JPH07225302A - Transparent functional film containing functional superfine particle, transparent functional film and its production - Google Patents

Abstract

PURPOSE:To provide a transparent functional film which is a transparent functional film having a hard coating layer on a transparent plastic base material, exhibits the function of functional superfine particles by arranging the functional superfine particles so as to deviate extremely at a high density and has an excellent adhesion property of the hard coating layer and the functional superfine particle layer and an antireflection film and a process for producing these films. CONSTITUTION:The functional superfine particle layer 2 is formed on a release film 1. On the other hand, a resin compsn. for the hard coating layer is applied on the transparent plastic base material film 3 and both are laminated by pressurized contact to embed a part of the functional superfine particles 5 into the resin compsn. for the hard coating layer. This release film 1 is peeled after the laminated matter is cured. The functional superfine particle layer 2 of the resulted transparent functional film is partly embedded and fixed into the hard coating layer 4 and the functional superfine particles 5 deviate extremely from the surface of the hard coating layer 4 to the inside. The transparent functional film exposed with a part of the functional superfine particles 5 is obtd. if the release film l formed with the functional superfine particle layer 2 is subjected to pressurized contact while the hard coating layer 4 is in the dry state to touch.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a functional ultrafine particle having various functions such as an ultraviolet ray blocking effect, an antistatic effect and an antireflection effect in a coating film, particularly on the surface of a layer which is 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, in which the function of the functional ultrafine particles is exhibited by localizing the functional ultrafine particles. Furthermore, 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, an ultraviolet blocking effect, an antistatic effect,
By coating a transparent plastic substrate film with a transparent resin composition in which functional ultrafine particles having specific properties such as an antireflection effect are dispersed to form a functional coating film, ultraviolet blocking property, antistatic property or It is known to produce a transparent functional film having a function such as antireflection property.

Further, in such a transparent functional film,
Furthermore, in order to impart properties such as scratch resistance and chemical resistance,
As an intermediate layer on a transparent plastic substrate film, for example, a hard coat layer made of an ionizing radiation-curable resin or the like is formed, and a transparent resin composition having functional ultrafine particles dispersed thereon is applied to obtain a hard property. It is known to produce an applied transparent functional film.

[0004]

The transparent functional film containing the above-mentioned 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, a large amount of the functional ultrafine particles should be present in the film, but for this reason, the mixing ratio of the functional ultrafine particles dispersed in the resin must be high. However, there is a problem in that film formation becomes difficult. Further, in a transparent functional film having a hard coat layer such as an ionizing radiation curable resin, the adhesion between the hard coat layer and the transparent functional film is not sufficient, and there is a problem that the transparent functional film is easily peeled off. there were.

Therefore, in the present invention, in producing a transparent functional film, a transparent functional film and an antireflection film, functional ultrafine particles are localized in a high density in a hard coat layer to obtain functional ultrafine particles. By arranging as a layer, the function of the functional ultrafine particles can be exerted, and further, the transparent functional film, the transparent functional film, the antireflection film and the excellent adhesion between the hard coat layer and the functional ultrafine particles, It is an object to provide a method for producing them.

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

[0007]

Transparent functional film and transparent functional film : In order to solve the above-mentioned problems, the first transparent functional film of the present invention is
It is characterized in that it is 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.

The second transparent functional film of the present invention is
The functional ultrafine particles are localized and fixed from the interface with the air layer to the inside of the hard coat layer, and the thin film of the hard coat layer does not exist in the functional ultrafine particles in contact with the air layer. A part is a transparent functional film which is particularly exposed from the hard coat layer.

The transparent functional film of the present invention is characterized in that the above-mentioned first and second transparent functional films are respectively 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 a hard coat layer 4 applied on a transparent plastic substrate film 3. As shown in FIG. 1, the functional ultrafine particle layer 2 is mutually bonded by the binding force of each functional ultrafine particle 5 itself or by the binding force of the binder resin in such an amount that the functional ultrafine particles 5 are not completely buried. The functional ultrafine particle layer 2 is formed by binding and is buried in the hard coat layer 4 to the extent that a thin film of the resin for hard coat layer is formed. The hard coat layer 4 itself having the functional ultrafine particle layer 2 is the first transparent functional film of the present invention.

FIG. 2 shows a cross section of the 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 a hard coat layer 4 applied on a transparent plastic substrate film 3. As shown in FIG. 2, the functional ultrafine particle layer 2 is mutually bonded by the binding force of each functional ultrafine particle 5 itself or by the binding force of the binder resin in such an amount that the functional ultrafine particles 5 are not completely buried. The functional ultrafine particle layer 2 is formed by being bound, and the entire functional ultrafine particle layer 2 is formed by the hard coat layer 4
The functional ultrafine particles 5 are partly exposed from the surface of the hard coat layer 4. Therefore, the surface of the functional ultrafine particles 5 should not contain a thin film of the resin for the hard coat layer. Instead, it is in direct contact with the air layer. The hard coat layer 4 itself, which has the functional ultrafine particle layer 2 partially exposed, 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 localized 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. Furthermore, simply forming a layer containing functional ultrafine particles on the hard coat layer. It has an effect that the adhesion between the functional ultrafine particles and the hard coat layer is better than that.

Method for producing transparent functional film : The first method for producing the first and second transparent functional films of the present invention is (1) forming a functional ultrafine particle layer on a release film. (2) On the other hand, after the resin composition for hard coat layer is applied onto a transparent plastic substrate film, (3) when the resin composition for hard coat layer is diluted with a solvent, after solvent drying When the resin composition for the hard coat layer does not contain a solvent, 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 remain as they are. The surface of the substrate film on the resin composition side for the hard coat layer is pressure-bonded and laminated to bury the functional ultrafine particle layer in the resin composition for the hardcoat layer, or 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.

A variation of the first production method of the first and second transparent functional films of the present invention is (1)
A functional ultrafine particle layer is formed on a release film, and (2) on the other hand, 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 formed. After being dried with a solvent when diluted with a solvent, if the resin composition for the hard coat layer does not contain a solvent, the functional ultrafine particle layer of the release film obtained in the above step remains as it is. Side and the surface of the transparent plastic substrate film hard coat layer resin composition side obtained in the above step by pressure bonding and laminating, the functional ultrafine particle layer in the hard coat layer resin composition After burying or partially burying the functional ultrafine particle layer, (4) half-curing the laminate obtained in the above step, peeling the release film to form the functional ultrafine particle layer into the 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 the first manufacturing method for the first and second transparent functional films of the present invention described above. FIG. 3A shows a state in which the 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 state in which the release film 1 having the functional ultrafine particle layer 2 formed thereon is to be pressure-bonded to the transparent plastic substrate film 3 having the hard coat layer 4 formed thereon. Further, (c) shows a state in which both are crimped. In this pressure-bonded state, after the hard coat layer resin is cured, the release film 1 is peeled off, as shown in (d).

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

The first and second methods for producing a transparent functional film according to the present invention are (1) forming a functional ultrafine particle layer on a release film, and (2) the functional ultrafine particle layer. A resin composition for a hard coat layer is coated thereon so as to have a thickness equal to or larger than that of the functional ultrafine particle layer, and the functional ultrafine particle layer is embedded in the resin for a hard coat layer or the functional ultrafine particle. A part of the layer is buried and fully 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 the inside, and the hard coat layer is transparent through the adhesive layer. It is laminated with a plastic substrate film, and (4) the release film is peeled from the laminate obtained in the above step to transfer the hard coat layer to the transparent plastic substrate film side.

The first modified method of the transparent functional film according to the second aspect of the present invention is (1) forming a functional ultrafine particle layer on a release film, and (2) forming the functional ultrafine particle layer. A resin composition for a hard coat layer is coated thereon so as to have a thickness equal to or larger than that of the functional ultrafine particle layer, and the functional ultrafine particle layer is embedded in the resin for a hard coat layer or the functional ultrafine particle. Part of the 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 placed inside, and a transparent layer is formed through an adhesive layer. Laminating with a plastic substrate film, (4) peeling the release film from the laminate obtained in the step, transferring the hard coat layer to the transparent plastic substrate film side, and (5) half curing Tasai 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 above-mentioned first and second transparent functional films of the present invention. In FIG. 4 (a), a sol of functional ultrafine particles 5 is applied onto a release film 1 to form a functional ultrafine particle layer 2, and a resin composition for a hard coat layer is further coated with the functional ultrafine particles. The hard coat layer 4 is formed by coating so as to have a film thickness equal to or larger than that of the layer 2. In this step (a), the hard coat layer 4 may be fully cured or half cured (variant method). (B) is a state in which the release film 1 having the hard coat layer 4 obtained in the step (a) is to be laminated with the transparent plastic substrate film 3 via the adhesive layer 6. The adhesive layer 6 may be formed by coating the hard coat layer 4 or the transparent plastic substrate film 3. Further, (c) shows a state in which both are crimped. In this pressure-bonded state, the state where the release film 1 is peeled off is (d).

