JPH0894806A - Optically functional film and manufacturing method thereof - Google Patents

Abstract

(57) [Abstract] [Purpose] In the production of an optical functional film formed by coating a low refractive index layer using a resin, the low refractive index layer formed on the optical functional film should be a sufficiently thin film Provided are an optically functional film having excellent scratch resistance, a sufficiently low refractive index and being sufficiently transparent, and a method for producing the same. [Structure] The type I optically functional film of the present invention comprises:
A monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene is copolymerized on the transparent substrate film 1 through another layer 2 composed of one or more layers. Fluorine content is 60-70
A solvent-soluble resin composition comprising 100 parts by weight of a fluorine-containing copolymer (weight%) and 30 to 150 parts by weight of a polymerizable compound containing an ethylenically unsaturated group is applied to form a thin film having a thickness of 200 nm or less. A low refractive index layer 3 having a refractive index of less than 1.60, preferably 1.45 or less, which is provided with scratch resistance, is formed. Of the other layers 2, the layer in direct contact with the low refractive index layer 3 has a refractive index higher than that of the low refractive index layer 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical functional film having a low refractive index layer formed on the outermost surface by using a resin capable of forming a low refractive index layer and a method for producing the same. In particular, the optical functional film of the present invention has an antireflection function, and the optical functional film is useful for polarizing plates and liquid crystal display devices.

[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. In particular, in an optical functional film such as an antireflection film, a low refractive index layer is conventionally provided as the outermost surface layer.

Conventionally, there have been the following techniques for preventing light reflection. That is, a method of applying an antireflection coating on the surface of glass or plastic, a method of providing an ultrathin film such as MgF ₂ with a film thickness of about 0.1 μm or a metal deposition film on the surface of a transparent substrate such as glass, a plastic surface such as a plastic lens. There is a method of applying an ionizing radiation curable resin on the above and forming a film of SiO ₂ or MgF ₂ thereon by vapor deposition, and a method of forming a coating film having a low refractive index on the cured film of the ionizing radiation curable resin. It was

Film thickness of 0.1 μm formed on the glass
A thin film of MgF _{2 on} the order of will be further described. When the incident light is vertically incident on the thin film, a specific wavelength is λ ₀ , the refractive index of the antireflection film for this wavelength is n ₀ , the thickness of the antireflection film is h, and the refractive index of the substrate is n _g . Then, it is already known that the condition for the antireflection film to prevent 100% of light reflection and to transmit 100% of light needs to satisfy the relations of the following formulas (1) and (2). (Science Library Physics = 9 "Optics" pages 70-72,
Published by Science Co., Ltd. in 1980).

[0005]

[Equation 1] The refractive index of glass is n _g = about 1.5, the refractive index of MgF ₂ film is n ₀ = 1.38, and the wavelength of incident light λ ₀ = 5500Å
Since it is already known as (reference), when these values are substituted into the above equation (2), the thickness h of the antireflection film is about 0.1 μm.
It is calculated that m is optimal.

According to the above equation (1), the reflection of light is 100
%, It can be seen that it is sufficient to select a material whose refractive index of the upper coating film is approximately the square root of the refractive index of the lower coating film. It has been conventionally practiced to prevent light reflection by setting the refractive index of the coating film to a value slightly lower than the refractive index of the underlying coating film.

[0007]

When a low refractive index layer is provided by coating a resin on the outermost surface of an optical functional film such as an antireflection film, a thin film that satisfies the above conditions is formed. It is difficult, the coating film of the obtained low refractive index layer is not sufficient scratch resistance, moreover, it is difficult to have a sufficiently low low refractive index, sufficient transparency, all of these. Conventionally, there has been no one that satisfies the condition of.

Therefore, the present invention provides a method for producing an optical functional film in which a low refractive index layer is formed by coating a resin,
The low-refractive index layer can be a sufficiently thin film, has sufficient scratch resistance, and can have a sufficiently low refractive index, and the resulting optical functional film should be sufficiently transparent. It is an object of the present invention to provide an optically functional film and a method for producing the same.

[0009]

Optical functional film : The optical functional film of the present invention includes type I and type II.

The type I optically functional film of the present invention comprises, on a transparent substrate film, 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene through another layer consisting of one or more layers. %, The fluorine content ratio obtained by copolymerizing a monomer composition containing 60% is 60 to 70.
Using a resin composition comprising 100 parts by weight of a fluorine-containing copolymer (weight%) and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group, a thin film having a thickness of 200 nm or less and scratch resistance Refractive index of 1.60
A low refractive index layer of less than is formed, among the other layers, a layer which is in direct contact with the low refractive index layer has a refractive index higher than that of the low refractive index layer. .

Further, the type II optical functional film of the present invention is characterized in that, among the other layers in the type I optical functional film of the present invention, the layer which is in direct contact with the low refractive index layer is
It is characterized in that fine particles having a refractive index of 1.60 or more are localized and fixed from the interface with the low refractive index layer to the inside of the other layer. The optical functional film of type II of the present invention has, in addition to the above characteristics, a refractive index of the other layer in a portion where the fine particles are not localized and fixed, and is higher than the refractive index of the transparent substrate film. A rate is desirable.

In Type I and Type II of the optical functional film of the present invention, the low refractive index layer comprises 30 to 90% by weight of vinylidene fluoride and 5 to 6% of hexafluoropropylene.
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 50% by weight, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. Part of the resin composition, and particularly the fluorine-containing copolymer contains hexafluoropropylene in an amount of 5 to 50% by weight of the monomer component. In the low refractive index layer to be used, a low refractive index of 1.45 or less can be realized, and particularly, in the fluorine-containing copolymer, vinylidene fluoride 30 to 9 is used.
Since it contains 0% by weight of the monomer component, the solvent solubility of the obtained resin composition is increased and the coating suitability is improved,
The film thickness can be a thin film of 200 nm or less suitable for antireflection. Furthermore, in the resin composition to be applied,
Polymerizable compound having ethylenically unsaturated group 30-150
Since the weight part is included, the resulting coating film has excellent scratch resistance and mechanical strength. Further, since each resin component has high transparency, the low refractive index layer formed using the resin composition containing these components is excellent in transparency.

FIG. 1 is a sectional view of a type I optically functional film of the present invention. The optically functional film is formed by coating another layer 2 mainly made of a resin on a transparent substrate film 1, and further, on the other layer 2, a layer for a low refractive index layer as described above. When a solvent-soluble resin composition is applied, a thin film having a film thickness of 200 nm or less has a refractive index of 1.6.
The low refractive index layer 3 of less than 0 (preferably 1.45 or less) is formed.

The type I optically functional film of the present invention has an air layer (refractive index 1.0) and a low refractive index layer 3 (refractive index less than 1.60) from the air in contact with the inside of the optically functional film. , Preferably 1.45 or less), other layer 2
(Refractive index 1.60 or more) and transparent substrate film 1 (refractive index lower than that of the other layer 2) enable efficient antireflection. It is desirable that the refractive index of the other layer 2 be higher than that of the transparent substrate film 1, and in such a case, reflection at the interface between the transparent substrate film 1 and the other layer 2 is desired. The effect of preventing is further added.

