JP3332605B2 - Transparent functional film containing functional ultrafine particles, transparent functional film, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for coating functional ultrafine particles having various functions such as an ultraviolet ray blocking effect, an antistatic effect and an antireflection effect in a coating film, in particular, on the surface of a layer in contact with or close to air. The present invention relates to a transparent functional film, a transparent functional film, and a method for producing the same, which exhibit the functions of the functional ultrafine particles by localizing the functional ultrafine particles. Further, the present invention relates to an antireflection film in which the transparent functional film has an antireflection function and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, ultraviolet blocking effect, antistatic effect,
By applying a transparent resin composition in which functional ultrafine particles having specific properties such as an anti-reflection effect are dispersed to a transparent plastic substrate film to form a functional coating film, ultraviolet blocking properties, antistatic properties or It is known to produce a transparent functional film having a function such as anti-reflection property.

[0003] Further, such a transparent functional film,
Furthermore, in order to impart properties such as abrasion resistance and chemical resistance,
On a transparent plastic substrate film, as a middle layer, for example, a hard coat layer made of an ionizing radiation curable resin or the like is formed, and the hard property is obtained by applying a transparent resin composition in which functional ultrafine particles are dispersed thereon. It is known to produce applied transparent functional films.

[0004]

The above-mentioned transparent functional film containing the functional ultrafine particles has the functional ultrafine particles dispersed in the transparent functional film due to its production method. In order to further enhance the function of the functional ultrafine particles, it is necessary to increase the amount of the functional ultrafine particles in the film.However, the mixing ratio of the functional ultrafine particles dispersed in the resin must be increased. In such a case, there is a problem that film formation becomes difficult. Further, in a transparent functional film having a hard coat layer such as an ionizing radiation curable resin, there is a problem that the hard coat layer is not sufficiently adhered to the transparent functional film, and the transparent functional film is easily peeled off. there were.

Accordingly, the present invention provides a method for producing a transparent functional film, a transparent functional film, and an anti-reflection film, in which functional ultrafine particles are localized at a high density in a hard coat layer, thereby obtaining functional ultrafine particles. By arranging as a layer, the function of the functional ultrafine particles can be exerted, and the transparent functional film, the transparent functional film, the antireflection film, and the adhesiveness between the hard coat layer and the functional ultrafine particles are excellent. It is an object to provide a method for producing them.

Another object of the present invention is to provide an antireflection film in which the transparent functional film has an antireflection function and a method for producing the same.

[0007]

Means for Solving the Problems Transparent functional film and transparent functional film : In order to solve the above-mentioned problems, the first transparent functional film of the present invention comprises:
It is characterized by being a transparent functional film in which the functional ultrafine particles are localized and fixed from the interface with the air layer to the inside of the hard coat layer.

Further, the second transparent functional film of the present invention comprises:
The functional ultrafine particles are polarized and fixed from the interface with the air layer to the inside of the hard coat layer, and the functional ultrafine particles in contact with the air layer do not have a thin film of the hard coat layer, and the functional ultrafine particles A feature is that the transparent functional film is partially exposed particularly from the hard coat layer.

The transparent functional film of the present invention is characterized in that the first and second transparent functional films are formed on a transparent plastic substrate film.

FIG. 1 shows a cross section of the first transparent functional film of the present invention. The transparent functional film has a functional ultrafine particle layer 2 formed from the surface to the inside of the hard coat layer 4 applied on the transparent plastic base film 3. As shown in FIG. 1, the functional ultrafine particle layers 2 are mutually connected by the binding force of each functional ultrafine particle 5 or by the binding force of a binder resin in such an amount that the functional ultrafine particles 5 are not completely buried. The outermost layer of the functional ultrafine particle layer 2 is buried in the hard coat layer 4 to such an extent that a thin film of the resin for the hard coat layer is formed. The hard coat layer 4 having the functional ultrafine particle layer 2 is the first transparent functional film of the present invention.

FIG. 2 shows a cross section of a second transparent functional film of the present invention. The transparent functional film has a functional ultrafine particle layer 2 formed from the inside to the surface of the hard coat layer 4 applied on the transparent plastic substrate film 3. As shown in FIG. 2, the functional ultrafine particle layers 2 are mutually connected by the binding force of each functional ultrafine particle 5 or by the binding force of a binder resin in such an amount that the functional ultrafine particles 5 are not completely buried. The entirety of the functional ultrafine particle layer 2 is bonded to the hard coat layer 4.
The functional ultrafine particles 5 are not completely buried, and a part of the functional ultrafine particles 5 is exposed from the surface of the hard coat layer 4. Not in direct contact with the air layer. The hard coat layer 4 itself having the partially exposed functional ultrafine particle layer 2 is the second transparent functional film of the present invention.

In the first and second transparent functional films or transparent functional films of the present invention, as described above, the functional ultrafine particles are poled and fixed from the interface with the air layer to the inside of the hard coat layer. Therefore, without using a large amount of functional ultrafine particles, it has the effect of easily expressing the properties of functional ultrafine particles with a small amount, and furthermore, simply forming a layer containing functional ultrafine particles on the hard coat layer This has the effect that the adhesiveness between the functional ultrafine particles and the hard coat layer is better than the above.

Method for producing transparent functional film : The first method for producing the first and second transparent functional films of the present invention comprises the following steps : (1) forming a functional ultrafine particle layer on a release film; (2) On the other hand, after coating the resin composition for a hard coat layer on a transparent plastic substrate film, and (3) drying the solvent when the resin composition for a hard coat layer is diluted with a solvent, In the case where the resin composition for a hard coat layer does not contain a solvent, as it is, the surface of the release film obtained in the step on the side of the functional ultrafine particle layer and the transparent plastic obtained in the step The surface of the base film on the side of the resin composition for the hard coat layer is pressed and laminated, and the functional ultrafine particle layer is buried in the resin composition for the hard coat layer or a part of the functional ultrafine particle layer. Buried, (4) After full curing the resulting laminate was in serial process, characterized by transferring the peel to the functional ultrafine particle layer a transparent plastic substrate film side release film.

The first and second transparent functional films of the present invention have the following modifications of the first production method: (1)
A functional ultrafine particle layer is formed on a release film, and (2) a resin composition for a hard coat layer is coated on a transparent plastic substrate film, and (3) the resin composition for a hard coat layer is If the solvent is diluted with a solvent, after drying the solvent, if the resin composition for a hard coat layer does not contain a solvent, it is left as it is, and the functional ultrafine particle layer of the release film obtained in the step is obtained. Side and the surface of the transparent plastic substrate film obtained in the above step on the side of the resin composition for the hard coat layer of the transparent plastic substrate film are pressed and laminated to form a functional ultrafine particle layer in the resin composition for the hard coat layer. (4) The laminate obtained in the above step is half-cured, and then the release film is peeled off to make the functional ultrafine particle layer a transparent plastic. Base material Transferred to Irumu side, (5) forming another functional membrane on the half cured been the hard coat layer, characterized by (6) then be fully cured.

FIG. 3 is a process diagram of a first manufacturing method for the first and second transparent functional films of the present invention described above. FIG. 3A shows a state in which a sol of the functional ultrafine particles 5 is applied on the release film 1 to form the functional ultrafine particle layer 2. (B) shows a state in which the release film 1 on which the functional ultrafine particle layer 2 is formed is to be pressure-bonded to a transparent plastic substrate film 3 on which a hard coat layer 4 is formed. Further, (c) shows a state where both are pressed. The state in which the release film 1 is peeled off after the resin for the hard coat layer is cured in the pressed state is shown in FIG.

In the step (c), the resin for the hard coat layer may be fully cured (first production method), or in the step (c), the resin for the hard coat layer may be half-cured. Subsequently, the hard coat layer resin may be fully cured after the release film 1 is removed in the step (d) (a modification of the first manufacturing method). Separating the curing of the hard coat layer into half cure and full cure in this way, for example, in the case where a layer is further provided thereon after half cure, the adhesion between the hard coat layer and the layer thereon increases. There are advantages.

The second method for producing the first and second transparent functional films of the present invention comprises: (1) forming a functional ultrafine particle layer on a release film; and (2) forming the functional ultrafine particle layer. On top, the resin composition for a hard coat layer is applied so as to have a thickness not less than the thickness of the functional ultrafine particle layer, and the functional ultrafine particle layer is buried in the resin for the hard coat layer or the functional ultrafine particles. Part of the layer is buried and fully cured to form a hard coat layer. (3) The release film on which the hard coat layer is formed has the hard coat layer side inside, and is transparent through an adhesive layer. (4) Laminating with a plastic substrate film, releasing the release film from the laminate obtained in the above step, and transferring the hard coat layer to the transparent plastic substrate film side.

The second variant of the first method for producing a transparent functional film of the present invention comprises the steps of (1) forming a functional ultrafine particle layer on a release film, and (2) forming the functional ultrafine particle layer. On top, the resin composition for a hard coat layer is applied so as to have a thickness not less than the thickness of the functional ultrafine particle layer, and the functional ultrafine particle layer is buried in the resin for the hard coat layer or the functional ultrafine particles. A part of the layer is buried and half-cured to form a hard coat layer. (3) The hard coat layer side of the release film on which the hard coat layer is formed is turned inside, and transparent through an adhesive layer. (4) The release film is peeled off from the laminate obtained in the above step, and the hard coat layer is transferred to the transparent plastic substrate film side. The said har The coating layer to form another functional film, characterized in that to fully cure the hard coat layer (6).

FIG. 4 is a process diagram of a second manufacturing method for the first and second transparent functional films of the present invention described above. FIG. 4A shows a functional ultrafine particle layer 2 formed by applying a sol of functional ultrafine particles 5 on a release film 1, and further applying a resin composition for a hard coat layer to the functional ultrafine particles. This is a state in which coating is performed so as to have a thickness equal to or greater than the thickness of the layer 2 to form the hard coat layer 4. In the step (a), the hard coat layer 4 may be fully cured or half-cured (variation). (B) shows a state in which the release film 1 on which the hard coat layer 4 obtained in the step (a) is formed is to be laminated with the transparent plastic substrate film 3 via the adhesive layer 6. The adhesive layer 6 may be formed by applying to the hard coat layer 4 or may be formed by applying to the transparent plastic substrate film 3. Further, (c) shows a state where both are pressed. The state in which the release film 1 has been peeled off in this pressed state is (d).

In the step (a) of FIG. 4, when the resin for the hard coat layer is completely cured, the resin of the hard coat layer is fully cured after the release film 1 is removed in the step (d). Can be. Separating the cure of the hard coat layer into half cure and full cure in this way, for example, in the case where a layer is further provided thereon after half cure, the adhesion between the hard coat layer and the layer thereon increases. There are advantages.

