same temperature for 1 hour, and the dispersion liquid of translucent microparticles of this invention (A liquid) Got. The total solid concentration was found to be 32%, and the average particle diameter of the light-transmitting fine particles was 45 nm. Here, the average particle diameter was measured by the transmission electron microscope.

The coating material for the optical function layer obtained by disperse | distributing the mixture which consists of components of Table 1 for 30 minutes by the disper on one side of TAC (Kicaminolta Opto company; KC4UYW) which is a translucent gas which is 40 micrometers in thickness and 92% of total light transmittance. Applying in roll coating method (line speed; 20 m / min), preliminary drying for 20 seconds at air volume of 0.5 m / sec, 30-50 ° C., then drying at 100 ° C. for 1 minute, nitrogen atmosphere (nitrogen gas substitution) The coating film was cured by performing ultraviolet irradiation (lamp; condensing type high pressure mercury lamp, lamp output; 120 W / cm, etc. mercury: 2 lamps, irradiation distance; 20 cm). Thus, the optical laminated bodies of Example 1, 2, 4, and Comparative Examples 1-3 which have an optical function layer of 10.0 micrometers in thickness were obtained. Moreover, the optical laminated body of Example 3 was obtained for the film thickness of a translucent base being 80 micrometers, and the thickness of an optical function layer being 12.0 micrometers.

&Lt; Comparative Example 4 &

Except having made the thickness of the optical function layer into 2 micrometers, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 4 of this invention.

Adhesion, total light transmittance, haze, contact angle of water, curl, scratch resistance, pencil hardness, chemical resistance, antifouling property, interference stain and element ratio of fluorine using optical laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 4 It was measured and evaluated by the following method.

Adhesiveness

It was carried out according to the crosscut method of JIS K5600.

Moreover, the space | interval of cuts shall be 1 mm, and the number of cuts shall be 11 pieces. Evaluation shows the percentage of the number of the cross cut gratings not peeled off. For example, if five peeled off, it displays as 95/100.

Light rays  Transmittance

According to JIS K7105, it measured using the haze meter (brand name: NDH2000, the Nippon Color Corporation).

Hayes

According to JIS K7105, it measured using the haze meter (brand name: NDH2000, the Nippon Color Corporation).

Contact angle of water (θ / 2 law )

First, the contact angle of water on the surface of the optical functional layer was measured. Next, the contact angle of water on the saponified optical functional layer surface was measured. The contact angle of water was measured using the contact angle meter (brand name; Herma G-1 type contact angle meter, the product made by Herma) based on JISR3257 (the substrate glass surface wettability test method).

The saponification process of an optical laminated body follows the following procedures.

(1) Immersion in 55% of 6% aqueous sodium hydroxide solution for 2 minutes.

(2) Wash for 30 seconds.

(3) Immerse in sulfuric acid of 0.1 degreeC at 35 degreeC for 30 second.

(4) Wash for 30 seconds.

(5) Hot air drying at 120 ° C. for 1 minute.

The larger the contact angle, the higher the water repellent effect, the better the chemical resistance, wear resistance, and antifouling resistance. The contact angle before the saponification treatment is 90 ° or more, preferably 100 ° or more, and the contact angle after the saponification process is 70 ° or more, preferably 80 ° or more.

curl

First, the produced optical laminated body is left to stand for 16 hours in the environment (temperature 23 +/- 2 degreeC, humidity 50 +/- 5 RH%) shown to JISK5600-1-6 (temperature and humidity of curing and test). Next, the 10 cm x 10 cm measurement sample was cut out in the same environment, and the "measurement part" shown in FIG. 1 was measured on the flat plate so that an optical function layer might become upper. (Circle) and the thing of less than 10-30 mm, (triangle | delta), and the thing less than 30-50 mm were made into (circle) and 50 mm or more that the measured value was less than 0-10 mm.