2 and 3 are sectional views of the type II optically functional film of the present invention. 2 and 3 are fine particles formed from the surface of the other layer 2 coated on the transparent substrate film 1 to the inside thereof in the type I optical functional film of the present invention of FIG. The difference is that the layer 4 is present, and the other constitutions are the same as those of the type I optically functional film of the present invention.
In the type II optically functional film of the present invention, the fine particle layer 4 is bound to each other by the binding force of each fine particle 7 itself or by the binding force of the binder resin in an amount such that the fine particles 7 are not completely buried. Has been formed. Figure 2
Is particularly the case where the fine particle layer 4 is completely buried in the other layer 2, and FIG.
This is the case when it is not completely buried and part of it is exposed.

The type II optically functional film of the present invention has substantially the same function as the type I described above, but since the fine particle layer 4 is inserted thereinto, the fine particles 7 are dispersed uniformly in the resin. Also can enhance the function of the fine particles 7, and since the fine particle layer 4 is localized and fixed, the high refractive index fine particles are used as the fine particles 7, and the fine particles 7 are locally present near the low refractive index layer 3. When it is made into a material, there is an advantage that the antireflection effect is enhanced.

Fine irregularities may be formed on the outermost surface of the optical functional films of type I and type II of the present invention. In such a case, the optical functional film is
A function of further enhancing the antireflection effect and the antiglare effect is imparted.

Low Refractive Index Layer : The resin composition used in the low refractive index layer of the optical functional film of the present invention will be described in detail below.

The resin composition for the low refractive index layer used in the present invention is a fluorine-containing resin obtained by copolymerizing a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. 60%
To 70% by weight of a fluorine-containing copolymer 100 parts by weight and an ethylenically unsaturated group-containing polymerizable compound 30 to 1
It is characterized in that it is a resin composition comprising 50 parts by weight. This resin composition is used to form a low refractive index layer having a refractive index of less than 1.60 (preferably 1.45 or less), which is a thin film having a film thickness of 200 nm or less and has scratch resistance.

The fluorine-containing copolymer used in this low refractive index layer is a copolymer obtained by copolymerizing a monomer composition containing vinylidene fluoride and hexafluoropropylene. The ratio of each component in the product is 30 to 90 for vinylidene fluoride.
%, Preferably 40 to 80% by weight, particularly preferably 40 to 70% by weight, and hexafluoropropylene at 5 to 50% by weight, preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight. is there. This monomer composition further contains tetrafluoroethylene in an amount of 0 to 40% by weight, preferably 0 to 35% by weight, particularly preferably 10 to
It may contain 30% by weight.

Further, the monomer composition for obtaining this fluorine-containing copolymer contains other copolymerization components, for example, 20%, within a range not impairing the objects and effects of the present invention.
It may be contained in an amount of not more than 10% by weight, preferably not more than 10% by weight. Here, specific examples of the other copolymerization component include, for example, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, and 1,2-
Dichloro-1,2-difluoroethylene, 2-bromo-
3,3,3-trifluoroethylene, 3-bromo-3,
A polymerizable monomer containing a fluorine atom such as 3-difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, or α-trifluoromethacrylic acid is used. Can be mentioned.

The fluorine-containing copolymer obtained from such a monomer composition has a fluorine content of 60 to 70.
It is necessary that the content is 60% by weight, and the preferable fluorine content is 62 to 70% by weight, particularly preferably 64 to 68% by weight.

The fluorine-containing copolymer has good solubility in the solvent described below, especially when the fluorine-containing ratio is within the above specified range. Further, the fluorine-based resin composition used in the optical functional film of the present invention has excellent adhesion to various substrates by containing such a fluorine-containing copolymer as a component. Since it forms a thin film having high transparency and low refractive index and sufficiently excellent mechanical strength, it is possible to make mechanical properties such as scratch resistance of the surface of the base material sufficiently high, and It is extremely suitable for forming a protective film.

The fluorine-containing copolymer has a molecular weight of 5,000 to 20,000 in terms of polystyrene equivalent number average molecular weight.
It is preferably 0, particularly preferably 10,000 to 100,000. By using the fluorine-containing copolymer having a molecular weight of such a size, the viscosity of the resulting fluorine-based resin composition becomes a suitable size, and therefore, the fluorine-based resin composition having surely suitable coatability. Can be

Further, the fluorine-containing copolymer preferably has a refractive index of 1.45 or less, particularly 1.42 or less, and more preferably 1.40 or less. Refractive index is 1.45
When a fluorine-containing copolymer exceeding the above range is used, the thin film formed by the obtained fluorine-based coating has a small antireflection effect, and it may not be possible to form a sufficiently good antireflection film.

The polymerizable compound used in the present invention is irradiated with an active energy ray in the presence or absence of a photopolymerization initiator, or is heated in the presence of a thermal polymerization initiator, It is a compound having an ethylenically unsaturated group that causes addition polymerization.

As specific examples of such a polymerizable compound, the following compounds (a) to (v) can be used.

(A) Styrene, α-methylstyrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, divinylbenzene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1.
-Diphenylstyrene, p-methoxystyrene, N, N
-Dimethyl-p-aminostyrene, N, N-diethyl-
Aromatic vinyl compounds such as p-aminostyrene and vinyl pyridine; (b) (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamon bark Unsaturated nitriles such as acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile; (c) methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec
-Butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate,
n-octyl (meth) acrylate, 2-ethylhexyl- (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (d) 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl ( (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) Fluorine-containing (meth) such as ethyl (meth) acrylate Acrylic esters; (e) Methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, itaconic acid Unsaturated carboxylic acid esters such as diethyl, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate; (f) 2-hydroxyethyl (meth) acrylate, 2
-Hydroxyl group-containing (meth) acrylic acid esters such as hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; (g) (meth) acrylic acid monoesters of polyalkylene glycol such as polyethylene glycol and polypropylene glycol (H) Cyano group-containing (meth) such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate
Acrylic esters; (i) 2-phenoxyethyl (meth) acrylate, 2
-(Meth) acrylic acid aryloxyalkyl esters such as phenoxypropyl (meth) acrylate and 3-phenoxypropyl (meth) acrylate; (j) Alkoxy such as methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolypropylene glycol (Meth) acrylic acid monoesters of polyalkylene glycol; (k) (meth) acrylic acid monoesters of aryloxypolyalkylene glycol such as phenoxypolyethylene glycol and phenoxypolypropylene glycol; (l) ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol,
(Meth) acrylic acid diesters of alkylene glycols such as 1,6-hexanediol; (m) Poly (meth) acrylics of polyalkylene glycols (having 2 to 23 alkylene glycol units) such as polyethylene glycol and polypropylene glycol Acid diester, hydroxypolybutadiene at both ends,
(Meth) acrylic acid diesters of polymers having hydroxyl groups at both ends such as hydroxypolyisoprene at both ends, hydroxybutadiene-acrylonitrile copolymer at both ends, and hydroxypolycaprolactone at both ends; (n) glycerin, 1,2,4 -Butanetriol, trimethylolalkane (alkane has 1 to
It is 3. ), Tetramethylolalkane (the carbon number of the alkane is, for example, 1 to 3), and a (meth) acrylic acid diester, a (meth) acrylic acid triester or a (meth) polyhydric alcohol such as pentaerythritol. (Meth) acrylic acid oligoesters such as acrylic acid tetraesters; (o) (meth) acrylic acid triesters or (meth) acrylic acid tetraesters of polyalkylene glycol adducts of polyhydric alcohols having 3 or more valences ( (P) 1,4-cyclohexanediol, 1,4-benzenediol, 1,4-dihydroxyethylbenzene and other cyclic polyhydric alcohol (meth) acrylic acid oligoesters; (q) ) Polyester (meth) acrylate, epoxy (meth) acrylate , (Meth) acrylic acid oligoester prepolymers such as urethane, (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate; (r) (meth) acrylic acid, croton Unsaturated carboxylic acids such as acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid; (s) itaconic acid, maleic acid, fumaric acid, citraconic acid, Free carboxyl group-containing esters such as monomethyl ester, monoethyl ester, monopropyl ester, monobutyl ester, monohexyl ester, and monooctyl ester of unsaturated polycarboxylic acid such as mesaconic acid; (t) itaconic acid, maleic acid , Fumaric acid, citraconic acid, Polyesters such as dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester and dioctyl ester of unsaturated polycarboxylic acid such as saconic acid; (u) (meth) acrylamide, N-hydroxymethyl (meth ) Acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (Meth) acrylamide, N, N′-hexamethylenebis (meth) acrylamide, crotonic acid amide,
Unsaturated amides such as cinnamic acid amide; (v) vinyl acetate, vinyl propionate, vinyl butyrate,
Vinyl carboxylic acid esters such as vinyl bivalate, vinyl caproate, vinyl versatate and vinyl stearate.