The third method for producing the first and second transparent functional films of the present invention comprises (1) forming a functional ultrafine particle layer on a release film, and (2) forming the functional ultrafine particle layer. On top, the resin composition for a hard coat layer is applied so as to have a thickness not less than the thickness of the functional ultrafine particle layer, and the functional ultrafine particle layer is buried in the resin for the hard coat layer or the functional ultrafine particles. Part of the layer is buried, and (3) a release film coated with the resin composition for a hard coat layer is laminated with a transparent plastic substrate film with the side of the resin composition for a hard coat layer facing inside. (4) peeling off the release film from the laminate obtained in the above step, and transferring the hard coat layer to the transparent plastic substrate film side.

The third and second production methods of the transparent functional film of the present invention are modified as follows: (1) forming a functional ultrafine particle layer on a release film; On the ultrafine particle layer, a hard coat layer resin composition is applied so as to have a thickness equal to or more than the thickness of the functional ultrafine particle layer, and the functional ultrafine particle layer is buried in the hard coat layer resin or has a function. (3) a transparent plastic substrate film in which a part of the functional ultrafine particle layer is buried, and (3) a release film coated with the resin composition for hard coat layer has the side of the resin composition for hard coat layer facing inside. (4) peeling off the release film from the half-cured laminate obtained in the above step, and transferring the hard-coat layer to the transparent plastic substrate film side; (5) Half Forming another functional membrane on Yua been the hard coat layer, characterized in that to fully cure the hard coat layer (6).

FIG. 5 is a process diagram of a third manufacturing method for the first and second transparent functional films of the present invention. FIG. 5A shows a functional ultrafine particle layer 2 formed by applying a sol of the functional ultrafine particles 5 on the release film 1, and further forming a functional ultrafine particle with the resin composition for a hard coat layer thereon. This is a state in which the coating is performed so as to have a thickness equal to or greater than the thickness of the layer 2 to form the hard coat layer 4. In the step (a), the hard coat layer 4 has not yet been subjected to a curing treatment. (B) is a state in which the release film 1 on which the uncured hard coat layer 4 obtained in the step (a) is formed is to be laminated with the transparent plastic substrate film 3. Further, (c) shows a state where both are pressed. In this state (c), a hardening treatment is performed, and the hard coat layer 4 is fully cured or half cured. Next, the state in which the release film 1 is peeled is (d).

In the step (c), the resin composition for a hard coat layer may be fully cured, or in the step (c), the resin composition for a hard coat layer may be half-cured, Next, after the release film 1 is peeled off in the step (d), the hard coat layer 4 may be fully cured. Dividing the cure of the hard coat layer 4 into half cure and full cure as described above means that, for example, when a layer is further provided thereon after half cure, the adhesion between the hard coat layer 4 and the layer thereon There is an advantage that increases.

In each of the above methods for producing a transparent functional film, in particular, the functional ultrafine particle layer is not completely buried in the hard coat layer, and a part of the functional ultrafine particle layer is exposed from the hard coat layer. In order to produce a transparent functional film (the second transparent functional film of the present invention), the viscosity of the resin for the hard coat layer, the type of the resin, the surface tension of the resin, and the functional properties The second functional film of the present invention can be produced by considering the particle size of the ultrafine particles, the filling rate of the ultrafine particles, the wettability between the resin for the hard coat layer and the functional ultrafine particles, and the like.

Specifically, by selecting a resin having a high viscosity as the resin for the hard coat layer or having a dryness to the touch (described later) at the time of coating (in a dry state to the touch),
Part of the functional ultrafine particles is easily exposed. Alternatively, a resin having a low surface tension may be selected, or a resin having a small particle size and a high filling rate of the functional ultrafine particles may be used. In selecting the resin and the ultrafine particles, a resin having poor wettability may be selected.

FIG. 6 is a process diagram showing an example of a production method for the second transparent functional film of the present invention.
FIG. 6A shows a state in which a sol of the functional ultrafine particles 5 is applied on the release film 1 to form the functional ultrafine particle layer 2. (B) is a method in which a resin composition for a hard coat layer is applied on a transparent plastic substrate film 3 and the release film 1 on which the functional ultrafine particle layer 2 is formed is dried in a touch-dry state. This is a state in which crimping is to be performed, and (c) is a state in which crimping is performed. Since the release film 1 is pressure-bonded when the resin composition for a hard coat layer is dry to the touch, the entire functional ultrafine particle layer 2 on the release film 1 is completely contained in the hard coat layer 4. Not buried,
Part of the functional ultrafine particle layer 2 remains outside the hard coat layer. The state in which the release film 1 is peeled off after the ionizing radiation-curable resin is completely cured by irradiating ionizing radiation such as an electron beam or ultraviolet light in this pressed state.
It is.

Release film : Generally, a film obtained by subjecting a sheet to a release treatment such as silicon, fluorine, acryl-melamine or the like, or an untreated film is used. The surface may have unevenness. In this case, since the unevenness is formed on the surface of the final product, the obtained transparent functional film can be provided with an antireflection effect or an antiglare effect.

Functional ultra-fine particles : The functional ultra-fine particles used in the functional ultra-fine particle layer are ultra-fine particles having a size of 200 nm or less, and have functions such as ultraviolet blocking property, conductivity, antistatic property and anti-reflection property. Ones having. For example, to impart conductivity or antistatic property to a transparent functional film, use S
nO ₂ and ultrafine particles of ITO or the like is used, the low refractive index ultrafine particles and Sb ₂ O _5, ZnO, such as MgF ₂ and SiO ₂ to impart antireflection properties, ITO, SnO _2, such as TiO ₂ high Ultrafine particles of refractive index are used.

The production of the antireflection film using the high refractive index ultrafine particles is carried out by coating a coating material containing the high refractive index ultrafine particles with an inorganic material such as MgF ₂ or SiO ₂ having a low refractive index. , Sputtering, plasma CV with metal and metal materials
D or the like to form a single-layer or multi-layer thin film, or a low-refractive-index inorganic material such as MgF ₂ or SiO _2, or a low-refractive-index resin composition containing a metal material or the like to form a single-layer or multi-layer coating. By forming, an antireflection film can be obtained.

Further, in order to impart ultraviolet blocking properties, Sb ₂
Ultra fine particles such as O ₅ , ZnO, and TiO ₂ are used.

The surface of these functional ultrafine particles may be subjected to a hydrophobic treatment with a coupling agent, and a hydrophobic group is introduced into the surface of the functional ultrafine particles by such a hydrophobic treatment. Therefore, the resin becomes easily compatible with the ionizing radiation-curable resin, and the bond with the ionizing radiation-curable resin becomes stronger. As such a coupling agent, a silane coupling agent, a titanate coupling agent, an alumina coupling agent, or the like is used. The addition amount of the coupling agent is 0 (excluding 0) to 30 parts by weight, preferably 0 (0
) To 10 parts by weight.

When the surface of the functional ultrafine particles is inert such as MgF ₂ , an SiO ₂ sol is added in advance, the surface of the functional ultrafine particles is coated with SiO ₂ , and then treated with a coupling agent. You may. By such a coating treatment of SiO _2, a large number of hydrophilic groups can be introduced into the surface of the functional ultrafine particles, and a subsequent treatment with a coupling agent can surely introduce a large number of hydrophobic groups. The ultrafine particles are more easily blended into the resin, and the bonding property is increased.

Shape of Functional Ultrafine Particle Layer on Release Film
Forming methods: a method of forming the mold release functional ultrafine particle layer on the film, by applying what the sol of the functional ultrafine particle sol itself or functional ultrafine particles obtained by incorporating a binder resin on a release film Form. When the functional ultrafine particle layer is formed on the release film, the functional ultrafine particle can be formed by the binding action of the functional ultrafine particle itself without using a binder resin, but the binding action is weak. In such a case, a binder resin may be used as necessary. The amount of the binder resin is such that the functional ultrafine particles are not completely buried in the binder resin, and the functional ultrafine particles are bound to each other in a state where the surface of the functional ultrafine particles is exposed. Therefore, it is preferable to exhibit functionality, particularly when it is used for an antireflection film.

As such a binder resin, a general resin such as a thermosetting resin, a thermoplastic resin, or an ionizing radiation-curable resin is used.
Considering the adhesion to the resin, an ionizing radiation-curable resin is desirable, and the ionizing radiation-curable resin is preferably a solvent-dried semi-curable resin. Further, a coloring agent can be mixed in such a binder resin.

Transparent plastic substrate film : The transparent plastic substrate film suitable for the transparent functional film may be any transparent film, for example, triacetyl cellulose film, diacetyl cellulose film, acetate butyrate cellulose film. , Polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, trimethylpentene film, polyetherketone film, (meth) acrylonitrile film, etc. can be used. In particular, a triacetyl cellulose film and a uniaxially stretched polyester are preferably used because they are excellent in transparency and have no optical anisotropy. Usually, the thickness of about 8 μm to 1000 μm is suitably used.

Hard coat layer : The binder resin which can be used for the hard coat layer is any resin as long as it is transparent (for example, thermoplastic resin, thermosetting resin, ionizing radiation curable resin, etc.). ) Can also be used. In order to impart hard performance, the thickness of the hard coat layer is 0.5 μm or more, preferably 3 μm or more, whereby the hardness can be maintained, and the hard performance can be imparted to the antireflection film. .

In the present invention, “having a hard property” or “hard coat” is defined in JIS K540.
A pencil hardness test indicated by 0 indicates a hardness of H or higher.

In order to further improve the hardness of the hard coat layer, a reaction curable resin, that is, a thermosetting resin and / or an ionizing radiation curable resin is used as the binder resin used for the hard coat layer. Is preferred. The thermosetting resin includes phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine-urea cocondensation resin, silicon resin, A siloxane resin or the like is used, and a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like are added to these resins as necessary.

The ionizing radiation-curable resin preferably has an acrylate-based functional group, for example, a polyester resin or polyether resin having a relatively low molecular weight.
Acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin,
Polythiol polyene resin, oligomer or prepolymer of polyfunctional compound such as polyhydric alcohol such as (meth) acrylate, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone as reactive diluent And monofunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth)
Those containing a relatively large amount of acrylate or the like can be used.

Particularly preferably, a mixture of a polyester acrylate and a polyurethane acrylate is used. The reason is that polyester acrylate has a very hard coating and is suitable for obtaining a hard coat.However, polyester acrylate alone has low impact resistance and becomes brittle, so that the coating has high impact resistance and flexibility. Polyurethane acrylate is used in combination to impart properties. The mixing ratio of the polyurethane acrylate to 100 parts by weight of the polyester acrylate is 30 parts by weight or less. If it exceeds this value, the coating film is too soft and loses the hard property.