In the step (a) of FIG. 4, when the hard coat layer resin is completely half-cured, the hard coat layer resin is fully cured after the release film 1 is peeled off in the step (d). You can Thus, dividing the cure of the hard coat layer into a half cure and a full cure increases the adhesion between the hard coat layer and a layer thereabove, for example, when a layer is further provided thereon after the half cure. There are advantages.

The third and third methods for producing the transparent functional film of the present invention are (1) forming a functional ultrafine particle layer on a release film, and (2) the functional ultrafine particle layer. A resin composition for a hard coat layer is coated thereon so as to have a thickness equal to or larger than that of the functional ultrafine particle layer, and the functional ultrafine particle layer is embedded in the resin for a hard coat layer or the functional ultrafine particle. 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 being the inner side. Then, the hard coat layer is formed by full curing, and (4) the release film is peeled from the laminate obtained in the above step to transfer the hard coat layer to the transparent plastic substrate film side.

The modified method of the third production method of the first and second transparent functional films of the present invention is: (1) forming a functional ultrafine particle layer on a release film; A resin composition for a hard coat layer is coated on the ultrafine particle layer so as to have a film thickness equal to or larger than the film thickness of the functional ultrafine particle layer, and the functional ultrafine particle layer is embedded in the resin for the hard coat layer or has a function. (3) A transparent plastic substrate film with the side of the resin composition for a hard coat layer of the release film coated with the resin composition for a hard coat layer being the inner side. And half-cure to form a hard coat layer, and (4) release the release film from the half-cure laminate obtained in the above step to transfer 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 above-mentioned first and second transparent functional films of the present invention. In FIG. 5 (a), a sol of functional ultrafine particles 5 is applied onto a release film 1 to form a functional ultrafine particle layer 2, and a resin composition for a hard coat layer is further coated thereon with the functional ultrafine particles. It is a state in which the hard coat layer 4 is formed by coating so as to have a film thickness of the layer 2 or more. In this step (a), the hard coat layer 4 has not yet undergone the curing treatment. (B) is a state in which the release film 1 having the uncured hard coat layer 4 obtained in the step (a) is to be laminated with the transparent plastic substrate film 3. Further, (c) shows a state in which both are crimped. In the state of (c), a curing treatment is performed, and the hard coat layer 4 is subjected to full cure or half cure. Next, the state where the release film 1 is peeled off is (d).

In the step (c), the hard coat layer resin composition may be fully cured, or in the step (c), the hard coat layer resin composition may be half-cured. Then, the hard coat layer 4 may be fully cured after the release film 1 is peeled off in the step (d). In this way, the curing of the hard coat layer 4 is divided into half cure and full cure. For example, when a layer is further provided on the hard coat layer after the half cure, the adhesion between the hard coat layer 4 and the layer thereabove. Has the advantage of increasing.

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 (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 functionality 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 hard coat layer resin and the functional ultrafine particles, and the like.

Specifically, by selecting as the resin for the hard coat layer, one having a high viscosity or having a touch-drying property (described later) at the time of coating (touch-drying state),
It is easy to expose some of the functional ultrafine particles. Alternatively, it is also possible to select a resin having a low surface tension or a functional ultrafine particle having a small particle size and a high packing rate. Further, when 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 manufacturing method for the second transparent functional film of the present invention.
FIG. 6A shows a state in which the 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 release film 1 in which the functional ultrafine particle layer 2 is formed by applying a resin composition for a hard coat layer onto a transparent plastic substrate film 3 and the coating film is in a touch-free state. It is in a state of being crimped, and (c) is in a state of being crimped. Since the release film 1 is pressure-bonded when the resin composition for the hard coat layer is in a dry state 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,
A part of the functional ultrafine particle layer 2 will remain outside the hard coat layer. In this pressure-bonded state, ionizing radiation such as electron beam or ultraviolet ray is irradiated to completely cure the ionizing radiation-curable resin, and then the release film 1 is peeled off (d).
Is.

Release film : Generally, a release-treated film such as silicon, fluorine or acryl-melamine, or an untreated one is used. The surface may have unevenness, and in this case, since unevenness is formed on the surface of the final product, it is possible to impart an antireflection effect or an antiglare effect to the obtained transparent functional film.

Functional ultrafine particles : The functional ultrafine particles used in the functional ultrafine particle layer are ultrafine particles of 200 nm or less and have functions such as ultraviolet ray blocking property, conductivity, antistatic property and antireflection property. The thing which has is mentioned. For example, to impart conductivity or antistatic properties to the transparent functional film, S
Ultra-fine particles such as nO ₂ and ITO are used, and low-refractive-index ultra-fine particles such as MgF ₂ and SiO ₂ and high particles such as Sb ₂ O ₅ , ZnO, ITO, SnO ₂ and TiO ₂ are used to impart antireflection property. Ultrafine particles of refractive index are used.

The production of the antireflection film using the high-refractive-index ultrafine particles is carried out by applying a low-refractive-index inorganic material such as MgF ₂ or SiO ₂ on the coating film containing the high-refractive-index ultrafine particles. And metal materials such as evaporation, sputtering, plasma CV
A thin film is formed in a single layer or a multilayer by D or the like, or a coating film of a low refractive index resin composition containing a low refractive index inorganic material such as MgF ₂ or SiO ₂ or a metal material is formed in a single layer or a multilayer. When formed, it can be used as an antireflection film.

In order to impart an ultraviolet blocking property, Sb ₂
Ultrafine 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 such a hydrophobic treatment introduces a hydrophobic group to the surface of the functional ultrafine particles. , The ionizing radiation-curable resin is easily adapted to the 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 amount of the coupling agent added is 0 (not including 0) to 30 parts by weight, preferably 0 (0
Is not included) to 10 parts by weight.

When the surface of the functional ultrafine particles is inactive such as MgF ₂ , SiO ₂ sol is added in advance, and the surface of the functional ultrafine particles is coated with SiO ₂ and then treated with a coupling agent. May be. By such a coating treatment of SiO ₂ , many hydrophilic groups can be introduced on the surface of the functional ultrafine particles, and the subsequent treatment with the coupling agent can surely introduce more hydrophobic groups. The ultrafine particles become more compatible with the resin and the bondability increases.

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, it can be formed by the binding action of the functional ultrafine particles themselves without using a binder resin, but the binding action is weak. In such a case, a binder resin may be used if necessary. The amount of the binder resin should be such that the functional ultrafine particles are not completely embedded in the binder resin, and the functional ultrafine particles are bound to each other while the surfaces of the functional ultrafine particles are exposed. Therefore, it is preferable for exhibiting functionality, particularly when used for an antireflection film.

As such a binder resin, a general one such as a thermosetting resin, a thermoplastic resin or an ionizing radiation curable resin is used, but the lower layer (ionizing radiation curable resin) is used.
Considering the adhesiveness with, an ionizing radiation curable resin is desirable, and the ionizing radiation curable resin is desirably a solvent-drying semi-curable resin. Further, a colorant may 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. The thickness thereof is preferably about 8 μm to 1000 μm.

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

In the present invention, "having hard performance" or "hard coat" means 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, the binder resin used in the hard coat layer is a reaction curable resin, that is, a thermosetting resin and / or an ionizing radiation curable resin. It is preferable. The thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin, poly Siloxane resin or the like is used, and if necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. are used.

The ionizing radiation curable resin preferably has an acrylate 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 such as (meth) acrylate of polyfunctional compound such as polyhydric alcohol, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone as a 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 polyester acrylate and polyurethane acrylate is used. The reason is that polyester acrylate is suitable for obtaining a hard coat because the coating is very hard, but polyester acrylate alone has a low impact resistance and becomes brittle, so that the coating has impact resistance and flexibility. Polyurethane acrylate is used together to impart the property. The mixing ratio of polyurethane acrylate to 100 parts by weight of polyester acrylate is 30 parts by weight or less. This is because if the value exceeds this value, the coating film becomes too soft and loses its hardness.

