KR100254311B1 - Optical functional materials - Google Patents

Abstract

PURPOSE: An optical functional material is provided to obtain excellent moistureproofness, scratch resistance, adhesion to a substrate, transparency, low refractive index, and dye deterioration preventive property. CONSTITUTION: An antiglare layer(12) having a fine uneven surface is formed directly or through other layer(s) on a transparent substrate film(11). A layer(13) having a low refractive index, which is lower than that of the antiglare layer, is formed thereon. The refractive index of the antiglare layer is higher than that of a layer in contact with the antiglare layer on its surface remote from the layer having a low refractive index. An SiOx film is used as the layer(13) having a low refractive index.

Description

Optical functional materials

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to an optical functional film, and in particular, optical displays such as various displays such as word processors, computers, televisions, and the like, surfaces of polarizing plates used in liquid crystal display devices, transparent plastic-type sunglasses lenses, manual glasses lenses, and finder lenses for cameras. The present invention relates to an optical functional film suitable for a surface antireflection film such as window glass such as a cover of various instruments, an automobile, a train, and the like and a manufacturing method thereof.

Curving mirrors, back mirrors, large goggles, window glass, displays such as personal computers and word processors, and other commercial displays are transparent substrates such as glasses and plastics. When the visual information of objects, characters, and figures through these transparent substrates or the image from the reflective layer is observed through the transparent substrate in the mirror, the surface of these transparent substrates reflects light to provide internal visual information. There was a problem that became difficult to see.

Conventionally, the following technique was mentioned as an anti-reflective technique of light, for example. That is, a method of coating an anti-reflective paint on the surface of glass or plastic, a method of installing a thin film or metal deposited film such as MgF ₂ having a film thickness of about 0.1 μm on the surface of a transparent substrate such as glass, or a plastic surface of a plastic lens coating the ionizing radiation curing type resin, there is a method of forming by vapor deposition on the film of SiO ₂ or MgF _2, a method of forming a film of low refractive index on the cured film of an ionizing radiation curing resin.

The thin film of MgF ₂ having a thickness of about 1 μm formed on the glass will be described again. When incident light is incident perpendicularly to the thin film, a specific wavelength is set to λ ₀ , and when the refractive index of the antireflection film is n ₀ , the thickness of the antireflection film is h and the refractive index of the substrate is n _g , the reflection is made. It is well known that the prevention film prevents the reflection of light 100% and transmits the light 100% by satisfying the relationship between the following equations (1) and (2) (Science Library Physics = 9). Optical, pp. 70-72, issued by Science Co., Ltd., 1980.

------------(One)

-----------(2)

Since the refractive index of glass n _g = about 1.5, and the refractive index n ₀ = 1.38 of the MgF ₂ film and the wavelength of the incident light λ ₀ = 5500 kHz (reference), the values of the antireflection film are substituted into the above formula (2). h is calculated to be about 0.1 μm optimal.

According to Equation (1), in order to prevent 100% reflection of light, it is understood that a material whose upper coating film refractive index is about the square root of the lower coating film refractive index may be selected. It has conventionally been performed to prevent reflection of light by setting the upper coating film refractive index to a value slightly lower than that of the lower layer.

In addition, in order to prevent light from being darkened by diffusing reflection or diffusion transmission of light from the outside or the inside, antiglare treatment is performed on the surface of a display or the like. In such anti-glare treatment, for example, an anti-glare base material coated with a resin containing a filler such as silicon dioxide on the display surface or a resin containing a filler such as silicon dioxide on a transparent substrate is adhered to the display surface. .

In particular, a film-like polarizing element serving as a shutter of light is provided on the surface of a display such as a liquid crystal display, but since the polarizing element itself has poor hard performance, glass, a transparent plastic plate, or a transparent plastic film It is protected by transparent protective substrates, such as this, and the polarizing plate is formed. However, since the transparent protective substrate itself which consists of plastics, such as a transparent plastic board or a transparent plastic film itself, is also easy to perish, the thing which gave hard performance to the surface of such a polarizing plate is developed in recent years. As such a technique, it is described in Unexamined-Japanese-Patent No. 105738/1989, for example.

This publication discloses a transparent protective substrate provided with hard performance and anti-glare property, that is, a triacetate film for light control, to be bonded to a polarizing element to form a polarizing plate. This film is a triacetate film excellent in hard performance by providing a cured coating film made of an ultraviolet curable epoxy acrylate-based resin on one side of the unsaponified triacetate film. In order to provide anti-glare property to the triacetate film excellent in the said hard performance, the resin composition which added amorphous silica to the said ultraviolet curable epoxy acrylate resin is apply | coated to the surface of a triacetate film, and it hardens. When the triacetate film thus obtained is bonded to a polarizing element to form a polarizing plate, the saponification process is first performed with an alkali and then bonded with the polarizing element to increase the bonding property with the polarizing element or to prevent electrostatic discharge. .

However, in order to form an anti-glare reflective film by providing a layer that provides anti-glare and anti-glare at the same time on the base film, in order to provide a layer having at least these functions or other various layers such as an adhesive layer, For example, one or more layers must be provided between the base film and the outermost surface layer provided on the base film. In this case, the reflection of light occurs at the interface of each layer, and especially in the interface having a film thickness that is relatively thick (0.5 μm or more) and thicker than the wavelength of light, as formed by coating, such a tendency appears. There was a problem of lowering the antireflection effect.

On the other hand, the conventional antireflection film in which the antireflection layer was formed on the outermost surface on the transparent base film had a problem that the antireflection film formed had a weak hard performance and was easily damaged because the antireflection layer had a thickness of about 0.1 μm. .

Moreover, although an optical function film is normally laminated | stacked in the film provided with optical function, such as an antireflection film, such an optical film is not enough gas barrier property and is weak in moisture proof property. In particular, the polarizing element used for a liquid crystal display device is weak to moisture, and needs to provide moisture proof property.

Accordingly, a first object of the present invention is to provide an optical functional film having excellent gas barrier properties such as moisture resistance to an optical functional material constituting an optical material such as an antireflection film or an antireflection film.

A second object of the present invention is to provide an anti-glare anti-reflection film and a method for producing the same, which have anti-glare and / or anti-reflection, and can reduce reflection of light at an interface between respective layers therein.

A third object of the present invention is to provide an antireflection film and a method for producing the same in which hard performance is provided in addition to the second object.

FIG. 1 illustrates a laminated film in which a SiO _x deposition film having a refractive index of 1.46 is formed on a triacetyl cellulose (TAC) film having a refractive index of 1.49.

FIG. 2 shows a laminated film on which a hard coating layer (HC layer) having a refractive index of 1.49 and a SiO _x deposition film having a refractive index of 1.46 are formed thereon on a TAC base film having a refractive index of 1.49.

FIG. 3 shows a laminated film having a hard coating layer having a refractive index of 1.55 on top of a triacetyl cellulose film having a refractive index of 1.49 and a SiO _x deposition film having a refractive index of 1.46 thereon.

FIG. 4 shows a hard coating layer having a refractive index of 1.65 formed on a saponified triacetyl cellulose film having a refractive index of 1.49 and a primer layer having a refractive index of 1.55, and a resin obtained by dispersing high refractive index fine particles of ZnO thereon. a refractive index of 1.46 shows a laminated film is SiO _x deposited film formed.

FIG. 5 shows spectral reflectance curves of the laminated film shown in FIG. 1.

FIG. 6 shows spectral reflectance curves of the laminated film shown in FIG. 2.

FIG. 7 shows the spectral reflectance curves of the laminated film shown in FIG. 3.

8 shows a spectral reflectance curve showing that the pitch of the wavelengths increases as the film thickness becomes thinner.

FIG. 9 shows the spectral reflectance curve in the case where the refractive index of the HC layer is increased to 1.65 in the laminated film of FIG. 3.

FIG. 10 shows the spectral reflectance curves of the laminated film shown in FIG. 4.

FIG. 11 shows the spectral reflectance curves of a laminated film made of a TCA base film (refractive index 1.49) / high refractive index hard coating layer (refractive index 1.62 / low refractive index (refractive index 1.46)) and another laminated film.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A1.

It is sectional drawing which shows the laminated constitution of the antireflection film obtained in Example B1.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A2.

It is sectional drawing which shows the laminated constitution of the antireflective film obtained in Example B2.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A3.

It is a figure which shows the structure of the polarizing plate by which the anti-glare antireflection film of this invention was laminated.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A4.

It is a figure which shows the laminated constitution of the liquid crystal display device using the polarizing plate in which the anti-reflective film of this invention was laminated.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A5.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A8.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained in Example A9.

It is a figure which shows the laminated constitution of the polarizing plate by which the anti-glare antireflection film of this invention is laminated.

It is a figure which shows the laminated constitution of the liquid crystal display device using the polarizing plate in which the anti-glare antireflection film of this invention was laminated.

21 shows a conceptual diagram of light reflection.

22 is a diagram illustrating a concept of light transmission.

1,19,170 --- TAC base film,

2,120 --- HC layer, 3 --- SiOx deposited film

4,14,140 --- Primer Layer

11,110 --- Transparent base film 12,17 --- High refractive index antiglare layer

13,130 --- Low Refractive Index Layer 15 --- Adhesive Layer

16 --- clear hard coating layer 18 --- matte

20,160 --- polarizer 21,180 --- liquid crystal display

150 --- Antireflection Film

In order to achieve the first object described above, the optically functional film according to the present invention is characterized in that the contact angle of the surface with respect to water is made of a SiO _x film (x is 1.50 ≦ x ≦ 4.00) of 40 to 180 degrees. This SiO _x film is preferably a film formed by plasma CVD. In the present invention, it is preferred that the SiO _x film and the dynamic friction coefficient of 1 or less.

This optically functional film is typically capable of forming an SiO _x film (x is 1.50 ≦ x ≦ 4.00) directly or on another layer via a transparent layer film, preferably by plasma CVD. It can be formed at any position of.

In the anti-glare antireflection film of the present invention for achieving the above-mentioned second object, (1) an anti-glare layer mainly composed of an uneven binder resin having a fine surface on the transparent base film directly or through another layer is formed. (2) a low refractive index layer having a refractive index lower than the refractive index of the antiglare layer is formed on the antiglare layer, and (3) the refractive index of the antiglare layer is opposite to the low refractive index layer in contact with the antiglare layer. It is characterized in that it is higher than the refractive index of the layer (for example, a transparent base film, a plasma layer, an adhesive layer, a second hard coating layer, etc.).