Furthermore, in order to make the above-mentioned ionizing radiation-curable resin composition into an ultraviolet-curable resin composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime are used as photopolymerization initiators. Esters, tetramethylthiuram monosulfide,
Thioxanthone and n-butylamine, triethylamine, tri-n-butylphosphine and the like as a photosensitizer can be mixed and used. In particular, in the present invention, it is preferable to mix urethane acrylate as an oligomer and dipentaerythritol hexa (meth) acrylate as a monomer.

In order to impart flexibility to the hard coat layer, the solvent-drying resin may be contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin. As the solvent drying type resin, a thermoplastic resin is mainly used. The type of the solvent-dried thermoplastic resin to be added to the ionizing radiation-curable resin is commonly used, but especially when a mixture of polyester acrylate and polyurethane acrylate is used for the ionizing radiation-curable resin. Polymethyl methacrylate or polybutyl methacrylate can keep the hardness of the coating film high as the solvent-drying type resin. Moreover, in this case, since the refractive index of the main ionizing radiation-curable resin is close, the transparency of the coating film is not impaired.
In particular, it is advantageous in terms of low haze value, high transmittance, and compatibility.

When a cellulosic resin such as triacetyl cellulose is used as the transparent plastic substrate film, nitrocellulose, acetyl cellulose, cellulose acetate propionate, etc. may be used as the solvent-drying resin contained in the ionizing radiation-curable resin. Cellulose resins such as acrylate and ethylhydroxyethylcellulose are advantageous in terms of adhesion and transparency of the coating film.

The reason is that when toluene is used as a solvent for the above-mentioned cellulose-based resin, the transparent plastic base resin is used in spite of using toluene which is a solvent insoluble in triacetyl cellulose which is a transparent plastic base film. Even if the coating containing the solvent-drying resin is applied to the material film, the adhesion between the transparent plastic substrate film and the coating resin can be improved, and the toluene is used in the transparent plastic substrate film. This is because, since a certain triacetyl cellulose is not dissolved, the surface of the transparent plastic substrate film is not whitened, and there is an advantage that transparency is maintained.

When an ionizing radiation-curable resin is used as a binder resin in the hard coat layer, the curing method is a usual method of curing an ionizing radiation-curable resin, that is, curing by irradiation with an electron beam or ultraviolet rays. Can be. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type, High frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light beams such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. .

Half Cure : In the method for producing a transparent functional film of the present invention, half cure is defined as a. Ionizing radiation curable resin semi-crosslinked half cure,
b. An ionizing radiation-curable resin / thermosetting resin (or thermoplastic resin) blend type half cure, and c. Solvent drying type / half cure type composite half cure may be mentioned.

A. Ionizing radiation-curable resin semi-crosslinked half-cured It is formed by applying a normal ionizing radiation-curable resin and performing semi-crosslinking by adjusting the irradiation conditions of ionizing radiation such as ultraviolet rays or electron beams on the coating film. It refers to the state of half cure.

B. Ionizing radiation curable resin / thermosetting resin (or thermoplastic resin) blend type half cure Ionizing radiation curable resin is mixed with thermosetting resin or thermoplastic resin to apply resin composition and thermosetting resin In the case where is used, it refers to a half-cured state formed by applying heat to the coating film.

C. Solvent drying type, half-curing type composite half-curing A coating of a normal ionizing radiation-curable resin with a solvent applied to it, and drying of the solvent is applied to the coating film.
Further, it refers to a state in which half curing is performed by irradiation with ionizing radiation. The state of this half cure is described in JP-A-1-202.
This is the same as the semi-cured state described in JP-A-49-49.

Dry state to the touch : In producing the second transparent functional film of the present invention, it is necessary to expose a part of the functional ultrafine particle layer from the hard coat layer. For this purpose, when the applied coating film of the resin composition for a hard coat layer is in a touch-dry state, its viscosity is high, so that by contacting the functional ultrafine particle layer, all of the functional ultrafine particle layer is A part of the functional ultrafine particle layer is exposed without being completely buried in the hard coat layer. Further, by bringing the hard coat layer into a touch-dry state, there is an advantage that the adhesion between the hard coat layer and the functional ultrafine particle layer is improved.

In order to make the coating film of the resin composition for a hard coat layer dry to the touch, a method of using an ionizing radiation-curable resin having dryness to the touch, and a method of using an adhesive to the ionizing radiation-curable resin And a method of mixing a resin having the following formula:

The method of using the ionizing radiation-curable resin having dryness to the touch as described above includes, for example, the following (A)
An ionizing radiation-curable resin having a dryness to the touch shown in (b) can be used.

(A) A resin having a radical polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C.

Specifically, it is a resin obtained by polymerizing or copolymerizing the following monomers and introducing a radical copolymerizable unsaturated group by the following methods a) to d).

Monomers having a hydroxyl group: N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy And propyl (meth) acrylate.

Monomer having a carboxyl group: For example,
(Meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like.

Monomer having an epoxy group: for example, glycidyl (meth) acrylate and the like.

Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate and the like.

Monomers having an amino group: (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like.

Monomers having a sulfone group: 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like.

Monomer having isocyanate group: 2,4
-Adducts of a diisocyanate and a radical copolymer having active hydrogen, such as adducts of 1 mol to 1 mol of toluene diisocyanate and 2-hydroxyethyl (meth) acrylate.

Further, in order to adjust the glass transition temperature of the copolymer or to adjust the physical properties of the cured film, the above-listed monomers and the following compounds can be copolymerized. Such copolymerizable monomers include, for example, methyl (meth) acrylate, propyl (meth)
Examples include acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, gt-butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

By introducing a radical polymerizable unsaturated group into the polymerized or copolymerized monomer described above by the following methods a) to d), an ultraviolet curable resin or An ionizing radiation curable resin such as an electron beam curable resin is obtained.

A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.

B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the above-mentioned monomer having a hydroxyl group is subjected to a condensation reaction.

C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or monomer having a carboxyl group is subjected to an addition reaction. .

D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylate One mole to one mole of the adduct of the monomer is subjected to an addition reaction.

To carry out the above reaction, it is desirable to add a trace amount of a polymerization inhibitor such as hydroquinone and to carry out the reaction while sending dry air.

(B) A resin having a melting point of room temperature (20 ° C.) to 250 ° C. and having a radically polymerizable unsaturated group.

Specific examples include stearyl acrylate, stearyl (meth) acrylate, triacryl isocyanate, cyclohexanediol (meth) acrylate, spiroglycol diacrylate, spiroglycol (meth) acrylate, and the like.

The adhesive resin used in the method of mixing the adhesive resin into the ionizing radiation-curable resin gives the ionizing radiation-curable resin a viscosity. Generally, it can be formed from a mixture of an adhesive and an ionizing radiation-curable resin, but if the ionizing radiation-curable resin is not liquid in an uncrosslinked state and has tackiness, it can be used as it is. it can. In particular, in order to keep the hardness of the coating film high, a thermoplastic resin such as polymethyl methacrylate or polybutyl methacrylate can be suitably used for imparting viscosity to the ionizing radiation-curable resin.

Other resins suitable for imparting viscosity to the ionizing radiation-curable resin may be those conventionally used for adhesive tapes and adhesive seals, such as polyisoprene rubber, polyisobutylene rubber, and styrene butadiene. Rubber, rubber resins such as butadiene acrylonitrile rubber, (meth) acrylate resin, polyvinyl ether resin, polyvinyl acetate resin, polyvinyl chloride / vinyl acetate copolymer resin, polystyrene resin, polyamide resin, Tackifiers suitable for polychlorinated olefin resins, polyvinyl butyral resins, etc., for example, rosin, dammar, polymerized rosin, partially hydrogenated rosin, ester rosin, polyterpene resin, modified terpene, petroleum resin, cyclopentadiene Resin, phenolic resin,
Examples thereof include those to which a coumarone-indene-based resin is appropriately added, and those to which a softener, a filler, an antioxidant, and the like are further added as necessary.

The mixing ratio of the resin having adhesiveness to the ionizing radiation-curable resin is such that the ionizing radiation-curable resin is 100%.
It is preferable that the content be 50 parts by weight or less with respect to parts by weight for the purpose of bringing the coating film into a touch-dry state.

Antireflection Film and Method for Producing the Same : Two types of antireflection films of the present invention using low refractive index ultrafine particles as functional ultrafine particles, and high refractive index ultrafine particles as functional ultrafine particles There are two types, four types.

The first antireflection film of the present invention comprises:
A hard coat layer in which the low refractive index ultrafine particles are localized and fixed from the interface with the air layer to the inside of the hard coat layer is fixed on a transparent plastic substrate film, and the refractive index of the hard coat layer is The low refractive index ultrafine particles are higher in refractive index. This antireflection film is a transparent functional film shown in FIG.
This corresponds to the case where the functional ultrafine particles are low refractive index ultrafine particles.

The second antireflection film of the present invention comprises:
A hard coat layer in which the low refractive index ultrafine particles are localized and fixed from the interface with the air layer to the inside of the hard coat layer and a part of the low refractive index ultrafine particles are exposed from the surface of the hard coat layer is formed. Fixed on a transparent plastic substrate film, wherein the refractive index of the hard coat layer is higher than the refractive index of the low refractive index ultrafine particles. This antireflection film corresponds to the case where the functional ultrafine particles are low refractive index ultrafine particles in the transparent functional film shown in FIG.

The third antireflection film of the present invention comprises:
The hard coat layer in which the high refractive index ultrafine particles are poled and fixed from the surface to the inside of the hard coat layer is fixed on a transparent plastic substrate film on the back surface of the hard coat layer, and the high refractive index ultrafine particles are fixed. Wherein a low refractive index layer is further formed on the surface of the hard coat layer that is localized, and the refractive index of the hard coat layer is lower than the refractive index of the high refractive index ultrafine particles. I do. This antireflection film corresponds to the case where the functional ultrafine particles are high refractive index ultrafine particles in the transparent functional film shown in FIG.

The fourth antireflection film of the present invention comprises:
The hard coat layer, in which the high refractive index ultrafine particles are localized and fixed from the surface to the inside of the hard coat layer and a part of the high refractive index ultrafine particles are exposed from the surface of the hard coat layer, is formed of a transparent plastic base. Fixed on the material film,
On the surface of the hard coat layer where the high refractive index ultrafine particles are localized and a part of the high refractive index ultrafine particles are exposed from the surface of the hard coat layer, a low refractive index layer is further formed. And wherein the refractive index of the hard coat layer is lower than the refractive index of the high refractive index ultrafine particles. This antireflection film corresponds to the case where the functional ultrafine particles are high refractive index ultrafine particles in the transparent functional film shown in FIG.

The first method for producing an anti-reflection film according to the present invention is the same as the first method for producing the first transparent functional film, wherein the low refractive index ultrafine particles are used as the functional ultrafine particles. The present invention is characterized in that a resin composition for a hard coat layer having a refractive index higher than that of the ultrafine particles having a low refractive index is used for the resin composition for a hard coat layer.