Further, in order to make the above ionizing radiation curable resin composition into an ultraviolet curable resin composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime are used as photopolymerization initiators therein. Ester, tetramethylthiuram monosulfide,
Thioxanthones and n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used as a photosensitizer. Particularly 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, the hard coat layer may contain 10 parts by weight or more and 100 parts by weight or less of the solvent drying type resin with respect to 100 parts by weight of the ionizing radiation curable resin. A thermoplastic resin is mainly used as the solvent-drying resin. The type of solvent-drying type thermoplastic resin to be added to the ionizing radiation-curable resin is usually used, but especially when a mixture of polyester acrylate and polyurethane acrylate is used for the ionizing radiation-curable resin, it is used. As the solvent-drying resin used, polymethacrylic acid methyl acrylate or polymethacrylic acid butyl acrylate can keep the hardness of the coating film high. Moreover, in this case, since the refractive index is close to that of the main ionizing radiation curable resin, the transparency of the coating film is not impaired, and the transparency,
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, the solvent drying type resin contained in the ionizing radiation curable resin includes nitrocellulose, acetyl cellulose and cellulose acetate propio. Cellulose resins such as nate and ethyl hydroxyethyl cellulose are advantageous in terms of adhesion and transparency of the coating film.

The reason for this is that when toluene is used as the solvent in the above cellulose-based resin, the transparent plastic substrate is used in spite of the use of toluene, which is a non-soluble solvent for triacetyl cellulose, which is the transparent plastic substrate film. Even if the coating material containing this solvent-drying type resin is applied to the material film, the adhesion between the transparent plastic substrate film and the coating resin can be improved, and this toluene is a transparent plastic substrate film. This is because, since 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 for curing an ionizing radiation curable resin, that is, curing by irradiation with electron beams or ultraviolet rays. You can For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type, An electron beam or the like having an energy of 100 to 300 KeV is preferably used, and in the case of ultraviolet curing, ultraviolet rays or the like emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, carbon arc, 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 means the following a. Ionizing radiation curable resin half-crosslinking type half cure,
b. Ionizing radiation curable resin / thermosetting resin (or thermoplastic resin) blend type half cure, and c. Solvent dry type / half cure type composite half cure is mentioned.

A. Ionizing radiation-curable resin half-crosslinking type half cure It is formed by applying a normal ionizing-radiation-curable resin and adjusting the irradiation conditions of the ionizing radiation such as ultraviolet rays or electron beams to the coating film to perform half-crosslinking. 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 a resin composition, and then thermosetting resin When used, it means a state of half cure formed by applying heat to the coating film.

C. Solvent-drying / half-cure composite half-cure A coating film formed by applying a solvent to a normal ionizing radiation-curable resin and drying the solvent,
Further, it means a state of being half-cured by irradiating with ionizing radiation. The state of this half cure is as follows:
This is the same as the semi-cured state described in Japanese Patent Publication No. 49.

Touch- free state : 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. Therefore, since the viscosity of the coating film of the coated resin composition for a hard coat layer is high in the touch-free state, by contacting the functional ultrafine particle layer, the entire functional ultrafine particle layer is formed. Part of the functional ultrafine particle layer is exposed without being completely buried in the hard coat layer. Further, there is an advantage in that the hard coat layer and the functional ultrafine particle layer have good adhesion by making the hard coat layer dry to the touch.

In order to make the coating film of the resin composition for the hard coat layer dry to the touch, a method of using an ionizing radiation-curable resin having a touch-drying property and an adhesive property to the ionizing radiation-curable resin are used. A method of mixing a resin having

The method of using the above ionizing radiation curable resin having a touch-free property is, for example, the following (a):
The ionizing radiation curable resin having the dryness to the touch as shown in (b) can be used.

(A) A resin having a radically 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 monomers listed below and introducing a radical copolymerizable unsaturated group by the methods a) to d) described below.

Monomers having hydroxyl groups: For example, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy. Examples include propyl (meth) acrylate.

Monomers having a carboxyl group: For example,
Examples include (meth) acrylic acid and (meth) acryloyloxyethyl monosuccinate.

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

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

Monomers having isocyanate groups: 2,4
-Addition products of a diisocyanate and a radical copolymer having active hydrogen, such as an addition product of 1 mol to 1 mol of toluene diisocyanate and 2-hydroxyethyl (meth) acrylate.

Further, in order to control the glass transition temperature of the copolymer and the physical properties of the cured film, each of the above-listed monomers and the following compounds can be copolymerized. Examples of such a copolymerizable monomer include methyl (meth) acrylate and propyl (meth).
Examples thereof 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 radical-polymerizable unsaturated groups by the following methods a) to d) into a polymer obtained by polymerizing or copolymerizing each of the above monomers, an ultraviolet curable resin or An ionizing radiation curable resin such as an electron beam curable resin can be 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 a 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, a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylate ester Addition reaction is performed with 1 mol of monomer to 1 mol of adduct.

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

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

Specific examples include stearyl acrylate, stearyl (meth) acrylate, triacrylic isocyanate, cyclohexanediol (meth) acrylate, spiroglycol diacrylate, and spiroglycol (meth) acrylate.

The tacky resin used in the above method of mixing the ionizing radiation curable resin with the tacky resin imparts viscosity to the ionizing radiation curable resin. Generally, it can be formed from a mixture of a pressure-sensitive adhesive and an ionizing radiation-curable resin, but if the ionizing radiation-curable resin is not crosslinked in a liquid state and has an adhesive property, it can be used as it is. it can. In particular, in order to keep the hardness of the coating film high, thermoplastic resins such as polymethylmethacrylate and polybutylmethacrylate can be suitably used for imparting viscosity to the ionizing radiation curable resin.

In addition, the resin suitable for imparting viscosity to the ionizing radiation curable resin may be one which has been used in a conventionally known adhesive tape or adhesive seal, and examples thereof include polyisoprene rubber, polyisobutylene rubber and styrene butadiene. Rubber, rubber-based resin such as butadiene acrylonitrile rubber, (meth) acrylic ester-based resin, polyvinyl ether-based resin, polyvinyl acetate-based resin, polyvinyl chloride / vinyl acetate copolymer-based resin, polystyrene-based resin, polyamide-based resin, Suitable tackifier for polychlorinated olefin resin, polyvinyl butyral resin, etc., for example, rosin, dammar, polymerized rosin, partially hydrogenated rosin, ester rosin, polyterpene resin, terpene modified product, petroleum resin, cyclopentadiene resin Resin, phenolic resin,
Examples thereof include those to which a coumarone-indene resin has been appropriately added, and those to which a softening agent, a filler, an antiaging agent and the like have been added as required.

The mixing ratio of the adhesive resin to the ionizing radiation curable resin is 100 for the ionizing radiation curable resin.
It is preferable that the amount is 50 parts by weight or less with respect to parts by weight for the purpose of keeping the coating film dry to the touch.

Antireflection Film and Manufacturing Method Thereof: The antireflection film of the present invention comprises two kinds of ultrafine particles having low refractive index as functional ultrafine particles and ultrafine particles having high refractive index as functional ultrafine particles. There are two types, a total of four types.

The first antireflection film of the present invention is
From the interface with the air layer to the inside of the hard coat layer, the hard coat layer in which the low refractive index ultrafine particles are localized and fixed, is fixed on the transparent plastic substrate film, and the refractive index of the hard coat layer is The refractive index is higher than that of the ultrafine particles having a low refractive index and higher than that of the transparent plastic substrate film. This antireflection film corresponds to the case where the functional ultrafine particles in the transparent functional film shown in FIG. 1 are low refractive index ultrafine particles.

The second antireflection film of the present invention is
A low-refractive-index ultrafine particle is 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 particle is exposed from the surface of the hard-coat layer. Fixed on a transparent plastic substrate film, the refractive index of the hard coat layer is higher than the refractive index of the low refractive index ultrafine particles, and higher than the refractive index of the transparent plastic substrate film, To do. 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 is
A hard coat layer in which high refractive index ultrafine particles are localized 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 Is further localized on the surface of the hard coat layer is localized, a low refractive index layer is formed, the refractive index of the hard coat layer is within the range not exceeding the refractive index of the high refractive index ultrafine particles. It is characterized by being higher than the refractive index of the transparent plastic substrate film. This antireflection film corresponds to the case where the functional ultrafine particles in the transparent functional film shown in FIG. 9 are high refractive index ultrafine particles.