The anti-glare antireflection film of the present invention for achieving the above-described third object is (1) an anti-glare layer having a fine concavo-convex surface and hard performance is formed on the transparent base film directly or through another layer, (2 A low refractive index layer having a refractive index lower than the refractive index of the antiglare layer is formed on the antiglare layer, and (3) the refractive index of the antiglare layer is a layer in contact with the opposite side of the low refractive index layer that the antiglare layer is in contact with. It is characterized by higher than the refractive index.

Moreover, the manufacturing method of the anti-glare antireflection film of this invention (1) The resin composition containing the high refractive index microparticles | fine-particles which have a refractive index higher than the refractive index of a binder resin and the said binder resin on a transparent base film directly or via another layer. In addition, in the laminated constitution of the anti-glare antireflection film as a final product, the resin composition which has a refractive index higher than the refractive index of the layer directly contacting the lower side of the layer which uses the said resin composition is coated, (2 ) Laminate an embossed film on the mat having fine irregularities on the surface of the formed coating film with a fine concavo-convex surface toward the coating film, and (3) the resulting laminate is subjected to heat treatment and / or ionizing radiation treatment to cure the coating film. (4) The embossed film is peeled off from the laminate with the cured coating film. By Kim form an antiglare layer having a fine uneven surface, and (5) so as to form a low refractive index layer having a lower refractive index than that of the antiglare layer on the anti-glare layer obtained in the step.

Moreover, another manufacturing method of the anti-glare antireflection film of this invention contains (1) (1) high refractive index microparticles | fine-particles which have refractive index higher than the refractive index of the binder resin and the said binder resin on the mat-shaped embossing film which has a fine unevenness | corrugation on the surface. And a resin composition having a refractive index higher than that of the layer directly in contact with the bottom of the layer using the resin composition in the layer composition of the anti-glare antireflection film as the final product. And (2) On the other hand, an embossed film having a coating film formed in the above step, directly or via another layer, is laminated with the coating film inward, and (3) heat-treating the laminate. An ionizing radiation treatment is performed to cure the coating film, and (4) a laminate in which the coating film is cured. By peeling the said embossed film from water, the anti-glare layer which has a fine unevenness | corrugation is formed in the surface, (5) The low refractive index layer which has a refractive index lower than the said glare-proof layer is formed on the anti-glare layer formed at the said process.

Moreover, another manufacturing method of the anti-glare antireflection film of this invention contains the binder resin and high refractive index microparticles | fine-particles which have refractive index higher than the refractive index of the said binder resin on the mat-shaped embossing film which has a fine unevenness | corrugation on the surface. It is a resin composition, and in the laminated constitution of the anti-glare antireflection film as a final product, the resin composition which coats the resin composition which has a refractive index higher than the refractive index of the layer directly contacting the bottom of the layer which uses the said resin composition. To form a coating film, and (2) harden the coating film to obtain a high refractive index hard coating layer, and (3) a high refractive index hard coating layer of the above process through an adhesive layer on at least one surface of the transparent substrate film. The formed embossed film was laminated with the high refractive index hard coating layer inward, and (4) the adhesion After hardening the layer, the embossed film was peeled off from the laminate to transfer a high refractive index hard coating layer having fine irregularities on the surface thereof to the transparent base film side, and (5) the high refractive index hard coating layer on the high refractive index hard coating layer. It is characterized by providing a low refractive index layer having a refractive index lower than the refractive index.

Anti-reflection film according to another aspect of the present invention,

(1) The low refractive index layer which is a surface layer is formed in at least one surface of the transparent base film and the back surface through the other layer,

(2) at least one layer of the other layer is a hard coating layer mainly composed of a binder resin, and the hard coating layer is in direct contact with the low refractive index layer,

(3) The refractive index of the hard coating layer is higher than the refractive index of the layer in contact with the surface opposite to the low refractive index layer side of the hard coating layer.

Moreover, the manufacturing method of the antireflection film which concerns on this invention,

(1) It is a resin composition containing high refractive index microparticles | fine-particles which have a refractive index higher than the refractive index of binder resin and the said binder resin on at least one surface of the front surface and the back surface of a transparent base material film directly or another layer, and also of the said resin composition A coating film is formed by coating a resin composition having a refractive index higher than that of a layer directly in contact with the lower side of the layer using the resin composition in the layer structure of the antireflection film as the final product,

(2) curing the coating film to obtain a high refractive index hard coating layer;

(3) Next, a low refractive index low refractive index layer lower than the refractive index of the high refractive index hard coating layer is provided on the high refractive index hard coating layer.

Moreover, the manufacturing method of the antireflection film of this invention,

(1) A resin composition comprising a binder resin and high refractive index fine particles having a refractive index higher than that of the binder resin in a release film having a smooth surface, and the refractive index of the resin composition being a layer of an antireflection film as a final product. In the constitution, a coating film is formed by coating a resin composition having a refractive index higher than that of a layer directly in contact with the bottom of the layer using the resin composition.

(2) On the other hand, the release film in which the coating film of the said process was formed in at least one surface of the front surface and the back surface of a transparent base film directly or via another layer is laminated with the said coating film inside,

(3) performing heat treatment and / or ionizing radiation treatment on the laminate to cure the coating film;

(4) The high refractive index hard coating layer is transferred to the transparent base film by peeling the release film from the laminate having the cured coating film,

(5) Next, a low refractive index layer having a refractive index lower than that of the high refractive index hard coating layer is provided on the high refractive index hard coating layer.

In addition, another aspect of the present invention,

(1) A resin composition comprising a binder resin and high refractive index fine particles having a refractive index higher than that of the binder resin on a release film having a smooth surface, and the refractive index of the resin composition is a layer structure of an antireflection film as a final product. Coating a resin composition having a refractive index higher than that of the layer directly in contact with the bottom of the layer using the resin composition, to form a coating film,

(2) curing the coating film to obtain a high refractive index hard coating layer;

(3) Meanwhile, a release film having a high refractive index hard coating layer formed thereon in the above step by laminating an adhesive layer on at least one surface of the transparent base film and the back surface thereof with the high refractive index hard coating layer inward,

(4) after curing the adhesive layer, the release film is peeled off from a laminate to transfer the high refractive index hard coating layer to the transparent base film;

(5) Next, a low refractive index layer having a refractive index lower than that of the high refractive index hard coating layer is provided on the high refractive index hard coating layer.

Hereinafter, each structural requirement of the present invention will be described in more detail based on preferred embodiments.

Anti-glare and Anti-reflective

In the present invention, antiglare means the reflection of external light is diffused and diffused by fine irregularities on the surface of the antiglare layer formed on the surface of a display or the like, or by a mat member disposed inside the antiglare layer. It is a phenomenon that the projected by the decrease. In such an antiglare layer, the transmitted light from the display is diffused, so that there is a drawback that the resolution and contrast decrease.

In the present invention, the antireflection means that the reflection energy of external light is lowered due to the interference effect, so that the projection of the external light is slightly reduced, and the amount of transmitted light from the display is increased (because reflection is reduced), thereby increasing the resolution and contrast. Say the phenomenon. A conceptual diagram of light reflection is shown in FIG. 21, and a conceptual diagram of light transmission is shown in FIG. 22.

In the present invention, the anti-glare antireflection is intended to compensate for the deficiencies of both anti-glare and anti-reflective properties, and specular reflection of light, diffuse reflection, external light input, contrast, and the like are being improved. In particular, the anti-glare film has a defect in that light transmitted from the back is diffused and transmitted, and the image of the surface is darkened when the film is used in a display device. It is characterized by the fact that the reflection and the transmittance increase markedly and the image is bright, the contrast is increased, and the visibility is good. The properties of the anti-glare, anti-reflection, anti-glare anti-reflection will be compared in Table 1 below.

Item Anti-glare Antireflection Anti-glare reflection prevention Specular reflection Diffuse reflection External projection Projection transmission Amount of light Diffuse transmission Light Ambient light Amount of light (Aluminum transmission + Amount of light diffusion + Amount of light) Resolution Contrast Low Low Low Low Many Low Low Low Light low light high high high Little little little little little little little little little high

According to Table 1, since anti-glare antireflection is provided, it turns out that the optical characteristic calculated | required by a display is almost satisfied. In other words, the optical characteristics required for the display are those having a small surface specular reflection, having a low external light projection, having a large amount of transmitted light and appearing bright, a large amount of translucent and light, and having excellent resolution and contrast.

Transparent base film

Examples of the transparent base film include a triacetyl cellulose film, a diacetyl cellulose film, an acetate butyrate cellulose film, a polyester sulfone film, a polyacrylic resin film, a polyurethane resin film, a polyester film, a polycarbonate film, a polysulfone film, and a polyester Films, trimethylpentane films, polyester ketone films, (meth) acrylonitrile films, and the like can be used, but especially triacetyl cellulose films and uniaxially stretched polyesters are suitably used in view of excellent transparency and no optically anisotropy. Can be. The thickness of about 8 micrometers-about 1000 micrometers can be suitably used suitably.

Antiglare layer

Fine unevenness | corrugation is formed in the anti-glare layer surface of this invention. In the method of forming such fine concavo-convex, embossing is performed using a mat-shaped embossing film having fine concavo-convex on the surface, or a coating film is formed by an anti-glare coating material in which a mat material such as plastic beads is added to the binder resin or surface embossing It can carry out by using together and addition of a mat material. In the case of fine uneven embossing on the surface without using a mat material to impart antiglare (that is, a property of diffusing light emitted from the inside to prevent darkening), the transparency of the antiglare antireflection film obtained In particular, it has the effect of not being damaged.

As the embossing film used for the fine uneven | corrugated formation method by the said embossing, what provided desired unevenness | corrugation on plastic films, such as PET with mold release property, or the thing which formed the fine uneven | corrugated layer on plastic films, such as PET, etc. can be used. Such an embossed film can be laminated on the coating film of resin, for example on the coating film of ultraviolet curable resin, and can irradiate an ultraviolet-ray and harden a coating film.

In this case, if the embossing film is a film based on PET, there is a drawback in that curing of the ultraviolet curable resin is not satisfactory because the short wavelength of ultraviolet rays is absorbed into the film. Therefore, when applying an embossing film to the coating film of ultraviolet curable resin, it is necessary to use the thing with 20% or more of the transmittance | permeability of an embossing film in the ultraviolet range of 254 nm-300 nm.

The mat material used for the fine concavo-convex formation method by the addition of the mat material can be preferably used, for example, because plastic beads have high transparency and approximate matrix resin and refractive index. Thus, when the refractive index of a mat material is made as close as possible to the refractive index of resin, transparency of a coating film is not impaired and an anti-glare property can be raised further. As the plastic beads as the mat member, for example, acrylic beads, polycarbonate beads, polystyrene beads, vinyl chloride beads and the like can be used. It is preferable that the particle diameter of these plastic beads is 1-10 micrometers.