The second method for producing an antireflection film according to the present invention is the same as the method for producing a transparent functional film described above, except that the low refractive index ultrafine particles are used as the functional ultrafine particles, It is characterized in that a resin composition for a hard coat layer having a refractive index higher than the refractive index of the low refractive index ultrafine particles is used for the composition.

The first method for producing the third anti-reflection film of the present invention comprises (1) forming a high refractive index ultrafine particle layer on a release film, and (2) forming a transparent plastic substrate. On the material film, the high refractive index ultrafine particle layer
Coating the resin composition for a hard coat layer having a refractive index lower than the refractive index, and (3) drying the solvent when the resin composition for a hard coat layer is diluted with a solvent, and then drying the hard coat layer. When the resin composition for solvent does not contain a solvent as it is, the surface of the release film obtained in the step on the high refractive index ultrafine particle layer side, the transparent plastic substrate film obtained in the step The surface on the resin composition side for the hard coat layer is pressed and laminated, and the high refractive index ultrafine particle layer is buried in the resin composition for the hard coat layer or a part of the high refractive index ultrafine particle layer is buried. (4) After the cured product obtained in the above step is fully cured to form a hard coat layer, the release film is peeled off, and the high refractive index ultrafine particle layer is transferred to the transparent plastic substrate film side, 5) Then, And forming a low refractive index layer on the serial hard coat layer.

Further, a modification of the first production method for producing the third antireflection film of the present invention is as follows: (1) forming a high refractive index ultrafine particle layer on a release film; On the other hand, a resin composition for a hard coat layer having a refractive index lower than the refractive index of the high refractive index ultrafine particle layer is coated on a transparent plastic substrate film, and (3) the resin composition for a hard coat layer is When the solvent composition is diluted with a solvent, after drying the solvent, if the resin composition for a hard coat layer does not contain a solvent, the resin composition remains as it is, and the high refractive index ultrafine particles of the release film obtained in the step are obtained. The layer side surface and the hard coat layer resin composition side surface of the transparent plastic substrate film obtained in the above step are pressure-bonded and laminated to form a high refractive index ultrafine particle layer for the hard coat layer resin composition. Buried inside or highly bent Is buried a portion of the rate ultrafine particle layer,
(4) After half-curing the laminate obtained in the above step to form a hard coat layer, the release film is peeled off, and the high refractive index ultrafine particle layer is transferred to the transparent plastic substrate film side. A) forming a low refractive index layer on the half-cured hard coat layer; and (6) fully curing the hard coat layer.

The second production method for producing the third antireflection film of the present invention comprises the steps of (1) forming a high refractive index ultrafine particle layer on a release film, and (2) forming the high refractive index ultrafine particle layer. On the fine particle layer, a resin composition for a hard coat layer having a refractive index lower than the refractive index of the high refractive index ultrafine particle layer is applied so as to have a film thickness of the high refractive index ultrafine particle layer or more. The ultrafine particle layer is buried in the resin for the hard coat layer, or a part of the high refractive index layer ultrafine particle layer is buried and fully cured to form a hard coat layer. (3) The hard coat layer is formed. With the hard coat layer side of the release film facing inside, a transparent plastic substrate film is laminated via an adhesive layer, and (4) the release film is peeled from the laminate obtained in the above step to form a hard coat. Layer on a transparent plastic substrate Transferred to arm side, (5) then, and forming a low refractive index layer on the hard coat layer.

Further, the second modification of the second method for producing the antireflection film of the present invention is as follows: (1) forming a high refractive index ultrafine particle layer on a release film; the high-refractive index ultrafine particles layer, the refractive index of the high refractive index ultrafine particles layer
Applying a resin composition for a hard coat layer having a lower refractive index so as to be not less than the thickness of the high refractive index ultrafine particle layer, and burying the high refractive index ultrafine particle layer in the resin for the hard coat layer. Alternatively, a part of the high-refractive-index layer ultrafine particle layer is buried and half-cured to form a hard coat layer, and (3) the hard coat layer side of the release film on which the hard coat layer is formed is set to the inner side and adhered. (4) peeling off the release film from the laminate obtained in the above step, and transferring the hard coat layer to the transparent plastic substrate film side,
(5) A low refractive index layer is formed on the half-cured hard coat layer, and (6) the hard coat layer is fully cured.

The third production method for producing the third antireflection film of the present invention comprises the steps of (1) forming a high refractive index ultrafine particle layer on a release film; On the fine particle layer, a resin composition for a hard coat layer having a refractive index lower than the refractive index of the high refractive index ultrafine particle layer is applied so as to have a film thickness of the high refractive index ultrafine particle layer or more. The ultrafine particle layer is buried in the resin for the hard coat layer, or a part of the ultrafine particle layer of the high refractive index layer is buried in the resin for the hard coat layer. The resin composition for the hard coat layer is laminated with a transparent plastic substrate film with the side facing inward, and the composition is fully cured to form a hard coat layer. (4) The release film is peeled from the laminate obtained in the above step To make the hard coat layer transparent plastic Transferred to click the side of the substrate film (5)
Next, a low refractive index layer is formed on the hard coat layer.

Further, a modification of the third production method for producing the third antireflection film of the present invention is as follows: (1) forming a high refractive index ultrafine particle layer on a release film; the high-refractive index ultrafine particles layer, the refractive index of the high refractive index ultrafine particles layer
Applying a resin composition for a hard coat layer having a lower refractive index so as to be not less than the thickness of the high refractive index ultrafine particle layer, and burying the high refractive index ultrafine particle layer in the resin for the hard coat layer. Or buried a part of the high refractive index layer ultrafine particle layer,
(3) laminating the release film coated with the hard coat layer resin composition with a transparent plastic substrate film with the hard coat layer resin composition side facing in;
Half-cure to form a hard coat layer, (4)
The release film is peeled from the half-cured laminate obtained in the above step, and the hard coat layer is transferred to the transparent plastic substrate film side. (5) A low refractive index layer is formed on the half-cured hard coat layer. Forming (6)
The hard coat layer is fully cured.

In each of the above methods for producing an antireflection film, particularly, the high refractive index ultrafine particles are not completely buried in the hard coat layer, and a part of the high refractive index ultrafine particles is exposed from the hard coat layer. In order to manufacture the anti-reflection film (the fourth anti-reflection film of the present invention), increase the viscosity of the resin for the hard coat layer, select the type of the resin, and increase the surface tension of the resin. It can be produced by selecting and further considering the particle diameter of the high refractive index ultrafine particles, the filling rate of the ultrafine particles, the wettability between the resin for the hard coat layer and the high refractive index ultrafine particles, and the like.

Examples of the production method for producing the fourth antireflection film of the present invention include (1) forming a high refractive index ultrafine particle layer on a release film, and (2) forming a transparent plastic A resin composition for a hard coat layer having a refractive index lower than the refractive index of the high refractive index ultrafine particle layer is coated on a material film, and (3) a coating film of the resin composition for a hard coat layer is touched. When in the dry state, the surface on the high refractive index ultrafine particle layer side of the release film obtained in the above step and the surface on the coating side of the transparent plastic substrate film obtained in the above step are laminated by pressing. Then, a part of the high-refractive-index ultrafine particle layer is buried in the resin composition for a hard coat layer, and (4) the laminate obtained in the above step is fully cured to form a hard coat layer. Remove the film to form a high refractive index ultrafine particle layer. And transferred to a light plastic base film side, (5) Next, a method of forming a low refractive index layer and the like on the high refractive index ultrafine particles layer exposed in part from the hard coat layer.

Further, another example of the production method for producing the fourth antireflection film of the present invention is as follows: (1) forming a high refractive index ultrafine particle layer on a release film;
A resin composition for a hard coat layer having a refractive index lower than the refractive index of the high refractive index ultrafine particle layer is applied on a transparent plastic substrate film, and (3) a coating film of the resin composition for a hard coat layer When in the dry to the touch state, the surface on the high refractive index ultrafine particle layer side of the release film obtained in the above step and the surface on the coating side of the transparent plastic substrate film obtained in the above step are pressed. And laminating a part of the high refractive index ultrafine particle layer in the resin composition for the hard coat layer, and (4)
After the laminate obtained in the above step is half-cured to form a hard coat layer, the release film is peeled off, and the high refractive index ultrafine particle layer is transferred to the transparent plastic substrate film side. A method of forming a low-refractive-index layer on the high-refractive-index ultrafine particle layer partially exposed from the coat layer, and (6) then performing a full cure.

In the method for producing an antireflection film of the present invention, when a low refractive index layer is formed on a hard coat layer by painting or a vapor phase method, the low refractive index layer is formed on a half-cured hard coat layer. When you do
There is an advantage that the adhesion of the low refractive index layer is improved. The half cure is the same as that described for the transparent functional film.

High refractive index ultrafine particles in antireflection film
Sublayer : The high refractive index ultrafine particles used for the high refractive index ultrafine particle layer in the antireflection film of the present invention include, for example, Z
nO (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 1.71)
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. It is preferable to use ZnO, TiO ₂ , CeO _2, or the like among these high refractive index ultrafine particles, since a UV shielding effect is further provided to the antireflection film of the present invention. Further, by using SnO ₂ or ITO doped with antimony, the electron conductivity is improved, and the adhesion of dust due to the antistatic effect is prevented, or the antireflection film of the present invention is replaced with CR.
This is preferable because an electromagnetic wave shielding effect when used for T is obtained. The particle size of the high refractive index ultrafine particles is preferably 400 nm or less in order to make the hard coat layer transparent.

Low refractive index ultrafine particles in antireflection film
Sublayer : The low-refractive-index ultrafine particles used in the low-refractive-index ultrafine particle layer in the antireflection film of the present invention include, for example, L
iF (refractive index 1.4), MgF ₂ (refractive index 1.4), 3
NaF.AlF ₃ (refractive index 1.4), AlF ₃ (refractive index 1.4), Na ₃ AlF ₆ (cryolites, refractive index 1.3)
3) Inorganic materials such as SiO _x (x: 1.50 ≦ x ≦ 2.00) (refractive index: 1.35 to 1.48) are used.

Low refractive index layer in antireflection film : In the antireflection film of the present invention, a low refractive index layer is further provided on the surface of the hard coat layer where the high refractive index ultrafine particles are localized. I have. The low refractive index layer has a lower refractive index than the hard coat layer and the high refractive index fine particle layer. The refractive index n _L of this low refractive index layer is, of course, in a range lower than the refractive index n _H of the hard coat layer.

[0095]

(Equation 1) , The antireflection effect is improved, so that it is desirable to approach the condition of the above equation (1).

The low-refractive-index material used for forming the low-refractive-index layer may be any material as long as it satisfies the above conditions, and inorganic and organic materials can be used.