Antifouling

After drawing a 3 cm long line with an oil pen (brand name: Macy, ZEBRA) on the optical function layer of the produced optical laminated body, and leaving it to stand for 1 minute, to a clean wiper (article number: FF-390C Kuraray Kuraflex Co., Ltd.) It evaluated by the method of wiping off. After reciprocating rubbed 20 times with a 500 g / cm <2> load, (circle) and the case where there was an unpolished part were (triangle | delta) and the case where it was not wiped at all was made into x.

Chemical resistance

Reagents of ligroin, toluene, sulfuric acid (10%), NaOH (6%), ethanol, neutral detergent (family pure), hand cream (NIVEA), and hair liquid (success: morning hair water) are added dropwise to the surface of the optical functional layer Then, it was left to stand for 10 hours, and then evaluated by rubbing with a 500 g / cm 2 load and 20 times with a clean wiper (article number: FF-390C Kuraray Kuraflex Co., Ltd.). After wiping off, the presence or absence of a change in appearance was visually evaluated. The case where there is no change with respect to all the chemical | medical agents, the case where a change is confirmed also in any one chemical | medical agent, such as (circle) and whitening, was made into x.

Scratch resistance

Steel Wall # 0000 manufactured by Nippon Steelwall Co., Ltd. was installed in an anti-wear tester (Abrasion Tester, Model 339 manufactured by Fu Chien), and the optical functional layer surface was reciprocated 10 times at a load of 250 g / cm 2. Then, the wound of the abrasion part was confirmed under fluorescent lamp. ? When the number of wounds was 0,? When the number of wounds was less than 1-10,? When the number of wounds was less than 10-30,?

Surface Hardness (Pencil Hardness)

It measured in accordance with JIS 5400 using the pencil hardness meter (made by Yoshimitsu Precision Instruments). The number of measurements was made five times, and the number of wounds was counted. For example, 3 pencils were made 3/5 (3H) if there were no wounds. The pencil hardness made 4/5 (3H) or more favorable.

Interference speckle

Bonded through a pressure-sensitive adhesive layer with a refractive index of 1.5 (film thickness of 20 µm) on the surface of the cross nicol polarizing plate so that the optical functional layer is on the surface, and under a three-wavelength fluorescent lamp (manufactured by Matsushita Electric Industries Co., Ltd .: FLR40S-EX-N / MX, roughness 500 Visual evaluation by reflection). (Circle) and the case where it can confirm a little thinly when the interference | contamination stain | fever cannot be confirmed were made into (triangle | delta) and the case which can be confirmed clearly.

Element ratio of fluorine

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

Measuring device; Quantera SXM, made by R.

Acceptance angle of optoelectronics; 45 degrees

X-ray output; 25.0 W

Measured X-ray diameter; 100 탆

Pass Energy; 112.0 eV

Measuring element; C1s, O1s, F1s, Si2p

By ESCA, C1s, O1s, F1s, Si2p which exist to a depth of 5 nm from the optical functional layer surface were measured. An element ratio was calculated from the obtained element peak area.

Here, each component in Table 1 is demonstrated in detail.

Polyfunctional acrylate Kyoeisha Chemical PE3A: pentaerythritol triacrylate (trifunctional)

Polyfunctional urethane acrylate Kyoeisha Chemical UA-306H: pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (six functional)

Multifunctional acrylic Japanese gunpowder PET-30: pentaerythritol triacrylate (trifunctional)

Polyfunctional acrylic Dong-ah Synthesis M-305: pentaerythritol triacrylate (trifunctional)

Monofunctional acrylate Kyoeisha Chemical HOP-A: 2-hydroxypropyl acrylate (monofunctional)

Fluorinated acrylate Kyoisha Chemical LINC-3A: A mixture of 65% triacroylheptadecafluorononenyl pentaerythritol (4-functional) and 35% pentaerythritol tetraacrylate (4-functional) (Formula 8)

Fluorinated acrylate Kyoeisha Chemical LINK-102A: the compound represented by following formula (9)

[Formula 8]

[Chemical Formula 9]

The measurement results are summarized in Table 2.