Among the above, preferred polymerizable compounds are those containing 3 or more, particularly 4 or more, and further 4 to 15 ethylenically unsaturated groups in one molecule. Specific examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethanetri (meth) acrylate.
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, Examples thereof include dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, "U-15HA" (trade name, manufactured by Shin Nakamura Chemical Co., Ltd.). .

Further, among these compounds, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate are particularly preferable. preferable.

When the polymerizable compound used contains three or more ethylenically unsaturated groups in one molecule,
The obtained fluororesin composition forms a thin film having extremely good mechanical properties such as adhesion to a substrate and scratch resistance of the surface of the substrate.

The amount of the polymerizable compound used is 30 to 150 parts by weight, preferably 35 to 100 parts by weight, and particularly preferably 40 to 70 parts by weight, based on 100 parts by weight of the fluorine-containing copolymer.

If the proportion of the polymerizable compound used is too small, the thin film formed by the obtained coating material will have low adhesion to the substrate, while if the proportion used is too large, a thin film will be formed. Has a high refractive index, making it difficult to obtain a good antireflection effect.

In the fluorine-based resin composition used for the optical functional film of the present invention, the fluorine content in the total amount of the polymer-forming components including the fluorine-containing copolymer and the polymerizable compound is 30 to 55% by weight. , Especially 35-50
It is preferably in the weight%. When such conditions are satisfied, it is possible to reliably form a thin film that achieves the objects and effects of the present invention more sufficiently. A thin film formed by a fluorine-containing resin composition having an excessive fluorine content tends to have low adhesion to the base material, and mechanical properties such as scratch resistance of the surface of the base material slightly deteriorate. On the other hand, a thin film formed of a fluorine-based resin composition having an excessively low fluorine content tends to have a large refractive index and a low antireflection effect.

The solvent used for the optical functional film of the present invention has a boiling point of 50 at a pressure of 760 hectopascals from the viewpoint of the coating property of the fluororesin composition and the adhesion of the thin film formed to the substrate. Those in the range of to 200 ° C are preferable.

Specific examples of such a solvent include acetone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, methyl formate, ethyl formate,
Propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate,
Solvents consisting of ketones or carboxylic acid esters such as butyl acetate, isobutyl acetate, butyl acetate, amyl acetate, isoamyl acetate, diamyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, etc. Can be mentioned. These solvents may be used alone or as a mixture of two or more components, and solvents other than those exemplified above may be added within a range not impairing the performance of the resin composition.

The amount of the solvent used is usually 20 per 100 parts by weight of the total amount of the fluorine-containing copolymer and the polymerizable compound.
0 to 10000 parts by weight, preferably 1000 to 1000
0 parts by weight, particularly preferably 1200 to 4000 parts by weight.

When the amount of the solvent used is in this range, the viscosity of the fluororesin composition is adjusted to 0.5 to 5 cps (2) at which a preferable coating property as the resin composition can be obtained.
5 ° C.), particularly in the range of 0.7 to 3 cps (25 ° C.). It is possible to easily form a thin film having a thickness of 100 to 200 nm without coating unevenness, and it is possible to form a thin film having particularly excellent adhesion to a substrate.

The fluorine-based resin composition used for the optical functional film of the present invention is one which is cured by the polymerization reaction of the ethylenically unsaturated group of the polymerizable compound contained therein, and therefore the resin composition concerned. The coating film formed by applying the substance is subjected to a curing treatment for polymerizing the polymerizable compound to form a solid thin film.

As means for such a curing treatment, a means for irradiating the coating film of the fluororesin composition with active energy rays or a means for heating the coating film is used, whereby the curing aimed at by the present invention is achieved. Since a thin film in a state can be reliably and easily formed, it is extremely advantageous in practice and convenient in terms of a thin film forming operation.

When an electron beam is used as the active energy ray in the case where the fluorine-based resin composition used in the optical functional film of the present invention is cured by irradiation with the active energy ray, the fluorine-containing resin composition is used as the active energy ray. The desired curing treatment can be carried out without adding a polymerization initiator.

When a light ray such as an ultraviolet ray or a visible light ray is used as the active energy ray for the curing treatment, it is decomposed upon irradiation with the active energy ray to generate, for example, a radical, thereby polymerizing. A photopolymerization initiator that initiates the polymerization reaction of the compound is added to the fluororesin composition.

Specific examples of such a photopolymerization initiator include, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole and xanthone. , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4
-Methoxybenzophenone, thioxanthone, 2,2-
Dimethoxy-2-phenylacetophenone, 1- (4-
Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, triphenylamine, 2,4 6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone,
3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2-
(Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl-1-butanone, 4-benzoyl-4′-methyldiphenyl sulfide, benzyl, or BTTB and xanthine, thioxanthine,
Examples include coumarin, ketocoumarin, and combinations with other dye sensitizers.

Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-
Hydroxyl cyclohexyl phenyl ketone, 2,4
6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] 2-Phenylmethyl) -1-butanone and the like are preferable, and more preferably 1-hydroxylcyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2 Examples thereof include-(dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone.

Furthermore, when a heating means is used for the curing treatment, a thermal polymerization initiator which, for example, generates radicals by heating to initiate the polymerization of the polymerizable compound is added to the fluororesin composition. .

Specific examples of the thermal polymerization initiator include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide. tert
-Butyl peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like. be able to.

The addition amount of the photopolymerization initiator or the thermal polymerization initiator in the fluororesin composition used for the optical functional film of the present invention is 100 parts by weight in total of the fluorine-containing copolymer and the polymerizable compound. On the other hand, it is usually 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, particularly preferably 2 to 7 parts by weight. If the amount added exceeds 10 parts by weight, the handling of the resin composition and the mechanical strength of the formed thin film may be adversely affected, while if the amount added is less than 0.5 parts by weight, the curing rate is low. Becomes

The fluororesin composition used in the optical functional film of the present invention may contain various additives, if necessary, within a range not impairing the objects and effects of the present invention.
For example, sensitizers or polymerization accelerators composed of amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine; epoxy resins, polyamides, polyamideimides, polyurethanes,
Polymers or oligomers such as polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, silicone-based oligomer, polysulfide-based oligomer; phenothiazine, 2,6
Polymerization inhibitor such as di-tert-butyl-4-methylphenol; other than leveling agent, leak improver, surfactant, plasticizer, ultraviolet absorber, silane coupling agent, inorganic filler, resin particles, Pigments, dyes and the like can be added.