The fourth antireflection film of the present invention is
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 is exposed from the surface of the hard-coat layer. Fixed on the material film,
The high-refractive-index ultrafine particles are localized, and a low-refractive-index layer is further formed on the surface of the hardcoat layer on which a part of the high-refractive-index ultrafine particles is exposed from the surface of the hardcoat layer. The hard coat layer is formed so that the refractive index thereof is higher than that of the transparent plastic substrate film within a range not exceeding the refractive index of the high refractive index ultrafine particles. This antireflection film corresponds to the transparent functional film shown in FIG. 12 in which the functional ultrafine particles are high refractive index ultrafine particles.

The first antireflection film production method of the present invention is the same as the first production method for producing the first transparent functional film, wherein low refractive index ultrafine particles are used as the functional ultrafine particles. However, in that the resin composition for the hard coat layer having a refractive index higher than that of the low refractive index ultrafine particles and higher than that of the transparent plastic substrate film is used for the resin composition for the hard coat layer. It has characteristics.

The second method for producing an antireflection film of the present invention is the same as the above-mentioned second method for producing a transparent functional film, wherein ultrafine particles having a low refractive index are used as the functional ultrafine particles, and a resin for a hard coat layer is used. The composition is characterized in that a resin composition for a hard coat layer having a refractive index higher than that of the low refractive index ultrafine particles and higher than that of the transparent plastic substrate film is used.

The first production method for producing the third antireflection film of the present invention is (1) forming a high refractive index ultrafine particle layer on a release film, and (2) a transparent plastic substrate. On the material film, a resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film is applied within a range not exceeding the refractive index of the high refractive index ultrafine particle layer, (3 ) If the resin composition for the hard coat layer is diluted with a solvent, after solvent drying, if the resin composition for the hard coat layer does not contain a solvent, then it is obtained as it is in the above step. The surface of the release film on the high-refractive index ultrafine particle layer side and the surface of the transparent plastic substrate film on the resin composition side for the hard coat layer obtained in the above step are pressure-bonded and laminated to each other to obtain a high-refractive index Harvest the particle layer Some of either to bury the coating layer resin composition or a high refractive index ultrafine particle layer is embedded, and (4)
After the laminate obtained in the above step is fully cured 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, and (5) then, A low refractive index layer is formed on the hard coat layer.

Further, a modification of the first production method for producing the third antireflection film of the present invention is (1) forming a high refractive index ultrafine particle layer on a release film, and (2) On the other hand, a resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film is applied onto the transparent plastic substrate film within a range not exceeding the refractive index of the high refractive index ultrafine particle layer. (3) When the resin composition for a hard coat layer is diluted with a solvent, (3) after solvent drying, when the resin composition for a hard coat layer does not contain a solvent, it is as it is, The surface on the high refractive index ultrafine particle layer side of the release film obtained in the step and the surface on the resin composition side for the hard coat layer of the transparent plastic substrate film obtained in the step are pressure-bonded and laminated. , High refractive index The sublayer is embedded in the resin composition for the hard coat layer or a part of the high refractive index ultrafine particle layer is embedded, and (4) the laminate obtained in the above step is half-cured to form the hard coat layer. After that, the release film is peeled off, and the high refractive index ultrafine particle layer is transferred to the transparent plastic substrate film side, and (5) a low refractive index layer is formed on the half-cured hard coat layer, 6)
Then, the hard coat layer is fully cured.

The second production method for producing the third antireflection film of the present invention comprises (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, which has a refractive index higher than that of a transparent plastic substrate film described below within a range not exceeding the refractive index of the high refractive index ultrafine particle layer, is added to the high refractive index ultrafine particle layer. To a thickness not less than that of the high refractive index ultrafine particle layer to be buried in the resin for the hard coat layer, or a part of the high refractive index layer ultrafine particle layer to be fully cured to obtain a hard coating. Forming a coat layer, and (3) laminating the release film on which the hard coat layer is formed with the hard coat layer side inside, and laminating it with a transparent plastic substrate film via an adhesive layer; From the laminate obtained in The hard coat layer was transferred to the transparent plastic base film side was peeled off the mold film, (5)
Then, a low refractive index layer is formed on the hard coat layer.

Further, a modification of the second production method for producing the third antireflection film of the present invention is (1) forming a high refractive index ultrafine particle layer on a release film, and (2) On the high-refractive-index ultrafine particle layer, a resin composition for a hard coat layer having a higher refractive index than that of a transparent plastic substrate film described below is added in a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer. By coating so as to have a thickness of the refractive index ultrafine particle layer or more, the high refractive index ultrafine particle layer is embedded in the resin for the hard coat layer, or a part of the high refractive index layer ultrafine particle layer is embedded, Half-curing is performed 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 placed inside, and the hard coat layer is laminated with a transparent plastic substrate film through an adhesive layer, (4) La obtained in the above process The release film is peeled from the nate to transfer 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 layer. It is characterized in that the coat layer is fully cured.

The third production method for producing the third antireflection film of the present invention is (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, which has a refractive index higher than that of a transparent plastic substrate film described below within a range not exceeding the refractive index of the high refractive index ultrafine particle layer, is added to the high refractive index ultrafine particle layer. Of the high refractive index 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,
(3) Laminating with a transparent plastic substrate film with the resin composition for hard coat layer side of the release film coated with the resin composition for hard coat layer being inside.
Full curing is performed to form a hard coat layer, and (4) the release film is peeled from the laminate obtained in the above step to transfer the hard coat layer to the transparent plastic substrate film side, (5) and then the above It is characterized in that 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 (1) forming a high refractive index ultrafine particle layer on a release film, and (2) On the high-refractive-index ultrafine particle layer, a resin composition for a hard coat layer having a higher refractive index than that of a transparent plastic substrate film described below is added in a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer. By coating so as to have a thickness of the refractive index ultrafine particle layer or more, the high refractive index ultrafine particle layer is embedded in the resin for the hard coat layer, or a part of the high refractive index layer ultrafine particle layer is embedded, (3) The hard coating layer is laminated with a transparent plastic substrate film with the resin composition for the hard coating layer side of the release film coated with the resin composition for the hard coating layer being an inner side, and half-cured. And (4) the above step The release film is peeled off from the obtained half cure laminate to transfer the hard coat layer to the transparent plastic substrate film side, and (5) a low refractive index layer is formed on the half cured hard coat layer, (6) The hard coat layer is fully cured.

In each of the above methods for producing an antireflection film, in particular, the high refractive index ultrafine particles are not completely buried in the hard coat layer, and some of the high refractive index ultrafine particles are exposed from the hard coat layer. In order to produce an antireflection film (fourth antireflection film of the present invention), the viscosity of the resin for the hard coat layer is increased, the type of the resin is selected, and a resin having a large surface tension is used. It can be produced by selecting and further considering the particle size of the high refractive index ultrafine particles, the filling rate of the ultrafine particles, the wettability between the hard coat layer resin and the high refractive index ultrafine particles, and the like.

As an example of the production method for producing the fourth antireflection film of the present invention, (1) a high refractive index ultrafine particle layer is formed on a release film, and (2) a transparent plastic substrate is used. On the material film, a resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film is applied within a range not exceeding the refractive index of the high refractive index ultrafine particle layer, (3 ) When the coating film of the resin composition for the hard coat layer is in a dry state to the touch, the surface of the release film obtained in the above step on the high refractive index ultrafine particle layer side and the transparent plastic obtained in the above step The coated side surface of the base film is pressure-bonded and laminated, and a part of the high refractive index ultrafine particle layer is embedded in the resin composition for the hard coat layer,
(4) The laminate 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. Next, a method of forming a low refractive index layer on the high refractive index ultrafine particle layer partially exposed from the hard coat layer can be mentioned.

An example of another production method for producing the fourth antireflection film of the present invention is (1) forming a high refractive index ultrafine particle layer on a release film, and (2)
On a transparent plastic substrate film, a resin composition for hard coat layer having a refractive index higher than that of the transparent plastic substrate film is applied within a range not exceeding the refractive index of the high refractive index ultrafine particle layer. (3) When the coating film of the resin composition for the hard coat layer is in a dry state to the touch, the surface of the release film obtained in the step on the high refractive index ultrafine particle layer side and the surface obtained in the step The surface of the transparent plastic substrate film on the coated side is pressure-bonded and laminated to bury a part of the high refractive index ultrafine particle layer in the resin composition for the hard coat layer. After the cured laminate is half-cured 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) Part of the hard coat layer Before exposed The high refractive index ultrafine particles layer to form a low refractive index layer, then (6), and a method for 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 coating or a vapor phase method, it is formed on a half-cured hard coat layer and then full cure. 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
Child layer : The high refractive index ultrafine particles used in 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 1.7.
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 can be mentioned. Of these ultrafine particles having a high refractive index, it is preferable to use ZnO, TiO ₂ , CeO ₂ or the like because the antireflection film of the present invention is further provided with a UV shielding effect. In addition, by using SnO ₂ or ITO doped with antimony, the electron conductivity is improved, dust is prevented from adhering due to the antistatic effect, or the antireflection film of the present invention is used as a CR film.
When used for T, an electromagnetic wave shielding effect can be obtained, which is preferable. The particle diameter of the high refractive index ultrafine particles is preferably 400 nm or less in order to make the hard coat layer transparent.