As the low refractive index inorganic material, for example, Li
F (refractive index 1.4), MgF ₂ (refractive index 1.4), 3N
aF · AlF ₃ (refractive index 1.4), AlF ₃ (refractive index 1.4), Na ₃ AlF ₆ (cryolites, refractive index 1.3)
3) Inorganic materials such as SiO _x (x: 1.50 ≦ x ≦ 2.00) (refractive index: 1.35 to 1.48) are used.

A film formed of a low refractive index inorganic material has a high hardness, and in particular, a film formed of SiO _x (x: 1.
50 ≦ x ≦ 4.00, preferably 1.70 ≦ x ≦ 2.2
Forming the film of 0) is preferable because it has good hardness, excellent adhesion to the hard coat layer, and can reduce thermal damage to the transparent plastic substrate film as compared with other vapor phase methods.

As the low refractive index organic material, an organic substance such as a polymer into which a fluorine atom is introduced is preferable because its refractive index is as low as 1.45 or less. As a resin in which a solvent can be used, polyvinylidene fluoride (refractive index n = 1.40) can be mentioned because of its easy handling. When this polyvinylidene fluoride is used as the low refractive index organic material, the low refractive index layer has a refractive index of about 1.40,
In order to further lower the refractive index of the low refractive index layer, a low refractive index acrylate such as trifluoroethyl acrylate (refractive index n = 1.32) is used in an amount of 10 to 300 parts by weight, preferably 100 to 200 parts by weight. You may add by weight.

Incidentally, this trifluoroethyl acrylate is a monofunctional type, and therefore, the film strength of the low refractive index layer is not sufficient.
It is desirable to add dipentaerythritol hexaacrylate (abbreviation: DPHA, tetrafunctional type) which is an ionizing radiation-curable resin. Although the film strength of DPHA increases as the amount of addition increases, the amount of addition is preferably small from the viewpoint of lowering the refractive index of the low refractive index layer, and 1 to 50 parts by weight, preferably 5 to 20 parts by weight is added. It is recommended that

The low-refractive-index layer is formed by depositing a low-refractive-index inorganic material on the high-refractive-index hard coat layer.
Sputtering, ion plating, plasma CV
A single-layer or multi-layer coating is performed by forming a single-layer or multi-layer film by a vapor phase method such as D, or by applying a low-refractive-index resin composition or a low-refractive-index organic material containing a low-refractive-index inorganic material. It can be performed by forming a film.

In particular, S formed by the plasma CVD method
The iO _x film has a higher density and a higher gas barrier property than a normal vacuum deposited film. Therefore, when the anti-reflection film of the present invention is used by laminating it on a polarizing element, there is an advantage that the polarizing element, which is considered to be vulnerable to moisture, has a moisture-proof function. Table 1 below shows experimental data indicating the superiority of the SiO _x film formed by the plasma CVD method. The films subjected to the moisture-proof experiment were a triacetylcellulose film (denoted as TAC), and a film formed by forming a 7 μm-thick hard coat resin coating on the triacetylcellulose film [denoted as HC (7 μm) / TAC. To a film thickness of 1 on a triacetylcellulose film.
μm of a vinylidene fluoride coating film [K coat: expressed as vinylidene fluoride (1 μm) / TAC], a film thickness of 100 on a triacetyl cellulose film
0 ° SiO _x plasma CVD film formed [S
iO _x (1000 °) / TAC] was used. Each of these films was subjected to a humidity of 90% and a temperature of 40 ° C.
The moisture permeability per day was measured according to the JIS moisture-proof test.

[0103]

[Table 1] According to Table 1, it can be seen that SiO _x (1000 °) / TAC has the lowest moisture permeability and is excellent in moisture proof properties. In addition, K coat: vinylidene fluoride (1 μm) / T
Although AC has a somewhat good moisture-proof property, it is not preferable to use it as an optical material because its coating film is soft and yellows over time.

When a dye or the like is used in the polarizing element or other layers, the plasma CVD film can prevent the deterioration thereof. Since the SiO _x film formed by the plasma CVD method has a high density, it becomes a scratch-resistant film.

Further, S formed by the plasma CVD method
iO _x film as compared to conventional vacuum evaporation film, the SiO _x film x
Is relatively easy to change, and while the value of x of a normal vacuum deposited film is less than 2 at most, the plasma C
The number of SiO _x films formed by the VD method can exceed 2. Therefore, the SiO _x film formed by the plasma CVD method can have a lower refractive index than a normal vacuum deposited film, and has an advantage that the obtained film has high transparency. Further, the SiO _x film formed by the plasma CVD method has better adhesiveness to the substrate than a normal vacuum deposited film.

[0106] The refractive index of the hard coat layer in the antireflection film: In one th and second antireflection film of the present invention, the refractive index of the hard coat layer, bending of the low refractive index ultrafine particles
Although the refractive index is higher than the refractive index, the layer configuration having such a refractive index can enhance the antireflection effect and prevent reflection at the interface between the hard coat layer and another layer. Change
To increase the anti-reflection effect, use a transparent plastic
The refractive index of the hard coat layer is higher than the refractive index of the material film
Is desirable. To increase the refractive index of the hard coat layer, use a binder resin having a high refractive index for the hard coat layer, or use high refractive index ultrafine particles with a refractive index higher than the refractive index of the hard coat layer for the hard coat layer. Add or use these methods together.

The binder resin having a high refractive index includes:
Resins containing an aromatic ring, halogenated elements other than F, for example, resins containing Br, I, Cl, etc., resins containing atoms such as S, N, P, etc., satisfying at least one of these conditions. Resin is desirable because it has a high refractive index.

Examples of the above resins include styrene resins such as polystyrene, polyethylene terephthalate, polyvinyl carbazole, and bisphenol A polycarbonate. Examples of the resin include polyvinyl chloride, polytetrabromobisphenol A glycidyl ether, and the like.

In the third and fourth antireflection films of the present invention, the refractive index of the hard coat layer itself in the portion where the high refractive index ultrafine particle layer does not exist is the same as that of the high refractive index ultrafine particle layer.
Although it is lower than the refractive index, by adopting a layer configuration having such a refractive index, the antireflection effect can be enhanced, and reflection at the interface between the hard coat layer and another layer can be prevented.
To further enhance the anti-reflection effect, use transparent plastic
The refractive index of the hard coat layer is higher than that of the base film
High is desirable.

Other layers : In the antireflection film of the present invention,
In addition to the above-described layers, layers for imparting various functionalities can be further provided. For example, a primer layer or an adhesive layer is provided on the transparent plastic substrate film for the purpose of improving the adhesiveness with the transparent plastic substrate film, and a plurality of hard coat layers are provided for improving the hard performance. Layers may be provided. The refractive index of the other layers provided between the transparent plastic substrate film and the hard coat layer as described above may be an intermediate value between the refractive index of the transparent plastic substrate film and the refractive index of the hard coat layer. preferable.

The other layer may be formed by coating directly or indirectly on the transparent plastic substrate film as described above, or by transferring a hard coat layer onto the transparent plastic substrate film by transfer. When forming, another layer may be applied and formed on the hard coat layer previously formed on the transfer film, and then transferred to a transparent plastic substrate film.

The lower surface of the antireflection film of the present invention may be coated with a pressure-sensitive adhesive, and this antireflection film can be used by attaching it to an object to be antireflection, for example, a polarizing element.

Polarizing plate and liquid crystal display device : By laminating the antireflection film of the present invention on a polarizing element,
A polarizing plate with improved antireflection properties can be obtained. As the polarizing element, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, a saponified ethylene-vinyl acetate copolymer film, or the like, which is dyed and stretched with iodine or a dye, can be used. When the base film of the antireflection film is, for example, a triacetylcellulose film, a saponification treatment is performed on the triacetylcellulose film in order to increase adhesiveness and prevent static electricity in the lamination process. This saponification treatment may be performed before or after applying the hard coat to the triacetyl cellulose film.

FIG. 13 shows an example of a polarizing plate using the antireflection film of the present invention. In the figure, reference numeral 12 denotes an antireflection film of the present invention, and the antireflection film 12 is laminated on a polarizing element 13.
On the other side, a triacetyl cellulose film (abbreviation: TA)
C film) 14 is laminated. Further, the antireflection film 12 of the present invention may be laminated on both surfaces of the polarizing element 13.

FIG. 14 shows an example of a liquid crystal display device using the antireflection film of the present invention. The polarizing plate shown in FIG. 13, that is, a polarizing plate having a layer structure composed of a TAC film / a polarizing element / an anti-reflection film is laminated on the liquid crystal display element 15. , A polarizing plate having a layer structure of TAC film / polarizing element / TAC film is laminated. Note that S
In a TN-type liquid crystal display device, a phase difference plate is inserted between a liquid crystal display element and a polarizing plate.

[0116]

【Example】

[Example 1] MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Chemical Industries, Ltd.) on a release film (MC-19: trade name, manufactured by Reiko Co., Ltd., the surface of which is subjected to acryl-melamine treatment) Coating is performed to a thickness of 100 nm.

On the other hand, on a triacetyl cellulose film having a thickness of 80 μm, an electron beam-curable resin (EXG: trade name, manufactured by Dainichi Seika) was applied so as to have a thickness of 5 μm / dry. The film and the coating film surface were bonded together and pressure-bonded and laminated, and an electron beam was irradiated at 4 Mrad at 10 m / min to cure the electron beam-curable resin, and then the release film was peeled off. The resulting transparent functional film had a total light transmittance of 95% (92% of a triacetyl cellulose film as a base film), and the surface was not damaged by nail scratches. This transparent functional film has a function as an antireflection film.

The transparent functional film obtained in Example 1 corresponds to the one shown in FIG.

Example 2 An MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Chemical Industries, Ltd.) and a fluorine-based acrylate (manufactured by Osaka Organic Chemicals) were used on the same release film as used in Example 1 above: A mixture obtained by mixing at a mixing ratio of 2 is applied so as to have a film thickness of 100 nm.

An electron beam-curable resin (X-12-2400, manufactured by Shin-Etsu Chemical Co., Ltd.) and PET having a refractive index of 1.68 were formed on a PET film.
A mixture of b ₂ O ₅ (manufactured by Nissan Chemical Industries) at a ratio of 1: 2 was applied so as to have a film thickness of 5 μm / dry, the release film was laminated, and an electron beam was irradiated at 4 Mrad at 10 m / min. Then, after the electron beam-curable resin was cured, the release film was peeled off. The obtained transparent functional film has a total light transmittance of 91% (PET film 87 as a base film).
%), The surface was not damaged by nail scratches. This transparent functional film has a function as an antireflection film.