Other layer : In the type I and type II optical functional films of the present invention, in the one or more layers between the transparent substrate film and the low refractive index layer, directly with the low refractive index layer. The refractive index of the other layer in contact is preferably higher than that of the low refractive index fine particles and higher than that of the transparent plastic substrate film. With the layer structure having such a refractive index, the antireflection effect can be enhanced and the reflection at the interface between the layers in contact with other layers can be prevented. The refractive index of the other layer in direct contact with the low refractive index layer is preferably 1.60 or more.

In the optically functional film of type II of the present invention, among the other layers, fine particles having a refractive index of 1.60 or more extend from the interface with the layer directly in contact with the low refractive index layer to the inside of the other layer. Since they are localized and fixed, there is an advantage that the function of the fine particles can be easily expressed with a small amount without using a large amount of the fine particles as compared with the case where the fine particles are dispersed in the resin. Since it is embedded in the layer (3), there is an effect that the adhesion between the fine particles and the other layer is better than when the fine particle layer is formed on the other layer.

Further, in the type II optical functional film of the present invention, the refractive index of the other layer in the portion where no fine particles are present is higher than that of the transparent base film. The ratio is preferable in order to prevent reflection at the interface between the transparent substrate film and the other layers.

Fine particles having a refractive index of 1.60 or more, which are localized and fixed from the interface with the low refractive index layer to the inside of the other layer, have an optical film thickness of λ / 4 or λ / 2 ( 450
(nm <λ <600 nm) is preferable in order to improve the antireflection effect.

To increase the refractive index of the other layer, a binder resin having a high refractive index is used for the other layer, or high refractive index fine particles having a refractive index higher than that of the other layer are used. It is added to a layer, the high refractive index fine particle layer is localized in another layer, or these methods are used in combination.

Examples of the high-refractive-index fine particles used in the method of adding the high-refractive-index fine particles to the other layer or the method of localizing the high-refractive-index fine particles in the other layer include, for example, ZnO (refractive index 1.9).
0), TiO ₂ (refractive index 2.3 to 2.7), CeO
₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.7
1), SnO ₂ , ITO (refractive index 1.95), Y ₂ O ₃
(Refractive index 1.87), La ₂ O ₃ (refractive index 1.95),
ZrO ₂ (refractive index 2.05), Al ₂ O ₃ (refractive index 1.
63) and the like.

Of these high refractive index fine particles, ZnO,
The use of TiO ₂ , CeO ₂ , Sb ₂ O ₅ or the like is preferable because the UV-shielding effect is further imparted to the optical functional film of the present invention. In addition, by using SnO ₂ or ITO doped with antimony, electron conductivity is improved, dust is prevented from being attached due to an antistatic effect, or an electromagnetic wave shielding effect is obtained when the optical functional film of the present invention is used in a CRT. Is obtained, which is preferable.
The particle size of the high refractive index fine particles is preferably 400 nm or less in order to make other layers transparent. In particular, in order to impart antireflection properties, low refractive index fine particles such as MgF ₂ and SiO ₂ or Sb ₂ O ₅ , ZnO, ITO, SnO ₂ and TiO _{2 are used.}
High refractive index fine particles such as

The fine particles used in the fine particle layer include 200
Examples of the ultrafine particles having a size of nm or less include those having a function of blocking ultraviolet rays, conductivity, antistatic properties, antireflection properties, and the like.

The surface of the fine particles having these functionalities may be subjected to a hydrophobic treatment with a coupling agent, and since such hydrophobic treatment introduces a hydrophobic group to the surface of the fine particles, it is ionized. It becomes easier to adapt to the radiation curable resin, and the bond with the ionizing radiation curable resin becomes stronger. As such a coupling agent, a silane coupling agent, a titanate coupling agent, an alumina coupling agent or the like is used. The amount of the coupling agent added is 0 (not including 0) to 30 parts by weight, preferably 0 (not including 0) to 10 parts by weight.

When the surface of the fine particles is inactive such as MgF ₂ , SiO ₂ sol may be added in advance and the surface of the fine particles may be coated with SiO ₂ and then treated with a coupling agent. By such a film treatment of SiO ₂ ,
Many hydrophilic groups can be introduced on the surface of the fine particles,
Subsequent treatment with the coupling agent can surely introduce more hydrophobic groups, and therefore the fine particles are more easily adapted to the resin and the binding property is increased.

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

As the resin that can be used in the other layers, any resin can be used as long as it is transparent (for example, thermoplastic resin, thermosetting resin, ionizing radiation curing resin). it can. However, in the optical functional film of the present invention, the resin forming the low refractive index layer,
Since the ionizing radiation-curable resin is mixed, when the ionizing radiation-curable resin is used as the resin for the other layer, there is an advantage that the coating films can be cured simultaneously by the ionizing radiation.

In order to impart hard performance to other layers,
Alternatively, in order to impart a hard performance to a certain one of the plurality of layers, the hardness can be maintained by setting the thickness of the layer to 0.5 μm or more, preferably 3 μm or more. Can be given.

In the present invention, "to impart hard performance" means to give a hardness of H or higher in the pencil hardness test shown in JIS K5400.

In order to further improve the hardness of the other layers, the binder resin is a reaction-curable resin, that is,
It is preferable to use a thermosetting resin and / or an ionizing radiation curable resin. 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-based functional group, for example, a polyester resin or polyether resin having a relatively low molecular weight,
Acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin,
Polythiol polyene resin, oligomer or prepolymer 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. Monofunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth), etc. 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 to other layers, the solvent drying type resin may be contained in an amount of 10 parts by weight or more and 100 parts by weight or less 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 it is advantageous in terms of transparency, particularly low haze value, high transmittance, and compatibility.

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

The reason is that when toluene is used as a solvent in the above-mentioned cellulose resin, the transparent substrate film is used in spite of using toluene which is a non-soluble solvent of triacetyl cellulose which is a transparent substrate film. Even if you apply a resin composition containing this solvent-drying resin,
Adhesion between the transparent substrate film and the coating resin can be improved, and since this toluene does not dissolve triacetyl cellulose, which is the transparent substrate film, the surface of the transparent plastic substrate film does not whiten. This is because there is an advantage that transparency is maintained.

When an ionizing radiation-curable resin is used as a binder resin in the other 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, Preferably 10
An electron beam or the like having an energy of 0 to 300 KeV is used, and in the case of ultraviolet curing, an ultraviolet ray or the like emitted from a light beam of an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp or the like can be used.

The above-mentioned fine particles used in the other layer may have a hydrophobic property imparted to the surface thereof by a coupling agent.

When there are a plurality of other layers, one of them may be an adhesive layer in contact with the transparent substrate film.

Method for forming fine particle layer: The fine particle layer is formed by applying a sol itself of fine particles or a sol of fine particles containing a binder resin. For example, when a fine particle layer is formed on process paper, it can be formed by the binding action of the fine particles themselves without using a binder resin, but it is necessary when the binding action is weak. According to the above, a binder resin may be mixed and used. The amount of the binder resin should be such that the fine particles are not completely embedded in the binder resin, and since the fine particles are bound to each other with the surface of the fine particles exposed, the functionality of the fine particles is expressed. In particular, it is preferable when used as 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. The ionizing radiation curable resin is used in the low refractive index layer in the present invention. Since it is included, an ionizing radiation-curable resin is preferable in consideration of the adhesion to the low refractive index layer, and the ionizing radiation-curable resin is preferably a solvent-drying semi-curable resin. Further, a colorant may be mixed in such a binder resin.