When these mat materials are added, since a mat material tends to settle in a resin composition, you may add inorganic fillers, such as a silica, in order to prevent settling. In addition, the more the inorganic filler is added, the more effective the prevention of settling of the mat member, but adversely affect the transparency of the coating film. Therefore, it is possible to prevent sedimentation if the inorganic filler having a particle size of 0.5 µm or less is preferably contained at less than 0.1% by weight, which does not impair the transparency of the coating film to the resin. This silica differs from the silica having a particle diameter of about 5 占 퐉, which is usually used as a conventional mat material, in that the particle size is very small, and its addition effect is also not effective for imparting antiglare properties. In addition, the amount of the use differs in that the conventional mat material is used in an amount of 1 to 30% by weight, whereas silica is used in an extremely small amount of 0.1% by weight or less. In addition, when carrying out this invention, without adding the inorganic filler which is an antisettling agent for preventing sedimentation of a mat material, since a mat material precipitates at the bottom at the time of using a paint, it can be used if it is made to stir well and makes it uniform.

As the binder resin usable in the antiglare layer, any resin (for example, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, or the like) can be used as long as there is transparency. In order to impart hard performance to the antiglare layer and to make the finally obtained antiglare antireflection film have excellent hard performance, the hardness of the antiglare layer can be maintained by setting the thickness of the antiglare layer to 0.5 µm or more, preferably 3 µm or more. Hard performance can be given to an anti-reflective film.

In addition, in this invention, "having a hard performance" or "hard coating" means showing hardness more than H by the pencil hardness test shown by JISK5400.

In order to further improve the hardness of the antiglare layer, it is preferable to use a reaction curable resin, that is, a thermosetting resin and / or an ionizing radiation curable resin as the binder resin used in the antiglare layer. The thermosetting resin may be a phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea copolymer resin, silicon resin, Polysiloxane resin etc. are used, A hardening agent, such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. can be used for these resins as needed.

Preferably, the ionizing radiation curable resin has an acrylate-based group, for example, a relatively low molecular weight polyester resin, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, or a spiroacetal resin. Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polybutadiene resins, polythiol polyene resins, polyhydric alcohols, and the like, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, Mono- and monomeric monomers such as methyl styrene and N-vinylpyrrolidone, for example, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, di Ethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) may be used containing an acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate with a relatively large amount.

Particularly suitable are mixtures of polyester acrylates and polyurethane acrylates. The reason is that the polyester acrylate is suitable for obtaining a hard coating because the coating film has a very high hardness, but the polyester acrylate alone has a low impact resistance and is soft, so that the polyurethane film has a high impact resistance and flexibility. It is using together acrylate. The compounding ratio of polyurethane acrylate is made into 30 weight part or less with respect to 100 weight part of polyester acrylates. When this value is exceeded, the coating film becomes too flexible and hardness disappears.

Furthermore, in order to make the said ionizing radiation curable resin composition into an ultraviolet curable resin composition, there exist acetophenone, benzophenone, Michler's benzoyl benzoate, (alpha)-amyloxime ester, tetramethyl thiuram monosulfide, thioxane as a photoinitiator in it. As tones and photosensitizers, n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used. In particular, in this invention, it is preferable to mix urethane acrylate as an oligomer, dipentaerythritol hexa (meth) acrylate, etc. as a monomer.

You may contain 10 weight part or more and 100 weight part or less of solvent-drying resin with respect to 100 weight part of ionizing radiation curable resins. As the solvent-drying resin, a thermoplastic resin is mainly used. As the kind of the solvent-drying thermoplastic resin added to the ionizing radiation curable resin, one commonly used is used, but in particular, in the case of using a mixture of polyester acrylate and polyurethane acrylate as the ionizing radiation curable resin, solvent drying is used. As the mold resin, polymethacrylate methyl acrylate or polymethacrylate butyl acrylate can keep the hardness of the coating film high. In addition, in this case, since the refractive index with the main ionizing radiation curable resin is approximated, it is advantageous in terms of transparency, particularly low haze value, high transmittance or compatibility, without impairing the transparency of the film.

Moreover, especially when using cellulose resins, such as a triacetyl cellulose, as a transparent base film, cellulose, such as nitro cellulose, acetyl cellulose, cellulose acetate propionate, ethyl hydroxyethyl cellulose, is a solvent-drying resin contained in an ionizing radiation curable resin. System resins are advantageous in terms of adhesion and transparency of the coating film.

The reason for this is that when toluene is used as the solvent in the cellulose-based resin, the toluene which is a non-soluble solvent of triacetyl cellulose, which is a transparent base film, is used. Even if coated, the adhesion between the transparent base film and the coating film resin can be improved, and since this toluene does not dissolve triacetyl cellulose, which is a transparent base film, the surface of the transparent base film is not whitened and transparency can be maintained. There is an advantage.

In the formation of the antiglare layer, a method by coating or a method by transfer may be used. In the method by an electron coating, it is possible to apply | coat and form the resin composition for the said glare-proof layer by the gravure reverse coating method etc., for example through the transparent base film directly or another layer. In the latter method, the resin composition for the antiglare layer is coated on the embossed film having fine irregularities on the surface by, for example, a gravure reverse coating method or the like to form a coating film. Laminating the coating film with the embossed film in which the coating film was formed in the above process directly or on another surface of the at least one surface of the coating layer, and the laminate was subjected to heat treatment and / or ionizing radiation treatment. Curing and then peeling off the embossed film from the laminate to form an antiglare layer, or curing the coating on the embossed film by heat treatment and / or ionizing radiation treatment before the lamination. Of the transparent base film through the adhesive layer after Even laminated on one side, and then the water from the laminate can be formed in the anti-glare layer by peeling off the embossing film.

Since the anti-glare layer in the present invention is a coating by coating, the film has a thickness of 0.5 µm or more as described above, and is formed by a vapor phase method (for example, vacuum deposition, sputtering, ion plating, plasma CVD method, etc.). Thicker than The anti-glare antireflection film thus obtained is given hard performance.

In order to raise the refractive index of an anti-glare layer, it can carry out by using binder resin which has a high refractive index, or adding high refractive index microparticles | fine-particles which have a refractive index higher than the refractive index of the binder resin used for an anti-glare layer, or using it together.

The binder resin having a high refractive index includes (1) a resin containing an aromatic ring, (2) a resin containing a halogenated element, for example, Br, I, Cl, etc., in addition to F, and (3) a resin containing atoms such as S, N, and P. And the like, and resins satisfying at least one of these conditions are preferable because of high refractive index. Examples of the resin of the above ① item include styrol resins such as polystyrene, polyethylene terephthalate, polyvinyl carbazole, and polycarbonate made of bisphenol A.

Examples of the resin of item ② include polyvinyl chloride, polytetrabromo bisphenol A glycidyl ether and the like, and the resin of item ③ is polybisphenol S glycidyl ether, polyvinyl pyridine and the like.

Examples of the high refractive index fine particles include ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.71), SnO ₂ , ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O ₃ (refractive index 1.63), and the like. Of these high refractive index fine particles, preferably ZnO, TiO ₂ , CeO ₂ or the like is used because the UV shielding effect is further imparted to the anti-glare antireflection film of the present invention. In addition, the use of SnO ₂ or ITO doped with acetylene improves the electronic conductivity, and prevents the adhesion of dust due to the antistatic effect, or the electromagnetic wave sealing effect when the anti-glare antireflection film of the present invention is used in a CRT. Good because you can get it. The particle size of the high refractive index fine particles is preferably 400 nm or more in order to make the antiglare layer transparent.

When ionizing radiation curable resin is used as a binder resin for an antiglare layer, the hardening method can be hardened by the conventional hardening method of an ionizing radiation curable resin, ie, irradiation with an electron beam or an ultraviolet-ray. For example, in the case of electron beam curing, various electron beams such as cockcroft-walton type, van de graaff type, resonant transformer type, insulated core transformer type, straight type, dynatron type, and high frequency type An electron beam having an energy of 50 to 1000 KeV, preferably 100 to 300 KeV, emitted from the accelerator is used, and in the case of ultraviolet curing, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp Ultraviolet light emitted from light rays such as light may be used.

Low refractive index layer

The low refractive index layer is formed so that it may contact on the said anti-glare layer or the hard-coat layer mentioned later. Although the refractive index n _L of this low refractive index layer is a range lower than the refractive index n _H of an anti-glare layer (or a hard-coat layer), as it becomes closer to following formula (3), antireflection effect improves, following formula (3) It is desirable to be close to the conditions of.

----------- (3)

The low refractive index material used for the formation of the low refractive index layer may be any one as long as it satisfies the above conditions, but the inorganic material can be preferably used since the hardness is high and the film can be formed by the vapor phase method. As a material for forming the low refractive index layer, for example, LiF (refractive index 1.4), MgF ₂ (refractive index 1.4), 3NaF-AlF ₃ (refractive index 1.4), AlF ₃ (refractive index 1.4), Na ₃ AlF ₆ (crystallization, refractive index) 1.33), inorganic materials such as SiO _x (x: 1.50 ≦ x ≦ 4.00, preferably 1.70 ≦ x ≦ 2.20) (refractive index of 1.35 to 1.48) and NaMgF ₃ (refractive index of 1.36) are used.

In the case where the low refractive index layer is formed on an antiglare layer having a fine concavo-convex surface, by forming a low refractive index layer, the low refractive index layer material is concentrated on the concave portion of the fine concavo-convex surface of the antiglare layer, and the surface of the low refractive index layer is flat. It is desirable to prevent this from happening. For this reason, it is preferable to form by a vapor phase method, for example, a vacuum vapor deposition method, sputtering method, reactive sputtering method, ion plating method, plasma CVD method, etc. in formation of a low refractive index layer. More preferably, forming the SiO _x (x: 1.50 ≦ x ≦ 4.00) film by plasma CVD is particularly favorable in terms of hardness and surface properties of the film, excellent adhesion to the resin layer, and other thermal damage to the transparent base film. Since it can reduce compared with the gas phase method, it is preferable. This SiO _x will be described in detail later.

As the low refractive index retention material, organic materials such as polymers into which fluorine atoms have been introduced are preferable because the refractive index is low at 1.45 or less, and polyvinylidene fluoride (refractive index n = 1.40), which is easy to handle as a resin which can be used as a solvent, can be used. Can be mentioned. When the polyvinylidene fluoride is used as the low refractive index organic material, the refractive index of the low refractive index layer is approximately 1.40. However, in order to lower the refractive index of the low refractive index layer, trifluoroethyl acrylate (refractive index n = 1.32) and Likewise, the low refractive index acrylate may be added in an amount of 10 parts by weight to 300 parts by weight, preferably 100 parts by weight to 200 parts by weight.