FIG. 7 shows a cross section of the transparent functional film obtained in Example 2, and the transparent functional film was
It has a functional ultrafine particle layer 2 formed from the inside to the surface of a hard coat layer 4 of an electron beam-curable resin applied on a transparent plastic substrate film 3. As shown in FIG. 7, the functional ultrafine particle layer 2
The functional ultrafine particle layer 2 is completely buried in the hard coat layer 4 made of an electron beam curable resin because it is bound by its own binding power and the binder resin 7. Further, Sb ₂ O ₅ ultrafine particles 8 (refractive index: 1.68) are mixed in the hard coat layer 4.

Example 3 As the release film of Example 1, a matte PE having fine irregularities on the surface was used.
A transparent functional film having an antireflection effect was produced under the same conditions as in Example 1 except that T (X-45: trade name, manufactured by Toray Industries, Inc.) was used.

FIG. 8 shows a cross section of the transparent functional film obtained in Example 3, and the transparent functional film was
It has a functional ultrafine particle layer 2 formed from the inside to the surface of a hard coat layer 4 of an electron beam-curable resin applied on a transparent plastic substrate film 3. As shown in FIG. 8, the surface of the functional ultrafine particle layer 2 has the same fine irregularities as the surface of the release film.

Example 4 As the release film of Example 2, a matte PE having fine irregularities on the surface was used.
A transparent functional film having an anti-reflection effect was produced under the same conditions as in Example 2 except that T (X-45: trade name, manufactured by Toray) was used.

Example 5 Release Film (MC-19:
(Trade name, manufactured by Reiko Co., Ltd., surface of which is subjected to acryl-melamine treatment)) was coated with a ZnO ultrafine particle dispersion having a refractive index of 1.9 to a thickness of 72 nm. On the other hand, an electron beam-curable resin (EXG: trade name, manufactured by Dainichi Seika) was applied on a triacetyl cellulose film (TAC film) having a thickness of 80 μm so as to be 5 μm / dry. Laminated with both coated surfaces together, irradiating with electron beam at 2 Mrad,
After the resin is semi-cured, the release film is peeled off and ZnO
The ultrafine particle layer was transferred to an electron beam-curable resin. On this transferred layer, a fluorine-based acrylate (Biscoat 8F:
(Trade name, manufactured by Osaka Organic Chemical Co., Ltd.) was applied to a thickness of 100 nm, irradiated with 3 Mrad of electron beam, and the resin layer was completely cured to obtain a transparent functional film having an antireflection effect. The resulting transparent functional film had a total light transmittance of 95%.

FIG. 9 shows a cross section of the transparent functional film obtained in Example 5. The transparent functional film,
On the transparent plastic substrate film 3, functional ultrafine particles 5 having a high refractive index are localized and fixed from the inside to the surface of the hard coat layer 4 of the electron beam-curable resin, and the outermost surface of the electron beam-curable resin is thin. The functional ultrafine particle layer 2 is completely covered with the film. Further, a low refractive index layer 9 is formed on this film to form a transparent functional film having an antireflection effect.

Example 6 Release Film (MC-19:
(Trade name, manufactured by Reiko, surface treated with acryl-melamine) coated with a ZnO ultrafine particle dispersion having a refractive index of 1.9 to a thickness of 72 nm, and triacetyl having a thickness of 80 μm. A ZnO ultrafine particle dispersion and an electron beam-curable resin (HN-5) are formed on a cellulose film (TAC film).
A: A resin (refractive index: 1.65) obtained by mixing 2: 1 by weight ratio of trade name, manufactured by Mitsubishi Yuka Co., Ltd. was applied so as to be 5 μm / dry. After laminating both, the resin was irradiated with an electron beam at 2 Mrad and the resin was semi-cured. Then, the release film was peeled off, and the ZnO ultrafine particle layer was transferred to the ultrafine particle dispersed electron beam-curable resin. On this transferred layer, a fluorine-based acrylate (Biscoat 8F: trade name, manufactured by Osaka Organic Chemicals) was added for 10 minutes.
Coating was performed to a thickness of 0 nm, and electron beam irradiation was performed at 3 Mrad to completely cure the resin layer to obtain a transparent functional film having an antireflection effect. The resulting transparent functional film is
The total light transmittance was 95%.

Example 7 Release Film (MC-19:
(Trade name, manufactured by Reiko, surface treated with acryl-melamine) coated with a ZnO ultrafine particle dispersion having a refractive index of 1.9 so as to have a thickness of 72 nm, and ZnO ultrafine particles dispersed on the layer. A resin (refractive index: 1.65) obtained by mixing the liquid and an electron beam-curable resin (HN-5A: trade name, manufactured by Mitsubishi Yuka) at a weight ratio of 2: 1 was applied so as to be 3 μm / dry. The film was irradiated with an electron beam at 10 Mrad to completely cure the resin. On this layer, a mixture of a urethane-based adhesive (Takelac: trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) and a curing agent mixed at a ratio of 6: 1 was used. It was coated and laminated with a triacetyl cellulose film having a thickness of 80 μm.

This film was aged at 40 ° C. for 3 days, and the release film was peeled off.
The film was formed with a thickness of 100 nm by a plasma deposition method. The transparent functional film thus obtained has a total light transmittance of 9
It was 5.1%.

Example 8 Release Film (MC-19:
(Trade name, manufactured by Reiko, surface treated with acryl-melamine) coated with a ZnO ultrafine particle dispersion having a refractive index of 1.9 so as to have a thickness of 72 nm, and ZnO ultrafine particles dispersed on the layer. A resin (refractive index: 1.65) obtained by mixing the liquid and an electron beam-curable resin (HN-5A: trade name, manufactured by Mitsubishi Yuka) at a weight ratio of 2: 1 was applied so as to be 3 μm / dry. The film is irradiated with an electron beam at 2 Mrad, the resin is half-cured, and a mixture of a urethane-based adhesive (Takelac: trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) and a curing agent mixed at a ratio of 6: 1 is applied on this layer. And laminated with an 80 μm thick triacetyl cellulose film.

This film was aged at 40 ° C. for 3 days, and after the release film was peeled off, a fluorine-based acrylate (Biscoat 8F: trade name, manufactured by Osaka Organic Chemical Co., Ltd.) was applied on this layer to a thickness of 100 nm. And the electron beam is 3Mr
Irradiation was performed to completely cure the resin layer to obtain a transparent functional film having an antireflection effect. The resulting transparent functional film had a total light transmittance of 95%.

Example 9 Release Film (MC-19:
(Trade name, manufactured by Reiko Co., Ltd., surface of which is treated with acryl-melamine) coated with a ZnO ultrafine particle dispersion having a refractive index of 1.9 so as to have a thickness of 72 nm, and an electron beam curing type is formed on the layer. Resin (EXG: trade name, manufactured by Dainichi Seika) is 5 μm / dry
It was applied so that After laminating the resin surface and a triacetyl cellulose film having a thickness of 80 μm, an electron beam was irradiated at 5 Mrd to completely cure the resin, and then the release film was peeled off. An SiOx film was formed on this layer with a thickness of 100 nm by a plasma deposition method. The transparent functional film thus obtained had a total light transmittance of 95.1%.

Example 10 Release Film (MC-1)
9: trade name, manufactured by Reiko, the surface of which is treated with acryl-melamine) is coated with a ZnO ultrafine particle dispersion having a refractive index of 1.9 to a thickness of 72 nm, and an electron beam is formed on the layer. 5 μm / d of curable resin (EXG: trade name, manufactured by Dainichi Seika)
ry. This resin surface and thickness 80μm
After laminating the triacetyl cellulose film, the resin was half-cured with an electron beam, and the release film was peeled off. On this layer, a fluorine-based acrylate (Biscoat 8F, trade name, manufactured by Osaka Organic Chemicals) is applied so as to have a thickness of 100 nm, and an electron beam is applied to the layer at 3 Mr.
The resin layer was completely cured by ad irradiation to obtain a transparent functional film having antireflection curing. The resulting transparent functional film had a total light transmittance of 95.3%.

Example 11 Release Film (MC-1)
9: trade name, manufactured by Reiko Co., Ltd., the surface of which is treated with acryl-melamine), coated with MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Chemical Industries, Ltd.) to a film thickness of 100 nm.

On the other hand, a blended resin of an electron beam-curable pressure-sensitive adhesive and an electron beam-curable resin was applied on a 100 μm-thick PET film so as to have a film thickness of 5 μm / dry, and the solvent was dried (100 ° C. After 30 minutes), the above-mentioned release film and the coating film surface were put together and pressure-bonded and laminated, and an electron beam was applied for 4 minutes.
After irradiating Mrad at 10 m / min to cure the electron beam-curable blend resin, the release film was peeled off. The obtained transparent functional film has a total light transmittance of 92%.
(87% of PET film as a base film), the surface was not damaged by nail scratches. This transparent functional film has a function as an antireflection film.

The transparent functional film obtained in Example 11 corresponds to the one shown in FIG.

Example 12 On the same release film as used in Example 11, MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Chemical) and fluorine-based acrylate (manufactured by Osaka Organic Chemical) were used: A mixture with a mixing ratio of 2 is 100 nm thick
It was coated so that it becomes.

A blend resin of an electron beam-curable adhesive and an electron beam-curable resin on a PET film, and a refractive index of 1.68
Of Sb ₂ O ₅ (manufactured by Nissan Chemical Industries, Ltd.) in a ratio of 1: 2 was coated so as to have a film thickness of 5 μm / dry, and the coating side of the PET film was coated with the release film. Laminate inside, electron beam 4Mrad, 10m
The release film was peeled off after curing the electron beam-curable blend resin by irradiating at a rate of / min. The resulting transparent functional film has a total light transmittance of 93% (PE film as a base film).
(T film 87%), the surface was not damaged by nail scratches. This transparent functional film has a function as an antireflection film.

FIG. 10 shows a cross section of the transparent functional film obtained in Example 12, and the transparent functional film is composed of an electron beam-curable pressure-sensitive adhesive applied on a transparent plastic substrate film 3 and an electron beam. It has a functional ultrafine particle layer 2 formed from the inside to the surface of a hard coat layer 4 of a resin blended with a curable resin. As shown in FIG. 10, the functional ultrafine particle layer 2 is bound by the binding force of each functional ultrafine particle 5 itself and the binder resin 7, and the entire functional ultrafine particle layer 2 is made of an electron beam-curable blend system. It is not completely buried in the hard coat layer 4 made of resin, and its surface is in direct contact with the air layer. Further, Sb ₂ O ₅ ultrafine particles 8 (refractive index: 1.68) are mixed in the hard coat layer 4.

Example 13 As a release film, a mat PET (X-4) having fine irregularities formed on the surface was used.
5: trade name, manufactured by Toray Industries, Inc.
An anti-reflection film was produced under the same conditions as described above.