Transparent substrate film : The material suitable for the transparent substrate film of the optical functional film of the present invention may be any film having transparency, for example, triacetyl cellulose film, diacetyl cellulose film, acetate butyrate. Cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, trimethylpentene film, polyetherketone film, (meth) acrylonitrile film, etc. are used. However, a triacetyl cellulose film and a uniaxially stretched polyester are particularly preferable because they are excellent in transparency and have no optical anisotropy. Its thickness is
Usually, those having a thickness of about 8 μm to 1000 μm are preferably used.

Manufacturing Method of Optically Functional Film : The following five manufacturing methods can be mentioned as the manufacturing method of the type I optically functional film of the present invention.

The first method for producing the above-mentioned type I optically functional film is (1) on the transparent substrate film, directly or through another layer, (2) the refractive index of the resin composition is: The refractive index of the layer directly contacting the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product is higher than the refractive index of the resin composition, to form a coating film,
(3) The obtained coating film is subjected to a heat treatment and / or an ionizing radiation treatment to be fully cured or half cured, and (4) the obtained fully cured or half cured coating film is covered with fluorine. 60% fluorine content obtained by copolymerizing a monomer composition containing 30 to 90% by weight of vinylidene chloride and 5 to 50% by weight of hexafluoropropylene.
To 70% by weight of a fluorine-containing copolymer 100 parts by weight and an ethylenically unsaturated group-containing polymerizable compound 30 to 1
Applying a solvent mixture of the resin composition consisting of 50 parts by weight,
A solvent is dried to form a coating film having a film thickness of 200 nm or less and a refractive index of less than 1.60 (preferably 1.45 or less), and (5) heating the coating film obtained by drying the solvent. Treatment and / or ionizing radiation treatment is performed to fully cure the coating film including other coating films.

FIG. 4 is a flow chart showing the first manufacturing method of the type I optical functional film. Figure 4
(A) shows a state in which another layer 2 is formed on the transparent substrate film 1 with or without an adhesive layer, a layer containing a functional material, or the like. FIG. 4B shows a state in which the coating film of the other layer 2 is subjected to a heat treatment and / or an ionizing radiation treatment to be fully cured or half cured. Figure 4
(C) shows a state in which the low refractive index layer 3 is formed by applying the resin composition for a low refractive index layer used in the present invention on the other layer 2. FIG. 4 (d) shows that the coating film obtained by drying the solvent is subjected to heat treatment and / or ionizing radiation treatment to form the coating film in another layer 2
It shows the state of full cure including the coating film.

The second method for producing the above-mentioned type I optically functional film is a method of using an adhesive for adhesion of the transparent substrate film and other layers. The refractive index of the product is higher than the refractive index of the layer directly in contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product, and a coating film is formed by coating the resin composition. Formed, and (2) the coating film obtained in the above step is subjected to a heat treatment and / or an ionizing radiation treatment to cause the coating film to half-cure or full-cure, and (3) the obtained half-cure or full-cure is performed. An adhesive layer is formed on either one of the coating film and the transparent substrate film, and (4) the process paper and the transparent substrate film are placed with the coating film side on the process paper inside through the adhesive layer. After laminating, the process paper is peeled off (5) The monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene is copolymerized on the half-cured or fully-cured coating film formed on the transparent substrate film. And 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, and a solvent mixture of a resin composition consisting of 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group are applied as a solvent. To form a coating film having a film thickness of 200 nm or less and a refractive index of less than 1.60 (preferably 1.45 or less), and (6) heat treating the coating film obtained by drying the solvent. And / or ionizing radiation treatment is performed to fully cure the coating film including other coating films.

FIG. 5 is a flow chart of the second manufacturing method of the above-mentioned type I optically functional film. FIG. 5 (a)
Means that the refractive index of the resin composition on the process paper 5 is higher than the refractive index of the layer directly contacting the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product,
This is a state in which a high resin composition is applied to form a coating film for the other layer 2. FIG. 5B shows a state in which the coating film of the other layer 2 is subjected to heat treatment and / or ionizing radiation treatment to completely cure the coating film. In FIG. 5C, the adhesive layer 6 is provided on either the other layer 2 side or the transparent substrate film 1 side, and the other layer 2 on the process paper 5 and the transparent substrate are interposed via the adhesive layer 6. The state in which the film 1 is laminated is shown. FIG. 5 (d) shows
The state where the process paper 5 is peeled from the laminate is shown.
FIG. 5 (e) shows that the resin composition for a low refractive index layer used in the present invention is further applied onto another layer 2 to form a coating film for the low refractive index layer 3, and heat treatment and / or ionizing radiation is performed. This shows a state in which the coating film including the coating film of the other layer 2 is fully cured by the treatment.

The third method for producing the above-mentioned type I optically functional film is a method in which an adhesive is not used for adhering the transparent substrate film and the other layers.
The refractive index of the resin composition is higher than the refractive index of the layer that is in direct contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product. (2) On the other hand, a transparent base film is prepared, and the process paper and the transparent base film are laminated with the coating film side of the process paper inside, and (3) the obtained laminate is half-coated. After curing or full curing, the process paper is peeled off, and (4) 30 to 90% by weight of vinylidene fluoride and hexa on the half-cured or fully-cured coating film formed on the transparent substrate film. 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing 5 to 50% by weight of fluoropropylene, and an ethylenically unsaturated group. The solvent mixture was applied in the resin composition comprising a polymerizable compound 30 to 150 parts by weight, a less thin thickness 200nm by drying the solvent and a refractive index of 1.
A coating film of less than 60 is formed, and (5) the coating film obtained by drying the solvent is subjected to heat treatment and / or ionizing radiation treatment to be fully cured including other coating films. And

The fourth production method of the above-mentioned type I optically functional film is a method of using an adhesive for adhering the transparent substrate film and the other layers. 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing 30 to 90% by weight of vinylidene and 5 to 50% by weight of hexafluoropropylene; A solvent mixture of a resin composition consisting of 30 to 150 parts by weight of a polymerizable compound having an unsaturated group is applied, and the solvent is dried to form a thin film having a thickness of 200 nm or less and a refractive index of less than 1.60 (preferably 1 .45 or less) to form a coating film (2)
The obtained coating film is in an uncured state, or the coating film is subjected to a heat treatment and / or an ionizing radiation treatment to be fully cured or half cured, and (3) the obtained coating film is
The refractive index of the resin composition is higher than the refractive index of the layer that is in direct contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product. A film is formed, and (4) the coating film obtained in the above step is subjected to heat treatment and / or ionizing radiation treatment to be fully cured including the other coating film, and formed on the paper in the (5) step. An adhesive layer is formed on either one of the fully cured coating film or the separately prepared transparent substrate film,
(6) After the process paper and the transparent substrate film are laminated with the coating film side on the process paper inside through the adhesive layer,
It is characterized in that the process paper is peeled off.

FIG. 6 is a flow chart of the fourth manufacturing method of the above-mentioned type I optically functional film. Figure 6 (a)
Is coating the resin composition for a low refractive index layer used in the present invention on the step paper 5 to form a coating film for the low refractive index layer 3 and full-curing or half-curing the coating film. Indicates the status. FIG. 6B shows a resin composition containing a binder resin and high refractive index fine particles having a refractive index higher than that of the binder resin on the low refractive index layer 3, and the resin composition The resin composition having a higher refractive index than the refractive index of the layer directly contacting the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product is applied, The state in which the coating film of the other layer 2 is formed and the coating film is fully cured is shown. FIG. 6 (c)
Is the low refractive index layer 3 and the other layer 2 formed on the process paper 5.
And the transparent substrate film 1 are laminated via the adhesive layer 6. FIG. 6D shows a state in which the process paper 5 is peeled from the laminate.