In Examples 1-4, C1s, O1s, F1s, and Si2p which exist to depth 200nm from the optical functional layer surface by ESCA were measured at 5 nm intervals. The ratio of the fluorine element ratio present from the surface of the optical functional layer to 5 nm divided by the average value of the ratio of the fluorine element present at every 5 nm depth obtained by measuring at a 5 nm interval from the depth of 5 nm to the depth of 200 nm of the surface of the optical functional layer is obtained. It was 20 or more in Examples 1-4.

The Example and comparative example of this invention ((beta)) are demonstrated below.

In addition, "part" shall mean a "weight part."

[Example 5]

As a paint for the hard coat layer, the paint obtained by stirring the mixture consisting of the following coating components in a disper for 1 hour on a surface of TAC (product name: KC4UYW manufactured by Konica Minolta Co., Ltd.), which is a resin film composed of a film thickness of 40 µm and a total light transmittance of 92%, After coating by a head coating method and drying at 100 ° C. for 1 minute, UV irradiation (irradiation distance 10 cm, irradiation time 30 seconds) was performed with a 120 W / cm condensing high pressure mercury lamp 2 in a nitrogen atmosphere to cure the coating film. The thickness of the hard coat layer was 19 µm, and the off-flavor width was 30 mm. Thus, the hard coat film of Example 5 was obtained.

150 parts of polyfunctional acrylate (product made in Kyoeisha Chemical company: light acrylate DPE-6A)

40 parts of polyfunctional urethane acrylate (product made by Shin-Nakamura Chemical Corporation: U-6HA)

Photoinitiator (product made by Chiba Specialty Chemical Company: Irgacure 184) 9 parts

? 1 leveling agent (Product name: Polyflow No. 77, manufactured by Kyoisha Chemical Co., Ltd.)

Solvent (MEK) 200 parts

[Example 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 film thickness of the hard coat layer was 10 μm and the off-flavor width was 20 mm.

[Example 7]

The hard coat film of Example 7 of this invention was changed into Example 5 except having changed the coating component for hard-coat layers into what is shown below, and making the film thickness of a hard-coat layer into 9 micrometers, and having a odor width of 15 mm. Got.

130 parts of polyfunctional acrylate (product made by Shin-Nakamura Chemical Corporation: A-DPH)

60 parts of polyfunctional urethane acrylate (product made by Nippon Synthetic Chemical Co., Ltd .: ultraviolet light UV-1700B)

Photoinitiator (product made in Chiba Specialty Chemicals company: Irgacure 127) nine parts

? 1 leveling agent (Product name: Polyflow No. 77, manufactured by Kyoisha Chemical Co., Ltd.)

Solvent (MEK) 120 parts

Solvent (MIBK) 80 parts

[Example 8]

The hard coat of Example 8 of the present invention in the same manner as in Example 5 except that the resin film was changed to TAC (trade name: TD80 manufactured by Fujifilm Opto-Materials Co., Ltd.) having a thickness of 80 μm, and the odor width was 29 mm. A film was obtained.

[Example 9]

The hard coat 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 a PET 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 odor width 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 film was 10 μm and the odor width was 5 mm.

[Comparative Example 8]

The hard coat film of the comparative example 8 was obtained like Example 5 except having changed the coating component for hard coat layers into what is shown below, and having made the film thickness of the hard coat layer into 15 micrometers, and the odor width of 10 mm.

40 parts of polyfunctional acrylate (product made in Kyoeisha Chemical company: light acrylate DPE-6A)

150 parts of polyfunctional urethane acrylate (product made by Shin-Nakamura Chemical Corporation: U-6HA)

Photoinitiator (product made in Chiba Specialty Chemicals company: Irgacure 184) nine parts

? 1 leveling agent (Product name: Polyflow No. 77, manufactured by Kyoisha Chemical Co., Ltd.)

Solvent (MEK) 200 parts

The hard coat films obtained in Examples 5 to 9 and Comparative Examples 5 to 8 were used to measure and evaluate curls, wrinkles, adhesiveness, and pencil hardness by the following methods. The results obtained are shown in Table 3.