FIG. 11 shows a cross section of the transparent functional film obtained in Example 13, and the transparent functional film is composed of an electron beam-curable pressure-sensitive adhesive applied on a transparent plastic substrate film 3 and an electron beam. It has a functional ultrafine particle layer 2 formed from the inside to the surface of a hard coat layer 4 made of a resin blended with a line-curable resin. As shown in FIG. 11, the surface of the functional ultrafine particle layer 2 has the same fine irregularities as the surface of the release film.

Example 14 On the surface of the transparent functional film obtained in the above Example 11, 100 fluorine-based acrylate (Biscoat 8F, trade name, manufactured by Osaka Organic Chemicals) was applied.
nm, and irradiate with 3 Mrad of electron beam.
The resin layer was completely cured to obtain a transparent functional film having an antireflection effect. The resulting transparent functional film had a total light transmittance of 95%.

FIG. 12 shows a cross section of the transparent functional film obtained in Example 14. The transparent functional film is formed on the transparent plastic substrate film 3 from the inside to the surface of the hard coat layer 4 of the blend resin of the electron beam curable pressure-sensitive adhesive and the electron beam curable resin applied. The functional ultrafine particle layer 2 is further provided with a low refractive index layer 9 on the functional ultrafine particle layer 2 to form a transparent functional film having an antireflection effect.

[0144]

According to the first and second transparent functional films or transparent functional films of the present invention, the functional ultrafine particles are poled and fixed from the interface with the air layer to the inside of the hard coat layer. Therefore, unlike the case where the functional ultrafine particles are simply mixed into the coating film, there is an effect that the properties of the functional ultrafine particles can be easily expressed in a small amount without using a large amount of the functional ultrafine particles. Further, there is an effect that adhesion between the functional ultrafine particles and the hard coat layer is better than simply forming a layer containing the functional ultrafine particles on the hard coat layer.
Also, the antireflection film of the present invention using low refractive index ultrafine particles or high refractive index ultrafine particles as functional ultrafine particles,
The same effect as that of the transparent functional film is obtained.

In the first and second antireflection films of the present invention, the refractive index of the hard coat layer is higher than that of the ultrafine particles having a low refractive index and higher than that of the transparent plastic substrate film. As a result, the antireflection effect can be enhanced, and reflection at the interface between the hard coat layer and another layer can be prevented.

In the third and fourth antireflection films of the present invention, the refractive index of the hard coat layer itself in the portion where the high refractive index ultrafine particle layer does not exist does not exceed the refractive index of the high refractive index ultrafine particle layer. Within this range, the refractive index is higher than the refractive index of the transparent plastic substrate film, so that the antireflection effect can be enhanced and the reflection at the interface between the hard coat layer and another layer can be prevented.

[Brief description of the drawings]

FIG. 1 shows a cross section of a first transparent functional film of the present invention.

FIG. 2 shows a cross section of a second transparent functional film of the present invention.

FIG. 3 is a process diagram of a first manufacturing method for a first transparent functional film of the present invention.

FIG. 4 is a process diagram of a second manufacturing method for the first transparent functional film of the present invention.

FIG. 5 is a process diagram of a third manufacturing method for the first transparent functional film of the present invention.

FIG. 6 is a process diagram of a manufacturing method for a second transparent functional film of the present invention.

FIG. 7 shows a cross section of the transparent functional film obtained in Example 2.

FIG. 8 shows a cross section of the transparent functional film obtained in Example 3.

FIG. 9 shows a cross section of a transparent functional film obtained in Example 5.

FIG. 10 shows a cross section of the transparent functional film obtained in Example 12.

FIG. 11 shows a cross section of the transparent functional film obtained in Example 13.

FIG. 12 shows a cross section of the transparent functional film obtained in Example 14.

FIG. 13 shows a layer configuration of a polarizing plate on which the antireflection film of the present invention is laminated.

FIG. 14 shows a layer structure of a liquid crystal display device using a polarizing plate on which the antireflection film of the present invention is laminated.

[Explanation of symbols]

First release film 2 functional ultrafine particle layer 3 transparent plastic substrate film 4 Hard coat layer 5 functional ultrafine particles 6 adhesive layer 7 binder resin 8 Sb ₂ O ₅ ultrafine particles 9 low refractive index layer 10 high-refractive index hardcoat Layer 11 Primer layer 12 Anti-reflection film 13 Polarizer 14 TAC film 15 Liquid crystal display

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08J 7/04 C08J 7/04 A G02B 1/11 G02B 1/10 A (72) Inventor Natsuko Yamashita Nagiko-cho, Shinjuku-ku, Tokyo 1-1-1 Dai Nippon Printing Co., Ltd. (72) Inventor Yuko Suzuki 1-1-1, Ichigaya Kaga-cho, Shinjuku-ku, Tokyo (72) Inventor Motohiro Oka Ichigaya, Shinjuku-ku, Tokyo 1-1-1, Kagacho Inspector, Dai Nippon Printing Co., Ltd. Toshiko Nakata (56) References JP-A-7-156326 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 G02B 1/10-1/12

Claims (43)