The fifth production method of the type I optical functional film is a method in which an adhesive is not used for adhering the transparent substrate film and the other layers, and
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene, A solvent mixture of a resin composition comprising 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group is applied, and the solvent is dried to form a thin film having a thickness of 200 nm or less and a refractive index of 1.60.
Less than (preferably 1.45 or less) to form a coating film,
(2) The obtained coating film is left in an uncured state, or the coating film is subjected to heat treatment and / or ionizing radiation treatment to be fully cured or half cured, and (3) on the obtained coating film. A resin composition having a refractive index higher than that of a layer in direct contact with a lower layer of a layer using the resin composition in the layer structure of the optical functional film as a final product. A film is formed, (4) a transparent substrate film is prepared separately, the process paper and the transparent substrate film are laminated with the coating film on the process paper inside, and then the process paper is peeled off. .

The following six production methods can be mentioned as the production method for the type II optically functional film of the present invention.

The first production method of the type II optical functional film of the present invention is a method of using an adhesive for adhering the transparent substrate film and other layers, and Coating with a low-refractive index resin composition diluted with a solvent and drying the solvent to form a low-refractive index layer having a film thickness of 200 nm or less and a refractive index of less than 1.60,
(2) The obtained low refractive index layer is in an uncured state, or the low refractive index layer is subjected to heat treatment and / or ionizing radiation treatment to be half-cured or full-cured, and (3) the obtained low refractive index. A fine particle layer having a refractive index of 1.60 or more is formed on the layer so that the optical film thickness is λ / 4 or λ / 2 (450 <λ <600 nm), and (4) on the obtained fine particle layer, (5) Forming a resin-based coating film, performing heat treatment and / or ionizing radiation treatment, and fully curing this coating film, including curing of other coating films, and forming (5) the obtained process paper. An adhesive layer is formed on the fully cured resin layer, or an adhesive layer is formed on a separately prepared transparent substrate film, and (6) through the adhesive layer and the process paper. After laminating the transparent substrate film with the resin layer formed on the process paper inside Characterized by peeling the casting papers.

FIG. 7 is a flow chart of the first production method of the type II optically functional film of the present invention. Figure 7
In (a), a low-refractive index layer 3 which is a thin film of the low-refractive index resin composition used in the present invention is formed on a process paper 5 by coating, and is subjected to heat treatment and / or ionizing radiation treatment. The state where the coating film is fully cured or half cured is shown.
FIG. 7B shows a state in which a fine particle layer 4 mainly containing fine particles 7 is formed on the low refractive index layer 3. FIG. 7C shows
A state in which a resin is applied on the fine particle layer 4 to form a coating film for the other layer 2 and the coating film is fully cured is shown. FIG. 7D shows another layer 2 of the film obtained in the above (c).
The side and the transparent base material film 1 are laminated via the adhesive layer 6. FIG. 7E shows a state in which the process paper 5 is peeled from the laminate.

The second method for producing the optically functional film of type II of the present invention is a method in which an adhesive is not used for adhering the transparent substrate film and the other layers. Coating a low refractive index resin composition diluted with a solvent and drying the solvent to form a low refractive index layer having a film thickness of 200 nm or less and a refractive index of less than 1.60,
(2) The obtained low refractive index layer is in an uncured state, or the low refractive index layer is subjected to heat treatment and / or ionizing radiation treatment to be half-cured or full-cured, and (3) the obtained low refractive index. A fine particle layer having a refractive index of 1.60 or more is formed on the layer so that the optical film thickness is λ / 4 or λ / 2 (450 <λ <600 nm). (4) On the other hand, on the transparent substrate film (5) A low-refractive index layer and a fine particle layer formed on the process paper and a resin layer on the transparent base film are in contact with each other to form a coating film mainly composed of a resin, and the process paper and the transparent base film. By laminating the two by pressure bonding, the fine particle layer is embedded in the resin layer or a part of the fine particle layer is embedded, and (6) the obtained laminate is subjected to heat treatment and / or ionizing radiation treatment. Go and do a full cure including curing other coatings, By peeling off the casting papers Ide, characterized in that transferring the low refractive index layer and the high refractive index fine particle layer.

FIG. 8 is a flow chart of the second production method of the type II optically functional film of the present invention. Figure 8
In (a), a low-refractive index layer 3 which is a thin film of the low-refractive index resin composition used in the present invention is formed on a process paper 5 by coating, and is subjected to heat treatment and / or ionizing radiation treatment. The state where the coating film is fully cured or half cured is shown.
FIG. 8B shows a state in which the fine particle layer 4 mainly containing the fine particles 7 is formed on the low refractive index layer 3. FIG. 8C shows
A transparent substrate film 1 is prepared, and this transparent substrate film 1
This is a state in which a coating film (other layer 2) mainly composed of a resin is formed on the top. FIG. 8D shows another layer 2 side on the transparent substrate film 1 obtained in the above (c) and the fine particle layer 4 on the process paper 5.
It shows a state in which it is fully cured including the curing of the other coating film 2 by laminating together with the side. The fine particle layer 4 is completely buried in the other layer 2 or a part of the fine particle layer 4 is buried. FIG. 8E shows a state in which the process paper 5 is peeled from the laminate.

A third production method of the optical functional film of type II of the present invention, which is a method in which an adhesive is not used for adhering the transparent substrate film and the other layers, Coating a low refractive index resin composition diluted with a solvent and drying the solvent to form a low refractive index layer having a film thickness of 200 nm or less and a refractive index of less than 1.60,
(2) The obtained low refractive index layer is in an uncured state, or the low refractive index layer is subjected to a heat treatment and / or an ionizing radiation treatment to be half-cured or full-cured, and (3) the obtained low refractive index. A fine particle layer having a refractive index of 1.60 or more is formed on the layer so that the optical film thickness is λ / 4 or λ / 2 (450 <λ <600 nm), and (4) on the obtained fine particle layer, A coating film mainly made of resin is formed, a transparent substrate film is prepared separately in (5), and the process paper and the transparent substrate film are laminated with the resin layer formed on the process paper inside.
(6) Heat treatment and / or
Alternatively, it is characterized by performing ionizing radiation treatment to perform full curing including curing of other coating films, and then peeling the process paper.

FIG. 9 is a flow chart of the third production method of the type II optically functional film of the present invention. Figure 9
In (a), a low-refractive index layer 3 which is a thin film of the low-refractive index resin composition used in the present invention is formed on a process paper 5 by coating, and is subjected to heat treatment and / or ionizing radiation treatment. The state where the coating film is fully cured or half cured is shown.
FIG. 9B shows a state in which the fine particle layer 4 mainly containing the fine particles 7 is formed on the low refractive index layer 3. FIG. 9C shows
A state is shown in which a resin is applied onto the fine particle layer 4 to form a coating film of another layer 2 mainly composed of a resin, and this coating film has not been fully cured. FIG. 9 (d) shows that the other layer 2 side of the process paper 5 obtained in (c) above and the separately prepared transparent substrate film 1 are laminated together, and the curing of the other layers is also included. Shows the state of full cure.
FIG. 9E shows a state in which the process paper 5 is peeled from the laminate.