(1.curl)

The hard coat films of Examples 5-9 and Comparative Examples 5-8 were produced 1.5 m in length. Next, as shown in Fig. 4A, the hard coat film 1 is placed on the horizontal pedestal 30 so that the coating surface is upward, and the four corners of the hard coat film 1 are horizontal. The pedestal 30 was fixed with a cello tape (registered trademark) 40.

Next, the hard coat layer was left to stand for 16 hours in an environment (temperature 23 ± 2 ° C., humidity 50 ± 5 RH%) shown in JIS K5600-1-6 (temperature and humidity of curing and testing).

Subsequently, the hard coat film 1 was placed at a site of 0.5 m from the end fixed with the cello tape (registered trademark) 40, and the height C from the horizontal pedestal 30 was measured, respectively. The height C bent is the distance from the center of the horizontal pedestal 30 to the hard coat film 1 as shown in FIG. 4 (b). It tested 5 times and made the average value the measured value of curl.

In addition, Curl | Karl is good ((circle)) 20 mm or less, and when it exceeds 20 mm, a hard coat film or various secondary processed products using the same (for example, the polarizing plate protective film which saponified to the hard coat film) Since it has a big influence on the production of, it was set to ×.

(2.wrinkle)

The case where ten wrinkles and the average space | interval of wrinkles in a coating direction were 10 mm or more and (circle), 5 mm or more and less than 10 mm was made into (triangle | delta), less than 5 mm, or the case where the film was cracked (cracked) or folded.

(3. Adhesion)

Adhesion was performed according to the crosscut method of JIS K5600.

Moreover, the space | interval of cuts shall be 1 mm, and the number of cuts shall be 11 pieces. Evaluation shows the percentage of the number of the cross cut gratings not peeled off. For example, if five pieces are peeled off, 95/100 is displayed.

(4. pencil hardness)

Pencil hardness was tested 5 times in accordance with JIS 5400 to count the number of scratches. For example, if 3 wounds were not found in a 3H pencil, 3/5 (3H) was performed.

As mentioned above, although the hard-coat film of Examples 5-9 has 4H or more of surface hardness (pencil hardness), since it was A * 1,500 <B, curling was hard to produce. In addition to these effects, cracks and wrinkles were less likely to occur.

On the other hand, since the hard coat films of Comparative Examples 5-8 do not satisfy the relation of A × 1,500 <B, cracks, wrinkles, curls are generated, or the surface hardness does not satisfy 4H or more. It was not available.

As mentioned above, according to this invention ((beta)), in the laminated constitution which laminated | stacked one layer of hard-coat layers on the resin film, it can provide the hard-coat film which is easy to produce curl, having excellent surface hardness.

Moreover, since the hard coat film of this invention ((beta)) satisfies the relationship of Ax1,500 <B, the process of making a hard coat film by Roll-to-Roll and its secondary processing process (for example, saponification) The hard coat film which curling hardly produces can be provided also when a process) is performed.

1 hard coat film
Cross section of 1a, 1b hard coat film
10 resin film
11a, 11b resin film cross section
Edges of 12a and 12b Resin Films
20 hard coat floors
Cross section of 21a, 21b hard coat layer
Edges of 22a and 22b Resin Films
30 horizontal pedestal
40 cello tape (registered trademark)

Claims (5)

The hard coat layer is laminated on the resin film,
Let the thickness of the hard coat layer be A (mm),
When the width (odor odor width) from the edge of the resin film to the edge of the hard coat layer is B (mm), A x 1,500 <B (where 0.003 mm ≤ A ≤ 0.020 mm) It is a hard coat film characterized by the above-mentioned. The method according to claim 1,
The elasticity modulus of the said resin film is 2 GPa-8 GPa, The hard coat film characterized by the above-mentioned. The method according to claim 1,
The thickness of the said resin film is 5-100 micrometers, The hard coat film characterized by the above-mentioned. The method according to claim 1,
The said hard coat layer contains radiation curable resin, and the volumetric shrinkage rate of the said radiation curable resin is 5 to 25%, The hard coat film characterized by the above-mentioned. The hard coat layer as described in any one of Claims 1-4 is provided with surface uneven structure, The anti-glare film characterized by the above-mentioned.

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