In addition, this trifluoroethyl acrylate is monofunctional, so that the film strength does not come out of the low refractive index layer. Thus, polyfunctional acrylate, for example, dipentaerythritol hexaacrylate (abbreviated as ionizing radiation curable resin) DPHA, tetrafunctional) is preferred. Although the film intensity | strength by this DPHA is so large that the addition amount is large, from the viewpoint of reducing the refractive index of a low refractive index layer, the addition amount is better, and it is recommended to add 1-50 weight part, Preferably it is 5-20 weight part.

The method of forming the low refractive index layer may be formed of a single layer or a multilayer by, for example, a gas phase method (vacuum deposition method, sputtering method, reactive sputtering method, ion plating method, plasma CVD method) with a low refractive index inorganic material on a high refractive index hard coating layer. The low refractive index resin composition or the low refractive index organic material containing the low refractive index inorganic material can be applied by a method of forming a single layer or a multilayer coating film.

Optical functional film

The SiO _x (x: 1.50 ≦ x ≦ 4.00) film used for the low refractive index layer is not limited to the use of the low refractive index layer, and can be widely used as an optical functional film. In particular, the SiO _x film formed by the CVD method, preferably by the plasma CVD method, has a higher density and higher gas barrier properties than the conventional vacuum vapor deposition film. In addition, it has excellent properties suitable for optical functional films. In particular, when the anti-reflection film in which the SiO _x film is formed by the plasma CVD method is laminated and used for the polarizing element because of excellent moisture resistance, there is an advantage that the moisture-proof function is imparted to the polarizing element which is weak to moisture.

Table 2 shows experimental data showing the superiority of the SiO _x film formed by the plasma CVD method. Examples of the film to be subjected to the moisture proof experiment include a coating film of a hard coating resin having a thickness of 7 μm on a triacetyl cellulose film (denoted as “TAC”) and a triacetyl cellulose film [“HC (7 μm) / TAC” To form a coating film of vinylidene fluoride having a thickness of 1 μm on the triacetyl cellulose film [expressed as “K coat: vinylidene fluoride (1 μm) / TAC”) or on a triacetyl cellulose film. A 1000 _x thickness SiO _x plasma CVD film was formed (indicated by "SiO _x (1000 kPa) / TAC"). Each of these films was measured for moisture permeability per day according to the moisture-proof experiment of JIS (Z0208) at a humidity of 90% and a temperature of 40 ° C.

Layer composition (top layer is left) Permeability (per day) TACHC (7 μm) TACK coat: vinylidene fluoride (1 μm) / TACSiO _x (1000 μs) / TAC 600 g / ㎡ 300 g / ㎡ 20 g / ㎡ 5 g / ㎡ or less

According to Table _{2, SiO x (1000Å) /} TAC has the best low in water vapor permeability if it can be seen that the moisture resistance is excellent. Although vinylidene fluoride (1 µm) / TAC has slightly good moisture resistance, it is not preferable to use it as an optical material because the coating film is soft and turns yellow over time.

In addition, when a dye or the like is used in the polarizing element or the other layers, the plasma CVD film has gas barrier properties, so that deterioration of the dye or the like can be prevented. The SiO _x film formed by the plasma CVD method becomes a scratch-resistant film because of its high density.

In addition, the plasma CVD method is relatively easy to change the x value of the SiO _x film as compared with the conventional vacuum vapor deposition film, and the plasma CVD method may be greater than 2, while the x of the normal vacuum vapor deposition film is less than two. Therefore, the SiO _x film formed by the plasma CVD method can be made to have a lower refractive index than a normal vacuum vapor deposition film, and the obtained film has an advantage of high transparency. In addition, the plasma CVD film has better adhesion with a substrate than a normal vacuum deposition film.

Table 3 shows the difference between the SiO _x film by vacuum deposition and the SiO _x film by plasma CVD.

Vacuum deposition Plasma CVD density Low (particles collide with each other to form a film with SiO _x agglomerates) High (SiO _x film after adhesion to substrate) content x <2 It exists also that x> 2. Oxygen content is higher than vacuum deposition. Gasbarrier Castle lowness height Transparency It is easy to become yellow. Transparent Refractive index height lowness Coefficient of friction height lowness

In the present invention, the silicon oxide film as the optical functional film is preferably made of a SiO _x film (x is 1.50 ≦ x ≦ 4.00) whose surface contact angle to water is 40 to 180 degrees. More preferably the contact angle is at least 70 degrees, particularly preferably at least 100 degrees. According to the findings of the present inventors, when the contact angle is 40 degrees or more, the antifouling property is improved, and a state suitable for use as an optical functional film is achieved.

In addition, the coefficient of kinetic friction of the SiO _x film is preferably 1 or less, more preferably 0.5 or less. The dynamic friction coefficient in this case is based on the measured value based on the method of JIS-K7125. As the coefficient of kinetic friction decreases, the lubricity on the surface of the membrane tends to increase, especially when it is 1 or less, and the scratch resistance or fracture resistance of the membrane surface increases, which is preferable.

The SiO _x film is preferably formed by CVD, preferably plasma CVD, as described above.

In the present invention, plasma CVD means a conventionally known method using plasma even in CVD. In general, plasma CVD uses electric energy together with thermal energy. That is, in plasma CVD, the source gas of the silicon oxide film to form is discharged in a CVD apparatus, and it plasma-forms, and film-forming reaction advances on the non-equilibrium state realized by this.

Particularly, in the present invention, this plasma CVD is performed under the following conditions, but it is preferable to form a silicon oxide film excellent in both optical properties and surface properties.

(a) Let organic siloxane be a raw material gas.

(b) The source gas is converted into plasma by discharge.

(c) CVD is carried out in the absence of an inorganic vapor deposition source.

(d) The film to be deposited is kept at a relatively low temperature.

(e) It is performed under the film forming conditions which exist in the SiO _x film | membrane in which undecomposed organosiloxane was produced | generated.

As the source gas, a silane or siloxane commonly referred to as an organic siloxane can be appropriately used as the organic siloxane. Specifically, methyltrimethoxysilane, dimethyl diethoxysilane, tetraethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyl trimethoxysilane, vinyl-tris (2-methoxyethoxy) silane, Tetramethoxysilane, trimethylethoxysilane, vinyltriacetoxysilane, ethyltriethoxysilane, tetrakis (2-ethylhexoxy) silane, vinyltrimethoxysilane, tetrakis (2-methoxyethoxy) silane , Methylphenyldimethoxysilane, tetrakis (methoxyethoxy ethoxy) silane, tetramethylsilane, dimethyldiethoxysilane, n-propyltrimethoxy silane, tetrakis (2-ethylbutoxy) silane, n-octyl Liethoxysilane, acetoxy propyltrimethoxysilane, tris (trimethylsiloxy) phenylsilane, octamethylcyclo tetrasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, 1,2,3,3-tetrakis (trimethylsiloxane Disiloxane, and pentamethyldisiloxane It can properly take advantage of the one or two or more.

In addition, in this invention, it is preferable not to use a solid inorganic silicon compound as a vapor deposition source. Further, by differentiating the present invention it is preferably carried out in the film forming conditions remaining in the SiO _x film of the raw material gas (organosiloxane) is generated. That is, the SiO _x film excellent in both optical properties and surface properties can be obtained by incorporation or removal of undecomposed organosiloxane into the silicon oxide film in which the raw gas is not completely decomposed, and in particular, the film forming condition is a contact angle of the film surface. It is advantageous to control the dynamic friction coefficient in a small range by increasing the.

In the process of forming SiO _x by plasma, the organic siloxane activated by the plasma collides with the substrate, and the organic siloxane adsorbed on the surface reacts with the activated organic siloxane or oxygen from the base layer. It is thought that the film grows while leaving and making a matrix of Si-O-Si. At this time, if the energy of the plasma is low or the concentration of the activated carbon in the plasma is low, the organic siloxane on the surface of the substrate is not completely decomposed, and the organic groups remain so that groups such as silicone rubber and silicon grease remain on the surface (some surfaces). It is thought that the property of water repellency or a friction coefficient becomes small by doing so.

However, when the decomposition of the organosiloxane is incomplete and the oxidation number of Si is small, the refractive index of the film formed inversely becomes large, and it is not practical as a low refractive index layer of the antireflection film. In addition, when the organic siloxane is completely decomposed and the organic group disappears from the surface, the refractive index becomes low, but the surface becomes hydrophilic, and contaminants easily stick to it, making it difficult to handle, increasing the friction coefficient, and easily causing scratches and the like, resulting in the surface layer of the antireflection film. It is necessary to pay attention to the control of the film formation conditions because the practicality becomes insufficient.

Hereinafter, the physical properties of the film formed by various methods are listed for reference.

Sample contact angle (℃) Friction index Refractive index Raw material SiO ₂ / HC / TAC 32 1.50 1.44 SiO 2 (Formation by bet-type plasma CVD) SiO _x / HC / TAC ① 50 1.10 1.42 HMDSO + O ₂ SiO _x / HC / TAC ② 104 0.44 1.44 HMDSO + O ₂ SiO _x / HC / TAC ③ 155 0.40 1.60 HMDSO + O ₂ (Formation by continuous plasma CVD) SiO _x / HC / TAC ① 55 0.45 1.42 HMDSO + O ₂ SiO _x / HC / TAC ② 102 0.47 1.44 HMDSO + O ₂ SiO _x / HC / TAC ③ 152 0.40 1.50 HMDSO + O ₂ (Formation by continuous plasma CVD, corona treatment on the surface) SiO _x / HC / TAC 59 0.92 1.44 HMDSO + O ₂ ( Formation by Vetch Plasma CVD) SiO _x / Hc / TAC 43.9 1.13 1.44 SiH 4 (Formation by vacuum deposition) SiO _x / Hc / TAC 11.2 1.12 1.50 SiOSiO _x / Hc / TAC 12.3 1.89 1.50 SiO Verification TAC 19

The meanings of the symbols in the table are as follows.

HC: hard coating layer

TAC: triacetyl cellulose

HMDSO: Hexamethyldisiloxane

SiO _x / HC / TAC: A structure in which HC and SiO _x layers are formed in order on the TAC layer

Different floor

In addition to each layer described above, the antireflection film of this invention can be further provided with the layer for providing various functionalities. For example, in order to improve the adhesion between the transparent base film and the hard coating layer, the hard coating layer and the antiglare layer may be separately provided to provide a primer layer or an adhesive layer on the transparent base film or to improve bead performance or anti-glare property. You may provide these, or each layer may be provided in multiple layers.