The low refractive index resin composition used in the first to third methods for producing the type II optically functional film of the present invention comprises vinylidene fluoride in an amount of 30 to 90% by weight.
And 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing 5 to 50% by weight of hexafluoropropylene, and a polymerization having an ethylenically unsaturated group. Sex compound 30-
A resin composition comprising 150 parts by weight can realize a sufficiently low refractive index of less than 1.60, preferably 1.45 or less, and since the resin composition is solvent-soluble, the film thickness is Can be a sufficiently thin film having a thickness of 200 nm or less, and since the low refractive index layer produced by this low refractive index resin composition has excellent scratch resistance and transparency,
It can be used particularly preferably.

The fourth production method of the above-mentioned type II optical functional film of the present invention is a method in which an adhesive is not used for adhering the transparent substrate film and the other layers. , A fine particle layer having a refractive index of 1.60 or more has an optical film thickness of λ
/ 4 or λ / 2 (450 <λ <600 nm). (2) On the other hand, a resin-based coating film is formed on the transparent substrate film, and (3) on the process paper. By embedding the process paper and the transparent substrate film by pressure bonding so that the formed fine particle layer and the resin layer formed on the transparent substrate film are in contact with each other, the fine particle layer is embedded in the resin layer. Or (4) subjecting the obtained laminate to heat treatment and / or ionizing radiation treatment to full-cure or half-cure this coating film to obtain (5) The process paper is peeled from the full-cured or half-cured laminate to transfer the fine particle layer to the transparent substrate film. (6) 30 to 90% by weight of vinylidene fluoride and hexafluoroproton The monomer composition containing 5 to 50% by weight of pyrene is copolymerized to give a fluorine content of 60.
To 70% by weight of a fluorine-containing copolymer 100 parts by weight and an ethylenically unsaturated group-containing polymerizable compound 30 to 1
Applying a solvent mixture of the resin composition consisting of 50 parts by weight,
A solvent is dried to form a coating film having a film thickness of 200 nm or less and a refractive index of less than 1.60 (preferably 1.45 or less). (7) Heating the coating film obtained by drying the solvent. Treatment and / or ionizing radiation treatment is performed to fully cure the coating film including other coating films.

FIG. 10 is a flow chart of the fourth production method of the type II optically functional film of the present invention. Figure 10
(A) is a process paper 5 on which a fine particle layer 4 having a refractive index of 1.60 or more is formed, and a transparent base film 1 is coated with a resin to form another layer 2, and A state in which the fine particle layer 4 is embedded in the other layer 2 and pressure-bonded to be laminated is shown. FIG. 10B shows a laminated state. In FIG. 10B, the fine particle layer 4 is
It may be completely buried in the other layer 2, or a part of the fine particle layer 4 may be exposed from the other layer 2. Figure 1
0 (c) is a state in which the process paper 5 is peeled from the laminate. FIG. 10 (d) shows that on the fine particle layer 4,
1 shows a state in which a low refractive index layer 3 which is a thin film of a low refractive index resin composition used in the present invention is formed by coating.

The fifth production method of the optical functional film of type II of the present invention is a method of using an adhesive for adhering the transparent substrate film and other layers, and A fine particle layer having a refractive index of 1.60 or more has an optical film thickness of λ / 4.
Or (2) a coating film mainly composed of a resin is formed on the fine particle layer formed on the obtained process paper so as to have a thickness of λ / 2 (450 <λ <600 nm). After being formed as described above, the fine particle layer is embedded in the coating film or a part of the fine particle layer is embedded, and (3) the obtained coating film is subjected to heat treatment and / or ionizing radiation treatment. Half-curing or full-curing, (4) forming an adhesive layer on the obtained half-cured or fully-cured coating film, or forming an adhesive layer on a transparent substrate film prepared separately, (5) After laminating the process paper and the transparent substrate film with the resin layer formed on the process paper inside through the adhesive layer, the process paper is peeled off to form the resin layer and the fine particle layer. Transferred to a transparent substrate film, (6) transferred layer On top, vinylidene fluoride 30-
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing 90% by weight and hexafluoropropylene of 5 to 50% by weight, and an ethylenically unsaturated group. Of a polymerizable compound having 30 to 150 parts by weight of a resin composition is applied, and the solvent is dried to form a thin film having a film thickness of 200 nm or less and a refractive index of less than 1.60 (preferably 1.45 or less). It is characterized in that a coating film is formed, and heat treatment and / or ionizing radiation treatment is carried out to fully cure the coating film including other coating films.

FIG. 11 is a flow chart of the fifth production method of the type II optically functional film of the present invention. Figure 1
1 (a) shows a state in which the fine particle layer 4 is formed on the process paper 5 and the other layer 2 is further formed on the fine particle layer 4 and full cure or half cure is performed. In FIG. 11B, an adhesive layer 6 is formed on either the other layer 2 side of the process paper 5 or the transparent substrate film 1 side, and both films are laminated via the adhesive layer 6. Shows the state. FIG. 11 (c)
Shows a state in which the process paper 5 is peeled off after the adhesive layer 6 is fully cured. FIG. 11D shows that the low refractive index layer 3, which is a thin film of the resin composition for a low refractive index layer used in the present invention, is further formed on the fine particle layer 4 by coating, and heat treatment and / or ionizing radiation is performed. The state where the coating film is fully cured by treatment is shown.

The sixth production method of the type II optically functional film of the present invention is a method in which an adhesive is not used for adhering the transparent substrate film and the other layers. A fine particle layer having a refractive index of 1.60 or more has an optical film thickness of λ /
4 or λ / 2 (450 <λ <600 nm), and (2) a coating film composed mainly of a resin is formed on the fine particle layer formed on the obtained process paper. It is formed so as to have a thickness of at least one, and the fine particle layer is embedded in the coating film, or a part of the fine particle layer is embedded, and (3) a transparent substrate film is separately prepared, and the process paper and the transparent The substrate film is laminated with the coating film on the process paper inside, and (4) the laminate is subjected to heat treatment and / or ionizing radiation treatment to half-cure or full-cure the coating film, and then the process paper. Is peeled off to transfer the resin layer and the fine particle layer onto the transparent substrate film, and (5) a monomer containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene on the transferred layer. The composition is copolymerized Fluorine content ratio is 60-70
A solvent mixture of a resin composition comprising 100 parts by weight of a fluorine-containing copolymer (weight%) and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group is applied, and the solvent is dried to a film thickness of 200 nm or less. Thin film with a refractive index of 1.6
It is characterized in that a coating film of less than 0 (preferably 1.45 or less) is formed, and heat treatment and / or ionizing radiation treatment is carried out to fully cure the coating film including other coating films.

In the above-mentioned method for producing each optical functional film, the significance of forming a coating film and then half-curing the coating film is to increase the adhesion between the coating films.

In each of the above methods for producing the optical functional film, particularly, the optical function in which the fine particle layer is not completely buried in the other layer and a part of the fine particle layer is exposed from the other layer. In order to produce a flexible film, the viscosity of the resin used in the other layer, the type of the resin, the surface tension of the resin, the particle size of the fine particles, the filling rate of the fine particles, and the resin used in the other layer. This can be achieved by considering the wettability with fine particles and the like.

Specifically, the resin used for the other layer has a high viscosity or is selected to have a touch-drying property (described later) at the time of coating (touch-drying condition), whereby The part is easily exposed. In addition, it is also possible to select a resin having a low surface tension or a resin having a small particle size and a high packing rate. Further, when selecting the resin and the fine particles, a resin having poor wettability may be selected.