Ultrafine particles with low refractive index in antireflection film
Child layer : 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 (cryolite, refractive index 1.3)
3), SiO _x (x: 1.50 ≦ x ≦ 2.00) (refractive index 1.35 to 1.48), and other inorganic materials 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 in which high refractive index ultrafine particles are localized. There is. 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 the range lower than the refractive index n _H of the hard coat layer, but the following formula (1)

[0095]

[Equation 1] Since the antireflection effect is improved as the value becomes closer to, it is desirable to bring the condition closer to the condition of the above formula (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 an inorganic material or an organic material 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 (cryolite, refractive index 1.3)
3), SiO _x (x: 1.50 ≦ x ≦ 2.00) (refractive index 1.35 to 1.48), and other inorganic materials are used.

A film formed of a low-refractive-index inorganic material has a high hardness, and in particular, a plasma CVD method is performed to obtain SiO _x (x is 1.
50 ≦ x ≦ 4.00, preferably 1.70 ≦ x ≦ 2.2
It is preferable that the film of (0) formed has good hardness and excellent adhesion to the hard coat layer, and can reduce heat damage to the transparent plastic substrate film as compared with other vapor phase methods.

As the low refractive index organic material, an organic material such as a polymer having a fluorine atom introduced therein is preferable because the refractive index thereof is as low as 1.45 or less. Polyvinylidene fluoride (refractive index n = 1.40) is mentioned as a resin that can be used as a solvent because it is easy to handle. When this polyvinylidene fluoride is used as the low refractive index organic material, the refractive index of the low refractive index layer is about 1.40,
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. Part by weight may be added.

Since this trifluoroethyl acrylate is a monofunctional type and therefore the film strength of the low refractive index layer is not sufficient, a polyfunctional acrylate, for example,
It is desirable to add dipentaerythritol hexaacrylate (abbreviation: DPHA, tetrafunctional type) which is an ionizing radiation curable resin. The film strength of DPHA increases as the amount of addition increases, but from the viewpoint of reducing the refractive index of the low refractive index layer, the amount of addition is preferably small, and is 1 to 50 parts by weight, preferably 5 to 20 parts by weight. Is recommended.

The low refractive index layer is formed by vapor deposition of 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 formed by a vapor phase method such as D, or a low-refractive-index resin composition or low-refractive-index organic material containing a low-refractive-index inorganic material is applied to form a single-layer or multi-layer coating. It can be performed by forming a film.

In particular, S formed by plasma CVD method
The iO _x film has a higher density and a higher gas barrier property than an ordinary vacuum deposited film. Therefore, it has an excellent moisture-proof property, and when the antireflection film of the present invention is laminated on a polarizing element for use, it has an advantage of fulfilling the moisture-proof function of the polarizing element which is considered to be weak against moisture. Table 1 below shows experimental data showing the superiority of the SiO _x film formed by the plasma CVD method. The film targeted for the moisture proof experiment is a triacetyl cellulose film (indicated as TAC), a film of a hard coat resin with a thickness of 7 μm formed on the triacetyl cellulose film [indicated as HC (7 μm) / TAC Yes], a film thickness of 1 on the triacetyl cellulose film
A coating film of vinylidene fluoride having a thickness of [m] [K coat: represented by vinylidene fluoride (1 μm) / TAC], a film thickness of 100 on a triacetyl cellulose film
A plasma CVD film of 0Å SiO _x formed [S
Using iO _x (1000Å) / TAC to display]. Each of these films, humidity 90%, temperature 40 ℃,
The moisture permeability per day was measured according to the moisture proof test of JIS.

[0103]

[Table 1] According to the above Table 1, it can be seen that SiO _x (1000 Å) / TAC has the least moisture permeability and is excellent in moisture resistance. In addition, K coat: vinylidene fluoride (1 μm) / T
Although AC has a slightly good moisture resistance, AC is not preferable as an optical material because its coating film is soft and yellows with time.

Further, when a dye or the like is used in the polarizing element or other layers, the plasma CVD film can prevent their deterioration. 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
The iO _x film has a higher _{x value} than the SiO _x film compared to a normal vacuum deposited film.
The value of C is relatively easy to change, and x of a normal vacuum-deposited film is less than 2, whereas plasma C
The SiO _x film 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 vapor deposition film, and the obtained film has an advantage of high transparency. Further, the SiO _x film formed by the plasma CVD method is superior in adhesiveness to the substrate as compared with the usual vacuum vapor deposition film.

Hard coat layer in antireflection film
Refractive index of : In the first and second antireflection films of the present invention, the refractive index of the hard coat layer is higher than the refractive index of the low refractive index ultrafine particles, and higher than the refractive index of the transparent plastic substrate film. Although it is high, the layer structure having such a refractive index can enhance the antireflection effect and prevent the reflection at the interface between the hard coat layer and other layers. To increase the refractive index of the hard coat layer,
A binder resin having a high refractive index is used in the hard coat layer, high refractive index ultrafine particles having a refractive index higher than that of the hard coat layer is added to the hard coat layer, or these methods are used in combination.

The binder resin having a high refractive index includes
Resins containing aromatic rings, halogenated elements other than F, for example, resins containing Br, I, Cl, etc., resins containing atoms such as S, N, P, etc. can be mentioned, and at least one of these conditions is satisfied. It is desirable because the resin has a high refractive index.

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

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. In the range, the refractive index is higher than that of the transparent plastic substrate film, but the layer structure having such a refractive index enhances the antireflection effect and improves the interface between the hard coat layer and other layers. It can prevent reflection.

Other layers : In the antireflection film of the present invention,
In addition to the layers described above, layers for imparting various functionalities can be additionally provided. For example, a primer layer or an adhesive layer may be 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 may be provided for improving the hard performance. You may provide a layer. 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 directly or indirectly coating on the transparent plastic substrate film as described above, or by transferring the 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 the transparent plastic substrate film.

An adhesive may be applied to the lower surface of the antireflection film of the present invention, and this antireflection film can be used by being attached 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 having improved antireflection property can be obtained. For this polarizing element, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which is dyed with iodine or a dye and stretched, can be used. When the base film of the antireflection film is, for example, a triacetyl cellulose film, the saponification process is performed on the triacetyl cellulose film in order to increase adhesiveness and prevent static electricity in this laminating 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, 12 is an antireflection film of the present invention, which is laminated on a polarizing element 13, while the polarizing element 13 is provided.
Triacetyl cellulose film (abbreviation: TA
C film) 14 is laminated. 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 of TAC film / polarizing element / antireflection film is laminated on the liquid crystal display element 15, and the other surface of the liquid crystal display element 15 is provided on the other surface. , A polarizing plate having a layer structure of TAC film / polarizing element / TAC film is laminated. In addition, S
In a TN type liquid crystal display device, a retardation plate is inserted between a liquid crystal display element and a polarizing plate.

[0116]

EXAMPLES Example 1 A release film (MC-19: trade name, manufactured by Reiko, whose surface is treated with acrylic-melamine) has MgF ₂ sol with a refractive index of 1.4 (Nissan (Manufactured by Kagaku Co., Ltd.) is applied to a film thickness of 100 nm.

On the other hand, an electron beam curable resin (EXG: trade name, manufactured by Dainichiseika) was coated on a triacetyl cellulose film having a thickness of 80 μm so that the film thickness would be 5 μm / dry, and the above-mentioned mold release was performed. The film and the coating film surface were aligned and laminated by pressure bonding, and the electron beam was irradiated at 4 Mrad and 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% (triacetylcellulose film 92% as a base film), and the surface was not scratched by nail scratches. This transparent functional film has a function as an antireflection film.