As described above, the refractive index of the other layer provided in the middle of the transparent base film and the antiglare layer is preferably set to the middle value of the refractive index of the transparent base film and the antiglare layer.

The method of forming another layer may be formed by applying it directly or indirectly on a transparent base film as mentioned above, and when embossing film (or fine unevenness | corrugation on the surface is formed in advance, in the case of transferring and forming a hard coat layer on a transparent base film), Another layer may be apply | coated and formed on the hard-coat layer formed on the formed embossing film), and then you may transfer to a transparent base film.

An adhesive agent or an adhesive may be apply | coated to the lower surface of the anti-glare antireflection film of this invention, and such an anti-reflection film can be used by making it stick to the surface of the object to be reflected.

Hard coating layer

As the binder resin usable in the hard coat layer, any resin (for example, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, etc.) can be used as long as there is transparency. In order to impart hard performance, the thickness of the hard coating layer is 0.5 µm or more, preferably 3 µm or more, so that the hardness can be maintained and hard performance can be imparted to the antireflection film.

In addition, in this invention, "having a hard performance" or "hard coating" means showing hardness more than H by the pencil hardness test shown by JISK5400.

In addition, in order to further improve the hardness of the hard coat layer, it is preferable to use a reaction curable resin, that is, a thermosetting resin and / or an ionizing radiation curable resin as the binder resin used in the hard coating layer. The thermosetting resin may be a phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea copolymer resin, silicon resin, Polysiloxane resin etc. are used, A hardening agent, such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. can be used for these resins as needed.

The ionizing radiation curable resin preferably has an acrylate-based functional group, for example, a relatively low molecular weight polyester resin, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, and a spiroacetal resin. Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polybutadiene resins, polythiol polyene resins and polyhydric alcohols, and ethyl (meth) acrylates, ethylhexyl (meth) acrylates, styrene, Monofunctional and polyfunctional monomers, such as methylstyrene and N-vinylpyrrolidone, for example, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, di Ethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) may be used containing an acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate with a relatively large amount.

Particularly suitable are mixtures of polyester acrylates and polyurethane acrylates. The reason is that the polyester acrylate is suitable for obtaining a hard coating because the coating film has a very high hardness, but the polyester acrylate alone has a low impact resistance and is soft, so that the polyurethane film has a high impact resistance and flexibility. It is using together acrylate. The compounding ratio of a polyurethane acrylate shall be 30 weight part or less with respect to 100 weight part of polyester acrylates. When this value is exceeded, the coating film becomes too flexible and hardness disappears.

Furthermore, in order to make the said ionizing radiation curable resin composition into an ultraviolet curable resin composition, there exist acetophenone, benzophenone, Michler's benzoyl benzoate, (alpha)-amyloxime ester, tetramethyl thiuram monosulfide, thioxane as a photoinitiator in it. As tones and photosensitizers, n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used. In particular, in this invention, it is preferable to mix urethane acrylate as an oligomer, dipentaerythritol hexa (meth) acrylate, etc. as a monomer.

You may contain 10 weight part or more and 100 weight part or less of solvent-drying resin with respect to 100 weight part of ionizing radiation curable resins. As the solvent-drying resin, a thermoplastic resin is mainly used. Solvents to be added to the ionizing radiation curable resin As the type of the dry thermoplastic resin is usually used, in particular, a solvent to be used when a mixture of polyester acrylate and polyurethane acrylate is used as the ionizing radiation curable resin. As the dry resin, polymethacrylate methyl acrylate or polymethacrylate butyl acrylate can keep the hardness of the coating film high. In addition, in this case, since the refractive index with the main ionizing radiation curable resin is approximated, it is advantageous in terms of transparency, in particular, low haze value, high transmittance or compatibility, without impairing the transparency of the coating film.

Moreover, especially when using cellulose resins, such as a triacetyl cellulose, as a transparent base film, cellulose, such as nitro cellulose, acetyl cellulose, cellulose acetate propionate, ethyl hydroxyethyl cellulose, is a solvent-drying resin contained in an ionizing radiation curable resin. System resins are advantageous in terms of adhesion and transparency of the coating film.

The reason for this is that when toluene is used as the solvent in the cellulose-based resin, the toluene which is a non-soluble solvent of triacetyl cellulose, which is a transparent base film, is used. Even if coated, the adhesion between the transparent base film and the coating film resin can be improved, and since this toluene does not dissolve triacetyl cellulose, which is a transparent base film, the surface of the transparent base film is not whitened and transparency can be maintained. There is an advantage.

In the formation of the hard coating layer, a coating method or a transferring method may be used. In the method by an electron coating, it is possible to apply | coat and form the resin composition for the said hard-coat layers by the gravure reverse coating method etc. directly or through a different layer to a transparent base film. In the latter method, the resin composition for the hard coating layer is coated on a release film having a smooth surface by, for example, a gravure reverse coating method or the like to form a coating film, and at least on the front and rear surfaces of the transparent base film. The release film having a coating film formed in the above process on one side or directly through another layer was laminated with the coating film inward, and the laminate was subjected to heat treatment and / or ionizing radiation treatment to cure the coating film. And then peeling the ionizing release film from the laminate to form a hard coating layer or curing the coating on the release film by heat treatment and / or ionizing radiation treatment before the lamination is performed. An adhesive layer is provided on at least one of the front and back surfaces of the transparent base film. Pieces and laminated to a release film and a coating film formed cured coating film of the process to the inside, then the water from the laminate by peeling off the release film, it is possible to form a hard coating layer.

Since the hard coat layer in this invention is a coating film by application | coating, the film thickness is 0.5 micrometer or more as mentioned above, and the film | membrane by a vapor phase method (for example, vacuum vapor deposition, sputtering, ion plating, plasma CVD method, etc.). Thicker than The antireflection film thus obtained is given hard performance.

In order to increase the refractive index of the hard coating layer, a binder resin having a high refractive index may be used, or high refractive index fine particles having a refractive index higher than that of the binder resin used for the hard coating layer may be added to the binder resin, or used in combination.

The binder resin having a high refractive index includes (1) a resin containing an aromatic ring, (2) a resin containing a halogenated element, for example, Br, I, Cl, etc., in addition to F, and (3) a resin containing atoms such as S, N, and P. And the like, and resins satisfying at least one of these conditions are preferable because of high refractive index.

Examples of the resin of the above ① may include styrol resins such as polystyrene, polyethylene terephthalate, polyvinyl carbazole, polycarbonate made of bisphenol A, and the like. Examples of the resin of item ② include polyvinyl chloride, polytetrabromo bisphenol A glycidyl ether and the like, and the resin of item ③ is polybisphenol S glycidyl ether, polyvinyl pyridine and the like.

Examples of the high refractive index fine particles include ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.71), SnO ₂ , ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O ₃ (refractive index 1.63), and the like. Of these high refractive index fine particles, preferably ZnO, TiO ₂ , CeO ₂ or the like is used because the UV shielding effect is further imparted to the antireflection film of the present invention. In addition, the use of SnO ₂ or ITO doped with acetylene improves the electron conductivity, and prevents the adhesion of dust due to the antistatic effect, or the electromagnetic wave sealing effect when the antireflection film of the present invention is used in the CRT. It is good because there is. The particle size of the high refractive index fine particles is preferably 400 nm or more in order to make the hard coat layer transparent.

When ionizing radiation curable resin is used as a binder resin for a hard coat layer, the hardening method can be hardened by the conventional method of hardening ionizing radiation curable resin, ie, irradiation with an electron beam or an ultraviolet-ray. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as cokecroft-walton type, vandegraph type, resonant transformer type, insulation core transformer type, linear type, dynatron type, and high frequency type, Preferably, an electron beam having an energy of 100 to 300 KeV is used, and in the case of ultraviolet curing, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, ultraviolet light from a metal halide lamp, etc. may be used. Can be.

Antireflection at the interface

FIG. 1 shows a laminated film in which a SiO _x deposition film 3 having a refractive index of 1.46 is formed on a triacetyl cellulose film having a refractive index of 1.49 (abbreviated as TAC base film) 1. The spectral reflectance curve of this laminated | multilayer film is shown in FIG.

FIG. 2 shows a laminated film having a hard coating layer (abbreviated HC layer) 2 having a refractive index of 1.49 and a SiO _x deposition film having a refractive index of 1.46 thereon on a TAC base film 1 having a refractive index of 1.49. The spectral reflectance curve of this laminated | multilayer film is shown in FIG.

FIG. 3 shows the increase in the refractive index of the HC layer in the laminated film of FIG. 2, the HC layer 2 having a film thickness of 6 μm having a refractive index of 1.55 on a TAC base film having a refractive index of 1.49, and a refractive index thereon. The laminated film in which the SiO _x vapor deposition film 3 which is this 1.46 was formed is shown. The spectral reflectance curve of this laminated | multilayer film is shown in FIG. When the spectral reflectance curve of FIG. 7 is combined with that of FIG. 6, the curve of FIG. 6 overlaps with the highest point in the wave height of FIG. 7 near the target wavelength of 550 nm (the wavelength which is said to be the most sensitive to the human eye). In other wavelength portions of 7, the reflectance is lowered as the crest is lowered.

Thus, it can be seen that the SiO _x deposited layer and the substrate TAC film, the refractive index of the HC layer of the medium when above the other layer, can be subjected to anti-reflection at the interface.

Moreover, the pitch of crest in the spectral reflectance curve of FIG. 8 shows that it becomes large when the film thickness becomes thin. This case is also found to be the same as the reflectance tendency shown in FIG. 5 and FIG. 8. In addition, the laminated constitution of the laminated | multilayer film which has the spectral reflectance curve of FIG. 8 consists of a base material TAC (refractive index 1.49) / HC layer (film thickness 3 micrometers, refractive index 1.55) / antireflection layer (film thickness 95 nm, refractive index 1.46).

FIG. 9: shows the spectral reflectance curve in the case where the refractive index of HC layer was raised to 1.65 in the laminated | multilayer film of FIG. In this way, when the refractive index of the HC layer is increased, the crest increases (deepens), and the reflectance can be reduced by that much.