(57) [Claims] 1. A transparent functional film, wherein the functional ultrafine particles are poled and fixed from the interface with the air layer to the inside of the hard coat layer. 2. The functional ultrafine particles are polarized and fixed from the interface with the air layer to the inside of the hard coat layer, and the functional ultrafine particles in contact with the air layer have a thin film of the resin for the hard coat layer. A transparent functional film, characterized in that a part of the functional ultrafine particles is exposed from the hard coat layer without performing. 3. The transparent functional film according to claim 1, wherein the surface of the transparent functional film has fine irregularities. 4. The transparent functional film according to claim 1, wherein the hard coat layer comprises a resin layer having a thickness of 0.5 μm or more. 5. The transparent functional film according to claim 1, wherein the hard coat layer contains an ionizing radiation curable resin as a main component. 6. A transparent functional film, wherein the transparent functional film according to claim 1, 2, 3, 4, or 5 is formed on a transparent plastic substrate film. 7. The transparent functional film according to claim 1, wherein the transparent functional film according to claim 1, 2, 3, 4, or 5 is formed on a transparent plastic substrate film via another layer. the film. 8. A hard coat layer in which ultra-fine particles of low refractive index are localized and fixed from the interface with the air layer to the inside of the hard coat layer, and (2) fixed on a transparent plastic substrate film. (3) The antireflection film, wherein the refractive index of the hard coat layer is higher than the refractive index of the ultrafine particles having a low refractive index. 9. (1) From the interface with the air layer to the inside of the hard coat layer, the ultra-fine particles of low refractive index are localized and fixed, and a part of the ultra-fine particles of low refractive index is partially removed from the surface of the hard coat layer. The exposed hard coat layer is fixed on (2) a transparent plastic substrate film, and (3) the refractive index of the hard coat layer is higher than the refractive index of the low refractive index ultrafine particles. Anti-reflection film. 10. The hard coat layer in which ultra-high refractive index ultrafine particles are localized and fixed from the surface to the inside of the hard coat layer, and (2) a transparent plastic substrate film on the back surface of the hard coat layer (3) a low refractive index layer is further formed on the surface of the hard coat layer on which the high refractive index ultrafine particles are localized; (4) a refractive index of the hard coat layer Is an antireflection film characterized by having a refractive index lower than that of the high refractive index ultrafine particles. (1) High refractive index ultrafine particles are localized and fixed from the surface to the inside of the hard coat layer, and a part of the high refractive index ultrafine particles is exposed from the surface of the hard coat layer. (2) the high-refractive-index ultrafine particles are localized, and a part of the high-refractive-index ultrafine particles is partially removed from the surface of the hard coat layer. A low refractive index layer is further formed on the exposed surface of the hard coat layer, and (4) the refractive index of the hard coat layer is lower than the refractive index of the high refractive index ultrafine particles. An anti-reflection film, characterized in that: 12. The anti-reflection film according to claim 8, 9, 10 or 11, wherein the surface of the anti-reflection film according to claim 8, 9, 10 or 11 has fine irregularities. 13. The hard coat layer has a thickness of 0.5 μm.
10. The method according to claim 8, comprising the resin layer described above.
13. The antireflection film according to 10, 11, or 12. 14. The anti-reflection film according to claim 8, wherein the hard coat layer comprises an ionizing radiation-curable resin as a main component. 15. The reflection according to claim 8, 9, 10, 11, 12, 13, or 14, wherein another layer is interposed between the hard coat layer and the transparent plastic substrate film. Prevention film. (1) forming a functional ultrafine particle layer on a release film; (2) applying a resin composition for a hard coat layer on a transparent plastic substrate film; When the resin composition for a hard coat layer is diluted with a solvent, the solvent is dried, and when the resin composition for a hard coat layer does not contain a solvent, it is left as it is in the above step. The surface of the functional ultra-fine particle layer side of the mold film and the surface of the transparent plastic substrate film obtained in the above step on the side of the resin composition for the hard coat layer are pressure-bonded and laminated to form the functional ultra-fine particle layer hard. Embedded in the resin composition for the coating layer or embedded in a part of the functional ultrafine particle layer; (4) after fully curing the laminate obtained in the above step, peeling off the release film to function Transparent ultrafine particle layer A method for producing a transparent functional film, comprising transferring the film to a plastic substrate film side. (1) forming a functional ultrafine particle layer on a release film; (2) applying a resin composition for a hard coat layer on a transparent plastic substrate film; When the resin composition for a hard coat layer is diluted with a solvent, the solvent is dried, and when the resin composition for a hard coat layer does not contain a solvent, it is left as it is in the above step. The surface of the functional ultra-fine particle layer side of the mold film and the surface of the transparent plastic substrate film obtained in the above step on the side of the resin composition for the hard coat layer are pressure-bonded and laminated to form the functional ultra-fine particle layer hard. Embedded in the resin composition for the coat layer or embedded in a part of the functional ultrafine particle layer; (4) half-curing the laminate obtained in the above step, and then releasing the release film to function In front of conductive ultrafine particle layer (5) Forming another functional film on the half-cured hard coat layer, and (6) Next, performing full curing on the half-cured hard coat layer. Manufacturing method. (18) A functional ultrafine particle layer is formed on a release film, and (2) a resin composition for a hard coat layer is coated on the functional ultrafine particle layer with a thickness of the functional ultrafine particle layer. Coating as described above, the functional ultrafine particle layer is buried in the resin for the hard coat layer or a part of the functional ultrafine particle layer is buried, fully cured to form a hard coat layer, (3) Laminating with a transparent plastic substrate film via an adhesive layer with the hard coat layer side of the release film having the hard coat layer formed inside, and (4) the laminate obtained in the above step A method for producing a transparent functional film, comprising: releasing a release film from a substrate and transferring a hard coat layer to a transparent plastic substrate film side. (19) A functional ultrafine particle layer is formed on a release film, and (2) a resin composition for a hard coat layer is coated on the functional ultrafine particle layer with a thickness of the functional ultrafine particle layer. Coating as described above, the functional ultrafine particle layer is buried in the resin for the hard coat layer or a part of the functional ultrafine particle layer is buried, half-cured to form a hard coat layer, (3) Laminating with a transparent plastic substrate film via an adhesive layer with the hard coat layer side of the release film having the hard coat layer formed inside, and (4) the laminate obtained in the above step (5) forming another functional film on the half-cured hard coat layer; (6) forming the functional film on the half-cured hard coat layer; The hard coat The method for producing a transparent functional film, characterized in that to fully cure the layer. 20. (1) forming a functional ultrafine particle layer on a release film; and (2) coating a resin composition for a hard coat layer on the functional ultrafine particle layer with a thickness of the functional ultrafine particle layer. By coating as described above, the functional ultrafine particle layer is buried in the resin for the hard coat layer or a part of the functional ultrafine particle layer is buried, (3) the resin composition for the hard coat layer The release film coated with is laminated with a transparent plastic substrate film with the side of the resin composition for a hard coat layer facing inside, and fully cured to form a hard coat layer. (4) Obtained in the above step A method for producing a transparent functional film, comprising: releasing a release film from the obtained laminate and transferring a hard coat layer to a transparent plastic substrate film side. 21. (1) A functional ultrafine particle layer is formed on a release film, and (2) a resin composition for a hard coat layer is coated on the functional ultrafine particle layer with a thickness of the functional ultrafine particle layer. By coating as described above, the functional ultrafine particle layer is buried in the resin for the hard coat layer or a part of the functional ultrafine particle layer is buried, (3) the resin composition for the hard coat layer The coated release film was laminated with a transparent plastic substrate film with the side of the resin composition for a hard coat layer facing inward, and half-cured to form a hard coat layer. (4) Obtained in the above step Peeling off the release film from the obtained half-cured laminate and transferring the hard coat layer to the transparent plastic substrate film side; (5) forming another functional film on the half-cured hard coat layer; (6) Before The method for producing a transparent functional film, characterized in that to fully cure the hard coat layer. 22. The method of embedding the functional ultrafine particle layer in the resin for the hard coat layer or embedding a part of the functional ultrafine particle layer includes the steps of:
It is controlled by the type of the resin, the surface tension of the resin, the particle size of the functional ultrafine particles, the filling rate of the ultrafine particles, and the wettability between the resin for the hard coat layer and the functional ultrafine particles. The method for producing a transparent functional film according to claim 16, 17, 18, 19, 20, or 21. 23. The resin composition for a hard coat layer,
The ionizing radiation-curable resin is used as a main component.
3. The method for producing a transparent functional film according to 2. 24. The resin composition for a hard coat layer,
The resin is in a touch-dry state at the time of coating, wherein the resin is in a dry state.
4. The method for producing a transparent functional film according to 3. 25. The resin composition for a hard coat layer,
18. An ionizing radiation-curable resin as a main component, and containing a thermosetting resin.
18. The method for producing a transparent functional film according to 18, 19, 20, 21, 22, 23 or 24. 26. The functional ultrafine particle layer formed on the release film contains a binder resin in such an amount that the functional ultrafine particles are not completely buried in the binder resin. Claims 16, 17, 18, 1
9. The method for producing a transparent functional film according to 9, 20, 21, 22, 23, 24 or 25. 27. The functional ultrafine particle, wherein the surface thereof is imparted with hydrophobicity by a coupling agent.
27. The method for producing a transparent functional film according to 2, 23, 24, 25 or 26. 28. The release film according to claim 16, wherein fine irregularities are formed on a surface of the release film.
17, 18, 19, 20, 21, 22, 23, 24, 2
28. The method for producing a transparent functional film according to 5, 26 or 27. 29. (1) forming a high-refractive-index ultrafine particle layer on a release film; and (2) a refractive index lower than the refractive index of the high-refractive-index ultrafine particle layer on a transparent plastic substrate film. (3) When the resin composition for a hard coat layer is diluted with a solvent, the solvent is dried, and then the resin composition for a hard coat layer is coated with a solvent. If it does not contain, as it is, the surface of the release film obtained in the above step on the high refractive index ultrafine particle layer side, the resin composition for the hard coat layer of the transparent plastic substrate film obtained in the above step The object side surface is pressed and laminated, and the high refractive index ultrafine particle layer is buried in the resin composition for the hard coat layer, or a part of the high refractive index ultrafine particle layer is buried in the resin composition for the hard coat layer. The laminate obtained in After forming a hard coat layer, the release film is peeled off and the high refractive index ultrafine particle layer is transferred to the transparent plastic substrate film side. (5) Then, a low refractive index layer is formed on the hard coat layer. Forming an anti-reflection film. 30. (1) forming a high-refractive-index ultrafine particle layer on a release film; and (2) a refractive index lower than the refractive index of the high-refractive-index ultrafine particle layer on a transparent plastic substrate film. (3) When the resin composition for a hard coat layer is diluted with a solvent, the solvent is dried, and then the resin composition for a hard coat layer is coated with a solvent. If it does not contain, as it is, the surface of the release film obtained in the above step on the high refractive index ultrafine particle layer side, the resin composition for the hard coat layer of the transparent plastic substrate film obtained in the above step The object side surface is pressed and laminated, and the high refractive index ultrafine particle layer is buried in the resin composition for the hard coat layer, or a part of the high refractive index ultrafine particle layer is buried in the resin composition for the hard coat layer. Half of the laminate obtained in After curing to form a hard coat layer, the release film is peeled off to transfer the high refractive index ultrafine particle layer to the transparent plastic substrate film side. (5) On the half-cured hard coat layer,
(6) A method for producing an antireflection film, wherein the hard coat layer is fully cured. 31. (1) a high refractive index ultrafine particle layer formed on a release film, (2) in the high refractive index ultrafine particles layer, refractive index lower than the refractive index of the high refractive index ultrafine particles layer Coating the resin composition for a hard coat layer having a thickness of the high refractive index ultrafine particle layer or more, or burying the high refractive index ultrafine particle layer in the resin for the hard coat layer or the high refractive index layer A part of the ultrafine particle layer is buried and fully cured to form a hard coat layer,
(3) Laminating with a transparent plastic substrate film via an adhesive layer with the hard coat layer side of the release film having the hard coat layer formed inside, and (4) the laminate obtained in the above step (5) Then, a low refractive index layer is formed on the hard coat layer to produce an anti-reflection film. Method. 32. (1) forming a high-refractive index ultrafine particles layer on a release film, (2) in the high refractive index ultrafine particles layer, refractive index lower than the refractive index of the high refractive index ultrafine particles layer Coating the resin composition for a hard coat layer having a thickness of the high refractive index ultrafine particle layer or more, or burying the high refractive index ultrafine particle layer in the resin for the hard coat layer or the high refractive index layer A part of the ultra-fine particle layer is buried and half-cured to form a hard coat layer. (3) The hard coat layer side of the release film on which the hard coat layer is formed is set to the inside, and via the adhesive layer (4) The release film was peeled off from the laminate obtained in the above step, and the hard coat layer was transferred to the transparent plastic substrate film side. (5) Half-cured The hard coat layer Low refractive index layer is formed, (6) the production method of the antireflective film, characterized in that to fully cure the hard coat layer. 33. (1) forming a high-refractive index ultrafine particles layer on a release film, (2) in the high refractive index ultrafine particles layer, refractive index lower than the refractive index of the high refractive index ultrafine particles layer Coating the resin composition for a hard coat layer having a thickness of the high refractive index ultrafine particle layer or more, or burying the high refractive index ultrafine particle layer in the resin for the hard coat layer or the high refractive index layer A part of the ultrafine particle layer is buried; (3) a transparent plastic substrate film with the side of the resin composition for hard coat layer of the release film coated with the resin composition for hard coat layer facing inside; Laminate,
(4) peeling off the release film from the laminate obtained in the above step to transfer the hard coat layer to the transparent plastic substrate film side; (5) A method for producing an antireflection film, comprising forming a low refractive index layer on a hard coat layer. 34. (1) forming a high-refractive index ultrafine particles layer on a release film, (2) in the high refractive index ultrafine particles layer, refractive index lower than the refractive index of the high refractive index ultrafine particles layer Coating the resin composition for a hard coat layer having a thickness of the high refractive index ultrafine particle layer or more, or burying the high refractive index ultrafine particle layer in the resin for the hard coat layer or the high refractive index layer A part of the ultrafine particle layer is buried; (3) a transparent plastic substrate film with the side of the resin composition for hard coat layer of the release film coated with the resin composition for hard coat layer facing inside; Laminate,
(4) peeling off the release film from the half-cured laminate obtained in the above step and transferring the hard-coat layer to the transparent plastic substrate film side; (6) A method for producing an antireflection film, comprising: forming a low refractive index layer on the cured hard coat layer; and (6) fully curing the hard coat layer. 35. The method of embedding the high-refractive-index ultrafine particle layer in the resin for the hard coat layer or embedding a part of the high-refractive-index ultrafine particle layer in the resin for the hard coat layer, , The surface tension of the resin, the particle size of the high refractive index ultrafine particles, the filling rate of the high refractive index ultrafine particles, and the wettability between the resin for the hard coat layer and the high refractive index ultrafine particles. 29. The method of claim 29, 30, or 3,
35. The method for producing a transparent functional film according to 1, 32, 33 or 34. 36. The resin composition for a hard coat layer,
The ionizing radiation curable resin is used as a main component.
6. The method for producing the antireflection film according to 5. 37. The resin composition for a hard coat layer,
The resin is in a dry-to-touch state at the time of coating, wherein the resin is in a dry state.
7. The method for producing an antireflection film according to item 6. 38. The resin composition for a hard coat layer,
31. An ionizing radiation-curable resin as a main component and containing a thermosetting resin.
The method for producing an antireflection film according to 31, 32, 33, 34, 35, 36 or 37. 39. The high refractive index ultrafine particle layer formed on the release film contains a binder resin in such an amount that the high refractive index ultrafine particles are not completely buried in the binder resin. Claims 29, 30, and 3
The method for producing an antireflection film according to 1, 32, 33, 34, 35, 36, 37 or 38. 40. The surface of the high refractive index ultrafine particles is provided with hydrophobicity by a coupling agent.
9, 30, 31, 32, 33, 34, 35, 36, 3,
40. The method for producing an antireflection film according to 7, 38 or 39. 41. The release film having fine irregularities formed on the surface thereof.
2, 33, 34, 35, 36, 37, 38, 39 or 4
0. The method for producing an antireflection film according to 0. 42. The low refractive index layer is formed by coating.
3, 34, 35, 36, 37, 38, 39, 40 or 4
2. The method for producing the antireflection film according to 1. 43. The low-refractive-index layer is formed by a vapor phase method.
3, 34, 35, 36, 37, 38, 39, 40 or 4
2. The method for producing the antireflection film according to 1.