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

Example 2 MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Kagaku) and fluorinated acrylate (manufactured by Osaka Organic Chemistry) were placed on the same release film as that used in Example 1 above. The mixture having the 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 S having a refractive index of 1.68 were formed on a PET film.
b ₂ O ₅ (manufactured by Nissan Kagaku Co., Ltd.) mixed at a ratio of 1: 2 was applied to give a film thickness of 5 μm / dry, and the release film was laminated and irradiated with an electron beam at 4 Mrad and 10 m / min. After curing the electron beam curable resin, the release film was peeled off. The obtained transparent functional film had a total light transmittance of 91% (PET film 87 as a base film).
%), The surface was not scratched 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 this Example 2. The transparent functional film is
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 is composed of the functional ultrafine particles 5.
It is bound by its own binding force and the binder resin 7, and the entire functional ultrafine particle layer 2 is completely buried in the hard coat layer 4 made of an electron beam curable resin. Further, in the hard coat layer 4, Sb ₂ O ₅ ultrafine particles 8 (refractive index 1.68) are mixed.

Example 3 As the release film of Example 1, matte PE having fine irregularities formed on its surface
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) was used.

FIG. 8 shows a cross section of the transparent functional film obtained in this Example 3. The transparent functional film is
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 is formed with the same fine concavo-convex pattern as the surface of the release film.

Example 4 As the release film of Example 2, mat PE having fine irregularities formed on its surface
A transparent functional film having an antireflection 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:
A ZnO ultrafine particle dispersion liquid having a refractive index of 1.9 was coated on a product name (manufactured by Reiko Co., Ltd., whose surface has been subjected to an acrylic-melamine treatment) to a thickness of 72 nm. On the other hand, an electron beam curable resin (EXG: trade name, manufactured by Dainichiseika) was coated on a triacetyl cellulose film (TAC film) having a thickness of 80 μm so as to have a thickness of 5 μm / dry. Both coated surfaces are laminated together and irradiated with an electron beam at 2 Mrad,
After the resin is semi-cured, the release film is peeled off to remove ZnO.
The ultrafine particle layer was transferred to an electron beam curable resin. Fluorine-based acrylate (biscoat 8F:
(Trade name, manufactured by Osaka Organic Chemical Co., Ltd.) was applied so as to have a thickness of 100 nm, and an electron beam was irradiated at 3 Mrad 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%.

FIG. 9 shows a cross section of the transparent functional film obtained in Example 5. The transparent functional film is
On the transparent plastic substrate film 3, the 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. It is completely covered with a film to form the functional ultrafine particle layer 2. 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 Co., Ltd., whose surface has been subjected to an acrylic-melamine treatment), and coated with a ZnO ultrafine particle dispersion liquid having a refractive index of 1.9 to have a thickness of 72 nm, while a triacetyl film having a thickness of 80 μm was applied. ZnO ultrafine particle dispersion liquid and electron beam curable resin (HN-5) on a cellulose film (TAC film).
A resin (refractive index 1.65) in which A: trade name, manufactured by Mitsubishi Yuka Co., Ltd. was mixed in a weight ratio of 2: 1 was applied so as to have a thickness of 5 μm / dry. Both were laminated and irradiated with an electron beam at 2 Mrad to semi-cure the resin, and then the release film was peeled off to transfer the ZnO ultrafine particle layer to the ultrafine particle dispersed electron beam curable resin. Fluorine-based acrylate (Biscoat 8F: trade name, manufactured by Osaka Organic Chemical Co., Ltd.) was applied to the transferred layer 10 times.
It was coated so as to have a thickness of 0 nm, irradiated with 3 Mrad of an electron beam, and the resin layer was completely cured to obtain a transparent functional film having an antireflection effect. The obtained transparent functional film is
The total light transmittance was 95%.

Example 7 Release Film (MC-19:
(Trade name, manufactured by Reiko Co., Ltd., whose surface has been treated with acrylic-melamine) and coated with a ZnO ultrafine particle dispersion liquid having a refractive index of 1.9 so as to have a thickness of 72 nm, and ZnO ultrafine particle dispersion on the layer. A resin (refractive index 1.65) in which a liquid and an electron beam curable resin (HN-5A: trade name, manufactured by Mitsubishi Yuka) were mixed at a weight ratio of 2: 1 was applied so as to have a thickness of 3 μm / dry. This film was irradiated with an electron beam at 10 Mrad to completely cure the resin, and a urethane adhesive (Takelac: trade name, manufactured by Takeda Yakuhin) was mixed with a curing agent in a ratio of 6: 1 on this layer. 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, the release film was peeled off, and then SiOx was formed on this layer.
The film was formed to a thickness of 100 nm by the plasma vapor 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 Co., Ltd., whose surface has been treated with acrylic-melamine) and coated with a ZnO ultrafine particle dispersion liquid having a refractive index of 1.9 so as to have a thickness of 72 nm, and ZnO ultrafine particle dispersion on the layer. A resin (refractive index 1.65) in which a liquid and an electron beam curable resin (HN-5A: trade name, manufactured by Mitsubishi Yuka) were mixed at a weight ratio of 2: 1 was applied so as to have a thickness of 3 μm / dry. This film was irradiated with an electron beam at 2 Mrad to half-cure the resin, and a urethane adhesive (Takelac: trade name, manufactured by Takeda Yakuhin) was mixed with a curing agent in a ratio of 6: 1 on this layer. And laminated with a triacetyl cellulose film having a thickness of 80 μm.

This film was aged at 40 ° C. for 3 days, the release film was peeled off, and then a fluorinated acrylate (Biscoat 8F: trade name, manufactured by Osaka Organic Chemical Co., Ltd.) was coated on this layer to a thickness of 100 nm. The electron beam to 3Mr.
The resin layer was completely cured by ad irradiation 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, made by Reiko, whose surface has been treated with acrylic-melamine) and coated with a ZnO ultrafine particle dispersion liquid having a refractive index of 1.9 so as to have a thickness of 72 nm, and an electron beam curing type on the layer. Resin (EXG: trade name, manufactured by Dainichiseika) 5 μm / dry
It was applied so that After laminating the resin surface and a triacetyl cellulose film having a thickness of 80 μm, the resin was completely cured by irradiating with an electron beam at 5 Mrd, and then the release film was peeled off. A SiOx film was formed on this layer by plasma deposition to have a film thickness of 100 nm. 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 Co., Ltd., whose surface has been subjected to an acrylic-melamine treatment) and coated with a ZnO ultrafine particle dispersion liquid having a refractive index of 1.9 to have a thickness of 72 nm, and an electron beam on the layer. Curable resin (EXG: trade name, manufactured by Dainichiseika) 5 μm / d
It was coated so that it would be ry. This resin surface and thickness 80 μm
After laminating the triacetyl cellulose film of 2), the electron beam was irradiated at 2 Mrad to half cure the resin, and then the release film was peeled off. Fluorine-based acrylate (Biscoat 8F, trade name, made by Osaka Organic Chemical Co., Ltd.) was coated on this layer to a thickness of 100 nm, and electron beam was applied for 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, made by Reiko, whose surface has been subjected to an acrylic-melamine treatment), MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Kagaku) was coated to a film thickness of 100 nm.

On the other hand, a PET resin having a thickness of 100 μm was coated with a blend resin of an electron beam curable adhesive and an electron beam curable resin so as to have a film thickness of 5 μm / dry, and dried by solvent (100 ° C.). , 30 minutes), and then press-bonding the release film and the coating surface to each other and applying an electron beam 4
After irradiation with 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% PET film as the base film), the surface was not scratched by nail scratches. This transparent functional film has a function as an antireflection film.

The transparent functional film obtained in this Example 11 corresponds to that shown in FIG.

Example 12 On the same release film as that used in Example 11, 1: 1 MgF ₂ sol having a refractive index of 1.4 (manufactured by Nissan Chemical) and fluorinated acrylate (manufactured by Osaka Organic Chemical) were used. A mixture with a mixing ratio of 2 has a film thickness of 100 nm.
It was applied so that

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.
Sb ₂ O ₅ (manufactured by Nissan Kagaku Co., Ltd.) in a ratio of 1: 2 was coated to a film thickness of 5 μm / dry, and the release film was coated on the coated surface of the PET film. Laminate with electron beam 4Mrad, 10m
The electron beam-curable blend-based resin was cured by irradiating the release film at a rate of 1 / min, and the release film was peeled off. The obtained transparent functional film had a total light transmittance of 93% (PE as a base film).
T film 87%), the surface was not scratched 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 this Example 12. The transparent functional film is an electron beam curable adhesive and an electron beam coated on a transparent plastic substrate film 3. It has a functional ultrafine particle layer 2 formed from the inside to the surface of a hard coat layer 4 of a blend resin 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 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, in the hard coat layer 4, Sb ₂ O ₅ ultrafine particles 8 (refractive index 1.68) are mixed.