Fig. 4 shows a HC layer having a refractive index of 1.65 on which a primer layer 4 having a refractive index of 1.55 is provided on a TAC base film 1 having a saponified refractive index of 1.49, and a resin having ZnO dispersed therein as high refractive index particles thereon. (2) to form, will also showing a laminated film formed of the SiO _x deposited film (3) is a refractive index of 1.46 on top of it. Here, this primer layer 4 was made into the layer which is thinner than HC layer 2, and the refractive index is about the middle of each refractive index of HC layer 2 and TAC base film 1. As shown in FIG. The spectral reflectance curve of this laminated film is shown in FIG. According to the spectral reflectance curve of Fig. 10, the spectral reflectance is one also being a value between 9 wavelength, the target wavelength 550 nm vicinity of In is reduced, the height of wave laminated material of low refractive index is lower than the SiO _x to the outermost surface It seems to have caused an effect.

However, since the HC layer and the primer layer are coating coating films such as a roll coat or the like, it is considered that the interface between the HC layer-transparent base film, the interface between the HC layer-primer layer, the interface between the primer-transparent base film is not clear, It is difficult to produce a difference in refractive index, and in fact, a wave height represented by a spectral reflectance curve is hard to occur.

11 shows the spectral reflectance curves of the laminated film of TAC base film (refractive index 1.49) / high refractive index hard coating layer (refractive index 1.62) / low refractive index (refractive index (1.46)), and for the comparison, only the TAC base film and the TAC base film The spectral reflectance curve of the laminated | multilayer film which consists of (refractive index 1.49) / normal hard-coat layer (refractive index 1.49) / low refractive index (refractive index 1.46) was also shown.

According to FIG. 11, the digging is almost lost in the short wavelength side.

Polarization Wave and Liquid Crystal Display

By laminating the anti-glare antireflective film of this invention to a polarizing element, it can be set as the polarizing plate in which anti-reflective property was improved. A polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, a saponified film of ethylene-vinyl acetate copolymerization system, etc. dyed and stretched with iodine or dye can be used for this polarizing element. In order to increase the adhesiveness in accordance with this laminate treatment and to prevent static electricity, when the transparent base film of the anti-glare antireflection film is, for example, a triacetyl cellulose film, saponification is applied to the triacetyl cellulose film. This saponification treatment may be before or after any triacetyl cellulose hard coating.

An example of the polarizing plate in which the anti-glare antireflection film of this invention was used is shown by FIG. In the drawings, a laminate composed of a TAC film (abbreviation of a triacetyl cellulose film) 19, a high refractive index antiglare layer 12, and a low refractive index layer 13 corresponds to the antiglare antireflection film of the present invention. The antireflection film is laminated on the polarizing element 20, while the TAC film 19 is laminated on the other side of the polarizing element 20. An adhesive bond layer is provided between each layer of this polarizing plate as needed. In particular, it is preferable to provide an adhesive layer between the high refractive index antiglare layer 12 and the TAC film 19 as a transparent base film. The layer structure of the polarizing plate shown in FIG. 19 can be easily displayed with a TAC film // polarizing element / anti-glare antireflection film.

An example of the liquid crystal display device in which the anti-glare antireflection film of this invention was used is shown by FIG. The polarizing plate of the laminated constitution which consists of a polarizing plate shown in FIG. 19, ie, a TAC film / polarizing element / anti-glare antireflection film on the liquid crystal display element 21 is laminated, and TAC is provided on the other side of the liquid crystal display element 21. The polarizing plate of the laminated constitution which consists of a film / polarizing element / TAC film is laminated. In the liquid crystal display of FIG. 20, a high refractive index layer may be further formed on the TAC film 19 side of the lowermost surface, and a low refractive index layer may be formed outside. In the STN type liquid crystal display device, a phase difference plate is inserted between the liquid crystal display element 21 and the polarizing plate. An adhesive layer is provided between each layer of this liquid crystal display device as needed.

14B shows an example of a polarizing plate in which an antireflection film according to another aspect of the present invention is used. In the figure, 150 is an antireflection film of the present invention, and as described above, the TAC film (abbreviation of triacetyl cellulose film) 170, the high refractive index hard coating layer 120, and the low refractive index layer 130 as a transparent base film are described. Formed. The antireflection film 15 is laminated on the polarizing element 160, and on the other hand, the TAC film 170 is laminated on the other side of the polarization small intestine 160. An adhesive bond layer is provided between each layer of this polarizing plate as needed. In particular, it is preferable to provide an adhesive layer between the high refractive index hard coating layer 120 and the TAC film 170 as a transparent base film. The layer structure of the polarizing plate shown in FIG. 14B can be simply represented by a TAC film / polarizing element / antireflection film. In addition, as another example of the polarizing plate in which the antireflection film of this invention was used, the antireflection film 150 of this invention may be laminated on both surfaces of the polarizing element 160.

An example of the liquid crystal display device in which the antireflection film of this invention was used is shown by FIG. On the liquid crystal display element 180, a polarizing plate shown in FIG. 14B, that is, a layered polarizing plate made of a TAC film, a polarizing element, and an antireflection film, is laminated, and a TAC film is provided on the other side of the liquid crystal display element 180. The polarizing plate of the laminated constitution which consists of a / polarizing element / TAC film is laminated. In the liquid crystal display of FIG. 15B, a hard coating layer 120 may be further formed on the lowermost TAC film 170 side, and a low refractive index layer 130 may be formed outside the high refractive index hard coating layer 120. . In the liquid crystal display shown in Fig. 15B, the backlight is irradiated from the bottom of Fig. 15B. In the STN type liquid crystal display device, a retardation plate is inserted between the liquid crystal display element and the polarizing plate. An adhesive bond layer is provided between each layer of this liquid crystal display device as needed.

Example A1

A triacetyl cellulose film (FT-UV-80: trade name, manufactured by Fuji Photo Film Co., Ltd., refractive index 1.49) having a thickness of 80 µm was prepared as a transparent base film. On the other hand, ZnO ultrafine particles having a refractive index of 1.9 (ZS-300: trade name, manufactured by Sumitomo Cement Co., Ltd.) and ionizing radiation curable resins having a refractive index of 1.52 (HN-3: trade name, manufactured by Mitsubishi Yuka Corporation) were mixed at a weight ratio of 2: 1. It was. The obtained resin composition was applied to the above-described triacetyl cellulose film by gravure reverse coating so as to have a film thickness of 7 μm / dry and dried to remove the solvent.

After laminating a matte PET film (X-45: trade name, manufactured by Toray Industries, Inc., 23 µm) having a fine concavo-convex surface on the triacetyl cellulose film having the above-mentioned dry resin layer through the resin layer, an electron beam was used. Irradiation of 4 Mrad at 150 KV cured the resin layer, and fine unevenness was formed on the surface of the resin layer by peeling off the mat PET film. Next, SiO _x was deposited on the fine concavo-convex surface of the resin layer by plasma CVD to form an SiO _x layer having a film thickness of 100 nm (refractive index of 1.46) to prepare an anti-glare antireflection film of Example 1.

The total light transmittance of the obtained anti-glare antireflection film was 93.5%, haze value was 9.0, and it was excellent in anti-reflective property and anti-glare property. Moreover, the surface pencil hardness was 3H and the hard performance was also excellent.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained by the said Example. 11 is a transparent base film, 12 is a high refractive index antiglare layer imparted hard performance, and 13 is a low refractive index layer.

Example A2

A triacetyl cellulose film (FT-UV-80: trade name, manufactured by Fuji Photo Film Co., Ltd., refractive index 1.49) having a thickness of 80 μm was immersed in a 2N KOH solution at 60 ° C. for 1 minute to saponify it, and a transparent base film (refractive index 1.49) It was made. On this transparent substrate film, a primer (refractive index: 1.55) prepared by adding 10 parts by weight of isocyanate as a curing agent to the resin was added to a vinyl chloride acetate resin (SBP Primer-G: trade name, manufactured by Daiichi Seka Co., Ltd.). The coating was applied with a gravure reverse coating to have a thickness of 탆 / dry, dried at 60 ° C. for 1 minute, and then etched at 40 ° C. for 2 days. On the obtained gravure layer, a hard coating layer having irregularities on the surface was formed in the same manner as in Example 1, and an SiO _x layer was formed thereon to prepare an anti-glare antireflection film of this example.

The total light transmittance of the obtained anti-glare antireflection film was 94%, and the haze value was 9.0, and it was excellent in anti-reflection property and anti-glare property. Moreover, the surface pencil hardness was 3H, and the hard performance was also excellent.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained by the present Example. 11 is a transparent base film, 14 is a primer layer, 12 is a high refractive index antiglare layer imparted with hard performance, and 13 is a low refractive index layer.

Example A3

ZnO ultrafine particles (ZS-300: trade name, product of Sumitomo Cement Co., Ltd., refractive index 1.9) and ionizing radiation curable resin (on a mat PET film (X-45: trade name, manufactured by Toray Industries, Inc., thickness: 23 µm)) having fine irregularities on the surface HN-2: The resin composition obtained by mixing the trade name, product of Mitsubishi Yuka, refractive index 1.54) in a weight ratio of 2: 1 was coated with a gravure reverse coating so as to have a thickness of 5 μm / dry, and then the electron beam was irradiated with 3 Mrad at 150 KV to cure the coating film. .

Apart from the mat PET film having the resin layer formed thereon, on the transparent substrate film used in Example 1, drying is performed by adding 10 parts by weight of isocyanate to the urethane adhesive (Takenate A310) as a curing agent to the adhesive resin. Laminated resin was apply | coated so that it might become 2 micrometers / dry, and the solvent in a coating film was dried and removed.

The matte PET film in which the resin layer manufactured above was formed on the transparent base film in which the obtained adhesive bond layer was formed was laminated through the resin layer. Subsequently, the adhesive layer was completely cured by etching at 50 ° C. for 3 days, and then the mat PET film was peeled off. The present embodiment by forming a SiO _x layer on the resin layer having a fine uneven surface obtained courtesy room to prepare a manifest anti-reflection film.

The total light transmittance of the obtained anti-glare antireflection film was 93.8%, and the haze value was 9.0, and it was excellent in anti-reflection property and anti-glare property. Moreover, the surface pencil hardness was 2H, and the hard performance was also excellent.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained by the said Example. 11 is a transparent base film, 15 is an adhesive layer, 12 is a high refractive index anti-glare layer provided with hard performance, and 13 is a low refractive index layer.

Example A4

ZnO ultrafine particles (ZS-300: trade name, product of Sumitomo Cement Co., Ltd., refractive index 1.9) and ionizing radiation curable resin (on a mat PET film (X-45: trade name, manufactured by Toray Industries, Inc., thickness: 23 µm)) having fine irregularities on the surface HN-2: The resin composition obtained by mixing the trade name, product of Mitsubishi Yuka, refractive index 1.54) in a weight ratio of 2: 1 was applied with a gravure reverse coating so that the film thickness was 5 μm / dry, and then the electron beam was irradiated with 3 Mrad at 150 KV to obtain water. The strata were semi-hardened.