Example 13 As a release film, a matte PET (X-4) having fine irregularities formed on its surface was used.
5: trade name, manufactured by Toray)
An antireflection film was manufactured under the same conditions as above.

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

Example 14 On the surface of the transparent functional film obtained in Example 11, 100% of fluorinated acrylate (Biscoat 8F: trade name, manufactured by Osaka Organic Chemical Co., Ltd.) was used.
coated so as to have a thickness of nm, and irradiated with an electron beam of 3 Mrad,
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 this Example 14. The transparent functional film is a function 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 applied electron beam curable adhesive and the electron beam curable resin. Functional ultrafine particle layer 2 and the low refractive index layer 9 is formed on the functional ultrafine particle layer 2 to form a transparent functional film having an antireflection effect.

[0144]

In the first and second transparent functional films or transparent functional films of the present invention, functional ultrafine particles are localized and fixed from the interface with the air layer to the inside of the hard coat layer. Therefore, unlike the case where the coating film is simply mixed with the functional ultrafine particles, it has the effect of easily exhibiting the properties of the functional ultrafine particles without using a large amount of the functional ultrafine particles. Further, it has the effect that the adhesion between the functional ultrafine particles and the hard coat layer is better than simply forming the 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 the functional ultrafine particles,
The same effect as that of the transparent functional film can be 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 low refractive index ultrafine particles and higher than that of the transparent plastic substrate film. Therefore, the antireflection effect can be enhanced, and reflection at the interface between the hard coat layer and other layers 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. Since it is higher than the refractive index of the transparent plastic substrate film in the range, it is possible to enhance the antireflection effect and prevent reflection at the interface between the hard coat layer and other layers.

[Brief description of 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 the 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 the transparent functional film obtained in Example 5.

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

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

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

FIG. 13 shows the layer structure of a polarizing plate laminated with the antireflection film of the present invention.

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

[Explanation of symbols]

1 Release Film 2 Functional Ultrafine Particle Layer 3 Transparent Plastic Substrate Film 4 Hardcoat Layer 5 Functional Ultrafine Particle 6 Adhesive Layer 7 Binder Resin 8 Sb ₂ O ₅ Ultrafine Particle 9 Low Refractive Index Layer 10 High Refractive Index Hardcoat Layer 11 Primer layer 12 Antireflection film 13 Polarizing element 14 TAC film 15 Liquid crystal display device

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location C08J 7/04 A (72) Inventor Toshio Yoshihara 1-1-1 Ichigaya-cho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Inventor Natsuko Yamashita 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Nihon Printing Inc. (72) Inventor Yuko Suzuki 1-1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo No. 1 in Dai Nippon Printing Co., Ltd. (72) Inventor Motohiro Oka 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd.

Claims (43)

[Claims] 1. A transparent functional film, wherein the functional ultrafine particles are localized and fixed from the interface with the air layer to the inside of the hard coat layer. 2. The functional ultrafine particles are localized 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, which is characterized in that some of the functional ultrafine particles are exposed from the hard coat layer. 3. The transparent functional film according to claim 1 or 2, 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 is a resin layer having a film 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, 2, 3, 4 or 5, which is formed on a transparent plastic substrate film via another layer. the film. 8. (1) A hard coat layer, in which ultrafine particles of low refractive index are localized and fixed from the interface with the air layer to the inside of the hard coat layer, (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 low refractive index ultrafine particles and higher than the refractive index of the transparent plastic substrate film. 9. (1) 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 transferred from the surface of the hard-coat layer. The exposed hard coat layer is (2) fixed on the transparent plastic substrate film, (3) the refractive index of the hard coat layer is higher than that of the low refractive index ultrafine particles, and the transparent An antireflection film having a refractive index higher than that of a plastic substrate film. 10. (1) A hard coat layer in which ultrafine particles of high refractive index 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 formed on the surface of the hard coat layer on which the high refractive index ultrafine particles are localized, and (3) a refractive index of the hard coat layer. Is an antireflection film having a refractive index higher than that of the transparent plastic substrate film within a range not exceeding the refractive index of the high refractive index ultrafine particles. (1) 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 is exposed from the surface of the hard coat layer. The hard coat layer is (2) fixed on the transparent plastic substrate film, (3) the high refractive index ultrafine particles are localized, and a part of the high refractive index ultrafine particles is transferred 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, (4) the refractive index of the hard coat layer does not exceed the refractive index of the high refractive index ultrafine particles. An antireflection film having a refractive index higher than that of the transparent plastic substrate film in the range. 12. The antireflection film according to claim 8, 9, 10 or 11, wherein the surface of the antireflection film according to claim 8, 9, 10 or 11 has fine irregularities. 13. The hard coat layer has a film thickness of 0.5 μm.
10. The resin layer as described above,
The antireflection film according to 10, 11, or 12. 14. The antireflection film according to claim 8, wherein the hard coat layer contains an ionizing radiation curable resin as a main component. 15. The reflection according to claim 8, wherein another layer is interposed between the hard coat layer and the transparent plastic substrate film. Prevention film. 16. (1) A functional ultrafine particle layer is formed on a release film, (2) On the other hand, a resin composition for a hard coat layer is applied on a transparent plastic substrate film, (3) The above When the hard coat layer resin composition is diluted with a solvent, after solvent drying, when the hard coat layer resin composition does not contain a solvent, the hard coat layer resin composition is left as it is, and the hard coating layer obtained in the above step is removed. The surface of the mold film on the side of the functional ultrafine particle layer and the surface of the transparent plastic substrate film on the side of the resin composition for the hard coat layer obtained in the above step are pressure-bonded and laminated to each other to harden the functional ultrafine particle layer. Immersed in the resin composition for the coat layer or a part of the functional ultrafine particle layer, (4) the laminate obtained in the above step is fully cured, and then the release film is peeled off to function. Transparent ultrafine particle layer A method for producing a transparent functional film, which comprises transferring to a plastic substrate film side. 17. (1) A functional ultrafine particle layer is formed on a release film, (2) On the other hand, a resin composition for a hard coat layer is applied on a transparent plastic substrate film, (3) The above When the hard coat layer resin composition is diluted with a solvent, after solvent drying, when the hard coat layer resin composition does not contain a solvent, the hard coat layer resin composition is left as it is, and the hard coating layer obtained in the above step is removed. The surface of the mold film on the side of the functional ultrafine particle layer and the surface of the transparent plastic substrate film on the side of the resin composition for the hard coat layer obtained in the above step are pressure-bonded and laminated to each other to harden the functional ultrafine particle layer. Immersed in the resin composition for the coat layer or a part of the functional ultrafine particle layer, and (4) the laminate obtained in the above step is half-cured, and then the release film is peeled off to function. Before the superfine particle layer Transfer to the transparent plastic substrate film side, (5) another functional film is formed on the hard-coated layer that has been half-cured, and (6) then full-curing, which is a transparent functional film. Manufacturing method. 18. A functional ultrafine particle layer is formed on a release film, and a resin composition for a hard coat layer is formed on 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, and the hard coat layer is formed by full curing, (3) The hard coat layer side of the release film having the hard coat layer formed inside is laminated with a transparent plastic substrate film via an adhesive layer, and (4) the laminate obtained in the above step. A method for producing a transparent functional film, characterized in that the release film is peeled off from the film and the hard coat layer is transferred to the transparent plastic substrate film side. 19. A functional ultrafine particle layer is formed on a release film, and a resin composition for a hard coat layer is formed on the functional ultrafine particle layer. By coating as described above, the functional ultrafine particle layer is embedded in the resin for the hard coat layer, or a part of the functional ultrafine particle layer is embedded, and half-cured to form the hard coat layer, (3) The hard coat layer side of the release film having the hard coat layer formed inside is laminated with a transparent plastic substrate film via an adhesive layer, and (4) the laminate obtained in the above step. From the release film to transfer the hard coat layer to the transparent plastic substrate film side, (5) forming another functional film on the half-cured hard coat layer, (6) The hard coat The method for producing a transparent functional film, characterized in that to fully cure the layer. 20. (1) A functional ultrafine particle layer is formed on a release film, and (2) a resin composition for a hard coat layer is provided on the functional ultrafine particle layer to form a film of the functional ultrafine particle layer. By coating as described above, the functional ultrafine particle layer is embedded in the resin for the hard coat layer, or a part of the functional ultrafine particle layer is embedded, (3) the resin composition for the hard coat layer (4) The release film coated with is laminated with a transparent plastic substrate film with the side of the resin composition for the hard coat layer being the inner side, and fully cured to form a hard coat layer. A method for producing a transparent functional film, which comprises releasing the release film from the obtained laminate and transferring the hard coat layer to the 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 provided on the functional ultrafine particle layer to form a film of the functional ultrafine particle layer. By coating as described above, the functional ultrafine particle layer is embedded in the resin for the hard coat layer, or a part of the functional ultrafine particle layer is embedded, (3) the resin composition for the hard coat layer (4) The release film coated with is laminated with a transparent plastic substrate film with the resin composition side for the hard coat layer inside, and half-cured to form a hard coat layer. The release film is peeled off from the obtained half cure laminate to transfer the hard coat layer to the transparent plastic substrate film side, (5) another functional film is formed 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 immersing the functional ultrafine particle layer in the resin for hard coat layer or burying a part of the functional ultrafine particle layer is performed by the following method:
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 hard coat layer resin 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,
An ionizing radiation-curable resin is a main component, which is characterized in that
2. The method for producing a transparent functional film as described in 2. 24. The resin composition for a hard coat layer,
It is a resin which is in a dry state to the touch when it is applied.
3. The method for producing a transparent functional film according to item 3. 25. The resin composition for a hard coat layer,
18. An ionizing radiation curable resin as a main component and 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 an amount such that the functional ultrafine particles are not completely embedded 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 particles are provided with hydrophobicity on the surface by a coupling agent, as claimed in claim 16, 17, 18, 19, 20, 21, 21.
A method for producing a transparent functional film according to 2, 23, 24, 25 or 26. 28. The release film has fine irregularities formed on the surface thereof.
17, 18, 19, 20, 21, 22, 23, 24, 2
The method for producing a transparent functional film according to 5, 26 or 27. 29. (1) A high refractive index ultrafine particle layer is formed on a release film, and (2) On the other hand, a range not exceeding the refractive index of the high refractive index ultrafine particle layer on a transparent plastic substrate film. And applying a resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film, and (3) when the resin composition for a hard coat layer is diluted with a solvent, After solvent drying, when the resin composition for the hard coat layer does not contain a solvent, the surface is on the high refractive index ultrafine particle layer side of the release film obtained in the step, and in the step. The surface of the resin composition for the hard coat layer of the obtained transparent plastic substrate film is pressure-bonded and laminated, and the high refractive index ultrafine particle layer is embedded in the resin composition for the hard coat layer or has a high refractive index. Ultrafine particle layer (4) The laminate obtained in the above step is fully cured to form a hard coat layer, and then the release film is peeled off to transfer the high refractive index ultrafine particle layer to the transparent plastic substrate film side. (5) Next, a method for producing an antireflection film, which comprises forming a low refractive index layer on the hard coat layer. 30. (1) A high-refractive-index ultrafine particle layer is formed on a release film, and (2) On the other hand, a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer on a transparent plastic substrate film. And applying a resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film, and (3) when the resin composition for a hard coat layer is diluted with a solvent, After solvent drying, when the resin composition for the hard coat layer does not contain a solvent, the surface is on the high refractive index ultrafine particle layer side of the release film obtained in the step, and in the step. The surface of the resin composition for the hard coat layer of the obtained transparent plastic substrate film is pressure-bonded and laminated, and the high refractive index ultrafine particle layer is embedded in the resin composition for the hard coat layer or has a high refractive index. Ultrafine particle layer (4) The laminate obtained in the above step is half-cured to form a hard coat layer, and then 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,
A method for producing an antireflection film, which comprises forming a low refractive index layer, and (6) then fully curing the hard coat layer. 31. (1) A high-refractive-index ultrafine particle layer is formed on a release film, (2) On the high-refractive-index ultrafine particle layer, within a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer. A resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film described below is applied so as to have a thickness of the high refractive index ultrafine particle layer or more, and the high refractive index ultrafine particle layer is formed. Embedded in the resin for the hard coat layer or a part of the ultrafine particle layer of the high refractive index layer and fully cured to form the hard coat layer, and (3) the mold release on which the hard coat layer is formed. The hard coat layer side of the film is placed inside, and the transparent plastic substrate film is laminated through the adhesive layer, and (4) the release film is peeled from the laminate obtained in the above step to make the hard coat layer transparent. Plastic substrate fill (5) Then, a low-refractive index layer is formed on the hard coat layer, which is a method for producing an antireflection film. 32. (1) A high-refractive-index ultrafine particle layer is formed on a release film, and (2) on the high-refractive-index ultrafine particle layer, within a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer. A resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film described below is applied so as to have a thickness of the high refractive index ultrafine particle layer or more, and the high refractive index ultrafine particle layer is formed. Embedded in the resin for the hard coat layer or a part of the ultrafine particle layer of the high refractive index layer and half-cured to form the hard coat layer, and (3) the mold release on which the hard coat layer is formed. The hard coat layer side of the film is placed inside, and the transparent plastic substrate film is laminated through the adhesive layer, and (4) the release film is peeled from the laminate obtained in the above step to make the hard coat layer transparent. Plastic substrate (5) A low-refractive index layer is formed on the half-cured hard coat layer, and (6) the hard coat layer is fully cured. 33. (1) A high-refractive-index ultrafine particle layer is formed on a release film, and (2) on the high-refractive-index ultrafine particle layer within a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer. A resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film described below is applied so as to have a thickness of the high refractive index ultrafine particle layer or more, and the high refractive index ultrafine particle layer is formed. Embedded in the resin for the hard coat layer or a part of the ultrafine particle layer for the high refractive index layer, and (3) the hard coat layer of the release film coated with the resin composition for the hard coat layer. Laminated with a transparent plastic substrate film with the resin composition side for the inside
Full curing is performed to form a hard coat layer, and (4) the release film is peeled from the laminate obtained in the above step to transfer the hard coat layer to the transparent plastic substrate film side, (5) and then the above A method for producing an antireflection film, which comprises forming a low refractive index layer on a hard coat layer. 34. (1) A high-refractive-index ultrafine particle layer is formed on a release film, and (2) on the high-refractive-index ultrafine particle layer, within a range not exceeding the refractive index of the high-refractive-index ultrafine particle layer. A resin composition for a hard coat layer having a refractive index higher than that of the transparent plastic substrate film described below is applied so as to have a thickness of the high refractive index ultrafine particle layer or more, and the high refractive index ultrafine particle layer is formed. Embedded in the resin for the hard coat layer or a part of the ultrafine particle layer for the high refractive index layer, and (3) the hard coat layer of the release film coated with the resin composition for the hard coat layer. Laminated with a transparent plastic substrate film with the resin composition side for the inside
Half-cure to form a hard coat layer, (4) Release the release film from the half-cure laminate obtained in the above step to transfer the hard coat layer to the transparent plastic substrate film side, (5) Half A low-refractive index layer is formed on the cured hard coat layer, and (6) the hard coat layer is fully cured, thereby producing an antireflection film. 35. The method of burying the high refractive index ultrafine particle layer in the resin for hard coat layer or burying a part of the high refractive index ultrafine particle layer is the viscosity of the resin for 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 hard coat layer resin and the high refractive index ultrafine particles. 29, 30 and 3 characterized in that
The method for producing a transparent functional film according to 1, 32, 33 or 34. 36. The resin composition for a hard coat layer,
An ionizing radiation-curable resin as a main component, 29, 30, 31, 32, 33, 34 or 3.
5. The method for producing an antireflection film according to item 5. 37. The resin composition for a hard coat layer,
The resin which is in a dry state to the touch at the time of coating, 29, 30, 31, 32, 33, 34, 35 or 3.
6. 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 a thermosetting resin, 31.
31. A method for producing an antireflection film as described in 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 an amount such that the high refractive index ultrafine particles are not completely embedded in the binder resin. Claims 29, 30, 3
1, 32, 33, 34, 35, 36, 37 or 38. 40. The surface of the high refractive index ultrafine particles is rendered hydrophobic by a coupling agent.
9, 30, 31, 32, 33, 34, 35, 36, 3
7. The method for producing an antireflection film according to 7, 38 or 39. 41. The release film has fine irregularities formed on the surface thereof.
2, 33, 34, 35, 36, 37, 38, 39 or 4
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
1. The method for producing an antireflection film as described in 1. 43. The low refractive index layer is formed by a vapor phase method.
3, 34, 35, 36, 37, 38, 39, 40 or 4
1. The method for producing an antireflection film as described in 1.