Apart from the mat PET film having the semi-cured resin layer formed thereon, an ionizing radiation curable resin (EXG40-9: trade name, manufactured by Daiichi Seka Co., Refractive Index 1.50) was used on the triacetyl cellulose film used in Example A1. After coating with gravure reverse coating so as to be µm / dry, drying the solvent of the coating film, laminating the mat PET film and the resin layer formed with the semi-cured resin layer prepared above, and irradiating the electron beam with 5 Krad at 150 KV The stratum was completely cured to remove the matte PET. The SiO _x layer in the same manner as Example 1 to be a resin layer having a fine uneven surface obtained was prepared in the embodiment room overt anti-reflection film was formed to a thickness of 100nm membrane.

The total light transmittance of the obtained anti-glare antireflection film was 93.5%, haze value was 9.0, and it was excellent in anti-reflection property and anti-glare property. Moreover, the surface pencil hardness was 3H, and the hard performance was also excellent.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained by the said Example. 11 is a transparent base film, 16 is a clear hard coating layer, 12 is a high refractive index antiglare layer imparted with hard performance, and 13 is a low refractive index layer.

Example A5

The saponified triacetyl cellulose film was primed as shown in Example A2 above as a transparent base film. Using this primer-treated film, it was carried out in the same manner as in Example A4, and the anti-glare antireflection film of Example A5 was prepared by forming a clear hard coating layer, a high refractive index antiglare layer and a low refractive index layer imparted with hard performance. .

The total light transmittance of the obtained anti-glare antireflection film was 93.5%, and the haze value was 9.0, and it was excellent in anti-reflection property and anti-glare property. Moreover, the surface pencil hardness was 3H, and the hard performance was also excellent.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained by the said Example. 11 is a transparent base film, 14 is a primer layer, 16 is a clear hard coating layer, 12 is a high refractive index antiglare layer provided with hard performance, and 13 is a low refractive index layer.

Example A6

ZnO ultrafine particles (ZS-300: trade name, product of Sumitomo Cement, Refractive Index 1.9) and touch drying on a mat PET film (X-45: trade name, manufactured by Toray Industries, Inc., 23 µm) having fine irregularities on the surface When the ionizing radiation curable resin (H-4000: trade name, product of Mitsubishi Yuka, refractive index 1.5) is mixed in a weight ratio of 2: 1 and coated with a gravure reverse coating so as to have a film thickness of 3 µm / dry, and then dried on a touch. It was dried at 60 ° C. for 1 minute.

Apart from the mat PET film with the resin layer dried on the touch, an ionizing radiation curable resin (EXG40-9: trade name, manufactured by Daiichi Seka Co., Ltd., refractive index 1.50) on the triacetyl cellulose film was 3 μm / dry. After applying the gravure reverse coating, and drying the solvent of the coating film, after laminating the mat PET film and the resin layer formed with the dried resin layer with respect to the touch prepared above, the electron beam was irradiated with 5Mrad at 150KV and the resin layer was Fully cured to release the matte PET film. The SiO _x layer was deposited on the resin layer having fine irregularities on the surface thus formed in the same manner as in Example 1 to form an SiO _x layer with a film thickness of 100 nm to prepare the anti-glare antireflection film of the above embodiment.

The total light transmittance of the obtained anti-glare antireflection film was 93.5%, and the haze value was 9.0, and it was excellent in anti-reflection property and anti-glare property. Moreover, the surface pencil hardness was 2H, and the hard performance was also excellent.

Example A7

The saponified triacetyl cellulose film was primed as shown in Example A2 above as a transparent base film. Using this primer-treated film, it was carried out in the same manner as in Example A4, and the anti-glare antireflection film of Example 7 was prepared by forming a clear hard coating layer, a high refractive index antiglare layer and a low refractive index layer imparted with hard performance. .

The total light transmittance of the obtained anti-glare antireflection film was 93.5%, and the haze value was 9.0, and it was excellent in anti-reflection property and anti-glare property. Moreover, the surface pencil hardness was 2H, and the hard performance was also excellent.

Example A8

Methyl polymethacrylate beads and ionizing radiation curable resins having a particle size of 5 µm on a triacetyl cellulose film (FT-UV-80: trade name, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 µm (HN-2: trade name, Gravure reverse so that the thickness of the resin mixed with Mitsubishi Yuka, refractive index 1.54) and ZnO ultrafine particles (ZS-300: trade name, Sumitomo Cement Co., Ltd., refractive index 1.9) with a weight ratio of 1:10:20 is 6 µm / dry. The coating was applied, and the electron beam was irradiated with 4 Mrad at 150 KV. As for the surface of the cured coating film formed on the triacetyl cellulose film, the fine unevenness | corrugation was formed by the fine particle of the methyl methacrylate bead. SiO _x was deposited on the cured coating film in the same manner as in Example A1 to form an SiO _x film having a thickness of 100 nm to prepare an anti-glare antireflection film of Example A8.

The total light transmittance of the obtained anti-glare antireflection film was 94%, haze value was 5.0, and it was excellent in anti-reflective property and anti-glare property. Moreover, the surface pencil hardness was 3H and the hard performance was also excellent.

It is sectional drawing which shows the laminated constitution of the anti-glare antireflection film obtained by the said Example. 11 is a high refractive index antiglare layer imparted with hard performance having a transparent base film, 17 is a mat material 18, and 13 is a low refractive index layer.

Example A9

As shown in Example A2, the saponified triacetyl cellulose film was used as a transparent base film, and then primed in the same form. Using this primer-treated film, it was carried out in the same manner as in Example A8 to form a high refractive index antiglare layer and a low refractive index layer imparted with hard performance to prepare an antiglare antireflection film of this example.

The total light transmittance of the obtained anti-glare antireflection film was 94%, the haze value was 5.0, and it was excellent in anti-reflective property and anti-glare property. Moreover, the surface pencil hardness was 2H, and also the hard performance was excellent.

18 is a cross-sectional view showing the layer structure of the anti-glare antireflection film obtained in the present example. 11 is a high refractive index anti-glare layer given with the hard performance which has a transparent base film, 14 is a primer layer, 17 is a mat material 18, and 13 is a low refractive index layer.

Example A10

Electron beam-curable resin (HN-3: trade name, Mitsubishi Yuka) and ZnO ultrafine particles (ZS-300) on a PET film (T-600: trade name, manufactured by DIA Hoyle Co., Ltd., 50 µm thick) having fine irregularities on its surface. , A resin manufactured by Sumitomo Cement Co., Ltd., with a refractive index of 1.9) in a weight ratio of 2: 1, was coated with a gravure reverse coat to be 7 μm / dry, and the electron beam was irradiated with 4 Mrad at an acceleration pressure of 175 KV to cure the resin layer. A high refractive index antiglare layer was formed. An adhesive (Takelac: trade name, product of Takeda Pharmaceutical Co., Ltd.) is coated on the high refractive index antiglare layer of the obtained PET film by gravure reverse coating to form an adhesive layer. Subsequently, a triacetyl cellulose film (FT-Uv) is formed through the adhesive layer. -80: Trade name, Fujifilm, thickness 80 micrometers) were laminated, and after etching at 40 degreeC for 3 days, PET film was peeled off and the high refractive index antiglare layer was transferred to the triacetyl cellulose film. The surface of the high refractive index antiglare layer on the triacetyl cellulose is the same as the surface shape of the PET film, and has fine irregularities. An additional high-refractive-index anti-glare layer on the SiO _x to be 100nm by a plasma CVD method to form a plasma CVD film of the low refractive index to give the present embodiment room overt anti-reflection film.

The total light transmittance of the obtained anti-glare antireflection film of this example was 94.5%, the haze value was 0.7, and the antireflection property was excellent. Moreover, the surface pencil hardness was 3H, and the hard performance was also excellent.

Comparative Example A

A triacetyl cellulose film (FT-UV-80: trade name, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 µm was prepared as a substrate, and an ionizing radiation curable resin (EXG40-9: trade name, product of Daiichi Seika Co., Ltd.) was prepared on the film. It was coated with gravure reverse coating to 7 μm / dry and the solvent was dried. After laminating a matte PET film (X-45: trade name, manufactured by Toray Industries, Inc., 23 µm in thickness) having fine irregularities on the surface of the dried resin, the resin layer was cured by irradiating electron beams at 150 KV at 4 Mrad. Next, the matte PET film was peeled off, and SiO _x was deposited on the fine concavo-convex surface of the resin surface to form a SiO _x film having a film thickness of 100 nm.

The total light transmittance of the film of the obtained comparative example was 91.8%, the haze value was 9.0, and antireflection property was reduced compared with the said Example. Moreover, the surface pencil hardness was 2H.

Example A11

The following samples were prepared.

Sample contact angle (℃) Friction index Refractive index Raw material (Formation by bet-type plasma CVD) SiO _x / HC / TAC ① 50 1.10 1.42 HMDSO + O ₂ SiO _x / HC / TAC ② 104 0.44 1.44 HMDSO + O ₂ SiO _x / HC / TAC ③ 155 0.40 1.60 HMDSO + O ₂

ZnO coating liquid (ZS-300: trade name, Sumitomo Cement Co., Ltd.) and binder resin (40-9: Trade name: Dainichisei) on a release film (MC-19: trade name, manufactured by Reiko Corporation) treated with acrylic-melamine resin on the surface CASA) was mixed with a solid content weight ratio of 2: 1, diluted with a solution of methyl ethyl ketone: toluene = 1: 1 in a solid content of 30% by weight, and applied to a dry film thickness of 6 탆 with a wire bar and dried. Cured with EB. In addition, an adhesive (subject: Takeda A-310 manufactured by Takeda Pharmaceutical Co., Ltd. and Takenate A-3 manufactured by Takeda Pharmaceutical Co., Ltd. as a curing agent in 6: 1) is applied to a film thickness of 4 μm when dried, and then the coated release The base material TAC film used for a product by a film and a final group was laminated, and it hardened | cured by etching at 40 degreeC for 2 days. Then, the release film was peeled off and subjected to CVD of SiOx under the following conditions to obtain an antireflection film.

Batch type plasma CVD apparatus film forming condition

Vacuum degree: 0.45 Torr

Power (Frequency): 100 W (13.56 MHz)

Process gas composition ratio: He: O ₂ : monomer = 100: 100: 1

Process gas flow rate: He + monomer, 25 sccm, O ₂ , 25 sccm

Vessel type plasma CVD apparatus film forming condition②

Vacuum degree: 0.45 Torr

Power (Frequency): 100 W (13.56 MHz)

Process gas composition ratio: He: O ₂ : monomer = 100: 100: 4.6

Process gas flow rate: He + monomer, 25 sccm, O ₂ , 25 sccm

Batch type plasma CVD apparatus film forming condition③

Vacuum degree: 0.45 Torr

Power (Frequency): 100 W (13.56 MHz)

Process gas composition ratio: He: O ₂ : monomer = 100: 100: 10

Process gas flow rate: He + monomer, 25 sccm, O ₂ , 25 sccm

Evaporator: Number using parts other than Enelva

Ball device

Deposition material: HMDSO (hexamethyldisiloxane, monomer)

_{Acid) + O 2 (HMDSO: O} 2 by the change in spring

To produce ①, ②, ③

Carrier Gas: He

Substrate Temperature: Room Temperature

Deposition Rate: 1.3Å / s

Film thickness: 1000Å

Example A12

The following samples were prepared.

Sample contact angle (℃) Friction index Refractive index Raw material (Formation by continuous plasma CVD) SiO _x / HC / TAC ① 83 0.90 1.42 HMDSO + O ₂ SiO _x / HC / TAC ② 102 0.47 1.44 HMDSO + O ₂ SiO _x / HC / TAC ③ 162 0.40 1.50 HMDSO + O ₂ (Formation by continuous plasma CVD, corona treatment on the surface) SiO _x / HC / TAC 58 0.92 1.44 HMDSO + O ₂

ZnO coating liquid (ZS-300: trade name, Sumitomo Cement Co., Ltd.) and binder resin (40-9: Trade name: Die) on a mat PET film having a film thickness of 25 μm having fine unevenness on the surface Nichi Seika Co., Ltd.) was mixed with a solid content weight ratio of 2: 1 to 30% by weight of solids with methyl ethyl ketone: toluene = 1: 1 solution, applied with a weir bar to a dry film thickness of 6 μm, and dried with dry EB. Cured. In addition, an adhesive (subject: Takeda A-310 manufactured by Takeda Pharmaceutical Co., Ltd. and Takenate A-3 manufactured by Takeda Pharmaceutical Co., Ltd. as a curing agent in 6: 1) is applied to a film thickness of 4 μm when dried, and then the coated release The base material TAC film used for a product by a film and a final group was laminated, and it hardened | cured by etching at 40 degreeC for 2 days. Then, the matted PET film was peeled off and CVD of SiOx was carried out by changing the conditions of the monomer HMDSO: O2 as follows to obtain an antireflection film.

Further, (2) further imparted hydrophilicity by corona discharge treatment to decrease the contact angle with water and increase the friction coefficient.

Continuous Plasma CVD Film Formation Conditions

Vacuum degree: 5 × 10 ^-2 Torr

Power (Frequency): 30 kW (40 kHz)

Process gas composition ratio: He: O ₂ : monomer = 16: 90: 1

Machine speed: 10m / min

Continuous Plasma CVD Film Formation Conditions

Vacuum degree: 5 × 10 ^-2 Torr

Power (Frequency): 30 kW (40 kHz)

Process gas composition ratio: He: O ₂ : monomer = 16: 16: 1

Machine speed: 10m / min

Continuous Plasma CVD Film Formation Conditions

Vacuum degree: 5 × 10 ^-2 Torr

Power (Frequency): 30 kW (40 kHz)

Process gas composition ratio: He: O ₂ : monomer = 16: 6: 1

Machine speed: 10m / min

Reference Example A1

The following samples were prepared.

Sample contact angle (degrees) Friction coefficient Refractive index Raw material (Variation by Vetch Plasma CVD) SiO _x / HC / TAC 43.9 1.13 1.44 SiH ₄

ZnO coating liquid (ZS-300: trade name, Sumitomo Cement Co., Ltd.) and binder resin (40-9: Trade name :) on a release film (MC-19: trade name, manufactured by Daiichi Seika Co., Ltd.) treated on the surface thereof with acrylic-melamine resin. Dainichi Seika Co., Ltd.) was mixed with a solid content weight ratio of 2: 1 to 30% by weight of solid with methyl ethyl ketone: toluene = 1: 1 solution, and applied with a weir bar to a dry film thickness of 6 μm, followed by drying EB. Hardened. In addition, an adhesive (subject: Takeda A-310 manufactured by Takeda Pharmaceutical Co., Ltd. and Takenate A-3 manufactured by Takeda Pharmaceutical Co., Ltd. as a curing agent in 6: 1) is applied to a film thickness of 4 μm when dried, and then the coated release The film and the substrate TAC film finally used in the product were laminated and cured by etching at 40 ° C. for 2 days. Then, the release film was peeled off and CVD of SiOx was carried out under the following conditions to obtain an antireflection film.

Batch type plasma CVD apparatus film forming condition③

Vacuum degree: 0.45 Torr

Power (Frequency): 100 W (13.56 MHz)

Process gas composition ratio: He: O ₂ : SiH ₄ = 100: 100: 4.6

Process gas flow rate: He + SiH ₄ , 25 sccm, O ₂ , 25 sccm

Evaporator: Number using parts other than Enelva

Ball device

Deposition Material: SiH4 + O ₂

Carrier Gas: He

Substrate Temperature: Room Temperature

Deposition Rate: 1.3Å / s

Film thickness: 1000Å

Reference Example A2

The following samples were prepared.

Sample contact angle (degrees) Friction coefficient Refractive index Raw material (Formation by means of evaporation) SiO _x / HC / TAC 32 1.50 1.44 SiO ₂

ZnO coating liquid (ZS-300: trade name, Sumitomo Cement Co., Ltd.) and binder resin (40-9: trade name: Die) on a release film (MC-19: trade name, manufactured by Daiichi Seika Co., Ltd.) treated with an acrylic-melamine resin on the surface. Nichi Seika Co., Ltd.) was mixed with a solid content weight ratio of 2: 1 to 30% by weight of solids with methyl ethyl ketone: toluene = 1: 1 solution, applied with a weir bar to a dry film thickness of 6 μm, and dried with dry EB. Cured. In addition, an adhesive (subject: Takeda A-310 manufactured by Takeda Pharmaceutical Co., Ltd. and Takenate A-3 manufactured by Takeda Pharmaceutical Co., Ltd. as a curing agent in 6: 1) is applied to a film thickness of 4 μm when dried, and then the coated release The film and the substrate TAC film finally used in the product were laminated and cured by etching at 40 ° C. for 2 days. Then, the release film was peeled off and vapor deposition of SiO ₂ was performed under the following conditions to obtain an antireflection film.

Evaporator: Cyntron BMC-700

Deposition Material: SiO ₂

Vacuum: 4 × 10- ² torr

Substrate Temperature: Room Temperature

EB Heat Deposition

Acceleration Voltage: 8 kV

Emisson: 40 mA

Deposition Rate: 4Å / s

Film thickness: 1000Å

Reference Example A3

The following samples were prepared.

Sample contact angle (degrees) Friction coefficient Refractive index Raw material (Film deposition by vacuum deposition method) SiO _x / HC / TAC 11.2 1.12 1.50 SiO SiO _x / HC / TAC 12.3 1.89 1.50 SiO

ZnO coating liquid (ZS-300: trade name, Sumitomo Cement Co., Ltd.) and binder resin (40-9: trade name: Die) on a release film (MC-19: trade name, manufactured by Daiichi Seika Co., Ltd.) treated with an acrylic-melamine resin on the surface. Nichi Seika Co., Ltd.) was mixed with a solid content weight ratio of 2: 1 to 30% by weight of solids with methyl ethyl ketone: toluene = 1: 1 solution, applied with a weir bar to a dry film thickness of 6 μm, and dried with dry EB. Cured. In addition, an adhesive (subject: Takeda A-310 manufactured by Takeda Pharmaceutical Co., Ltd. and Takenate A-3 manufactured by Takeda Pharmaceutical Co., Ltd., which is a curing agent in a 6: 1 ratio) was applied at a film thickness of 4 μm on drying, and then the coated release. The film and the substrate TAC film finally used in the product were laminated and cured by etching at 40 ° C. for 2 days. Then, the release film was peeled off and vapor deposition of SiO was performed under the following conditions to obtain an antireflection film.

Evaporator: Cyntron BMC-700

Deposition Material: SiO

Vacuum: 4 × 10- ² torr

Substrate Temperature: Room Temperature

EB Heat Deposition

Acceleration voltage: 5 kV

Emisson: 40 mA

Deposition Rate: 4Å / s

Film thickness: 1000Å

An antiglare layer having a fine uneven surface is formed on the transparent base film directly or through another layer (s), and a low refractive index layer lower than the refractive index of the antiglare layer is formed on the antiglare layer. The refractive index of the antiglare layer is higher than the refractive index of the layer in contact with the low refractive index layer that is in contact with the antiglare layer. As the low refractive index layer, an SiO _x film may be used. SiO _x film is an optical functional material that is excellent in gas barrier properties and pollution prevention properties as an optical functional film, and is excellent in moisture resistance, scratch resistance, adhesion to a substrate, transparency, low refractive index, dye deterioration prevention and other properties. .

The low refractive index layer as the surface layer is formed on the transparent substrate film via another layer, and at least one of the other layers is a hard coating layer having a thickness of 0.5 μm or more, has a high refractive index, and mainly consists of a resin. The high refractive index hard coating layer is in direct contact with the low refractive index layer. The refractive index of the high refractive index hard coating layer is higher than the refractive index of the layer facing the surface of the high refractive index hard coating layer on the side opposite to the low refractive index layer.

The antireflection film may be laminated and used as a polarizing plate or a liquid crystal display device.

Claims (2)

In the optically functional film in which the silicon oxide film is formed on a transparent base film directly or via another layer, The silicon oxide film has a contact angle of 40 to 180 degrees with respect to water, a coefficient of kinetic friction of 1 or less, and an SiO _x film (x is 1.50 ≦ x ≦ 4.00) formed by CVD. . The optical functional film according to claim 1, which is obtained by carrying out CVD under the following conditions. (a) Let organic siloxane be a raw material gas. (b) The source gas is subjected to plasma CVD in which plasma is discharged. (c) CVD is carried out in the absence of an inorganic vapor deposition source. (d) The film to be deposited is kept at a relatively low temperature. (e) It is performed under the film forming conditions existing in the SiO _x film in which undecomposed organosiloxane is formed.