Process paper : Also called a release film, generally, a sheet on which a release treatment such as silicon, fluorine or acryl-melamine is applied or an untreated one is used. The surface may be smooth or have irregularities,
When the final product has irregularities, irregularities are formed on the surface of the final product, so that the obtained optical functional film can be provided with an antireflection effect or an antiglare effect.

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.

Dry to the touch : In the production of the second transparent functional film of the present invention, it is necessary to expose a part of the functional fine particle layer from the hard coat layer. For that purpose, since the viscosity of the applied coating film of the resin composition for the hard coat layer is high when the film is dry to the touch, by contacting the functional fine particle layer, the entire functional fine particle layer is hard-coated. Part of the functional fine particle layer is exposed without being completely buried in the layer. Further, there is an advantage that the adhesion between the hard coat layer and the functional fine particle layer is improved 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 prepared 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 group: 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 monomers listed above 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 to the above-mentioned monomers polymerized or copolymerized by the following methods a) to d), 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 trace 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 room 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 adhesive resin used in the above method of mixing the ionizing radiation curable resin with the adhesive 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 for 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 acid 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 resin having adhesiveness 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.

On the lower surface of the optical functional film of the present invention,
An adhesive may be applied, 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 : The optical functional film of the present invention can be laminated on a polarizing element to form a polarizing plate having improved antireflection properties. This polarizing element is dyed with iodine or dye,
A stretched polyvinyl alcohol film, polyvinyl formal film, polyvinyl acetal film, ethylene-vinyl acetate copolymer saponified film, or the like can be used. When the base film of the optical functional film is, for example, a triacetyl cellulose film, the saponification process is performed on the triacetyl cellulose film in order to increase the adhesiveness and prevent static electricity in the laminating process. This saponification treatment may be performed before or after applying the hard coat to the triacetyl cellulose film.

FIG. 12 shows an example of a polarizing plate using the optical functional film of the present invention. In the figure, 14 is an optical functional film of the present invention having an antireflection property, and the optical functional film 14 is laminated on the polarizing element 11, while the other surface of the polarizing element 11 is a triacetyl cellulose film. (Omitted: TAC film) 12 is laminated. Moreover, the optical functional film 14 of the present invention may be laminated on both surfaces of the polarizing element 11.

FIG. 13 shows an example of a liquid crystal display device using the optical functional film of the present invention. Liquid crystal display element 13
The polarizing plate shown in FIG. 12, that is, the TAC film /
A polarizing plate having a layered structure composed of a polarizing element / optically functional film is laminated, and a polarizing plate having a layered structure composed of a TAC film / polarizing device / TAC film is laminated on the other surface of the liquid crystal display device 13. ing. In the STN type liquid crystal display device, a retardation plate is inserted between the liquid crystal display element and the polarizing plate.

[0134]

【Example】

[Example 1] A ZnO ultrafine particle dispersion liquid (ZS-30 having a refractive index of 1.90) on a release film (MC-19: trade name, manufactured by Reiko, whose surface is treated with acrylic-melamine).
0: trade name, made by Sumitomo Cement, particle size 10 nm) and electron beam curable resin with a refractive index of 1.53 (HN-5A: trade name, manufactured by Mitsubishi Yuka) were mixed at a weight ratio of 45: 1. The solution was applied so that the film thickness would be 72 nm / dry.

On the other hand, an ionizing radiation curable resin (EXG: trade name, manufactured by Dainichiseika Kogyo Co., Ltd.) having a refractive index of 1.50 was coated on a triacetyl cellulose film so as to have a film thickness of 5 μ / dry. The resin surface of was laminated with the ultrafine particle surface, and the obtained laminated film was irradiated with 2 Mrad of an electron beam to half-cure the resin. The release film was peeled off from the laminate film, and an ionizing radiation-curable fluororesin (KZ: trade name, manufactured by Japan Synthetic Rubber) having a refractive index of 1.43 was applied to the release surface [that is, 60 parts by weight of vinylidene fluoride, hexa Ionizing radiation-curable fluororesin composition obtained by mixing 40 parts by weight of dipentaerythritol hexaacrylate with 60 parts by weight of a fluorine-containing copolymer consisting of 20 parts by weight of fluoropropylene and 20 parts by weight of tetrafluoroethylene] 100 nm / dr
coating so that it becomes y, irradiating with 2 Mrad of electron beam,
The resin layer including the lower layer resin was fully cured.

The thus-obtained antireflection film had a total light transmittance of 95.3% and a reflectance of 550 nm of 0.3%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

[Example 2] Release film (MC-19:
Product name, made by Reiko, whose surface is treated with acrylic-melamine), and an ionizing radiation-curable fluororesin (KZ: product name, made by Japan Synthetic Rubber) with a refractive index of 1.43 and a film thickness of 10
It is coated so that it becomes 0 nm / dry, and the electron beam is 1 Mra.
The resin was half-cured by irradiation.

On this resin layer, a ZnO ultrafine particle dispersion having a refractive index of 1.90 (ZS-300: trade name, manufactured by Sumitomo Cement, particle size 10 nm) and an electron beam curable resin having a refractive index of 1.53 (HN- 5A: trade name, manufactured by Mitsubishi Yuka) 4 by weight
The solution mixed at a ratio of 5: 1 was applied so as to have a film thickness of 72 nm / dry.

An ionizing radiation curable resin (EXG: trade name, manufactured by Dainichiseika Kogyo Co., Ltd.) having a refractive index of 1.50 is coated on the ultrafine particle film formed by the above method so as to have a film thickness of 3 μ / dry. Then, the electron beam was irradiated with 5 Mrad, and the entire resin layer including the lower layer resin was fully cured. An adhesive (Takelac: trade name, manufactured by Takeda Yakuhin, curing agent: 14% on this cured resin layer
(Added) is applied so that the thickness becomes 4 μ / dry, and the refractive index is 1.
49 triacetyl cellulose films (FFUV-8
0: product name, manufactured by Fuji Film Co., Ltd., film thickness 80 μ) was laminated and aged at 40 ° C. for 3 days, and then the release film was peeled off.

The total light transmittance of the antireflection film thus obtained was 95.3%, and the reflectance at 550 nm was 0.3%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

[Example 3] Release film (MC-19:
Product name, Reiko, acrylic-melamine treated surface, ZnO ultrafine particle dispersion with a refractive index of 1.90 (ZS-300: product name, Sumitomo Cement, particle size 10n
m) and an electron beam curable resin having a refractive index of 1.53 (HN-5
A: A trade name, manufactured by Mitsubishi Petrochemical Co., Ltd.) was mixed at a weight ratio of 45: 1 to apply a solution having a film thickness of 72 nm / dry.

Ionizing radiation curable resin (EXG: trade name, manufactured by Dainichiseika Kogyo) having a refractive index of 1.50 on the ultrafine particle film.
To a film thickness of 3μ / dry, and apply 2M of electron beam.
The resin layer was half-cured by rad irradiation.

An adhesive (Takelac: trade name, manufactured by Takeda Pharmaceutical Co., Ltd., curing agent: 14% added) was added to this resin layer at 4 μ / dry.
And a triacetyl cellulose film having a refractive index of 1.49 (FFUV-80: trade name, manufactured by Fuji Film Co., Ltd., film thickness 80 μ), and aged at 40 ° C. for 3 days, and then a release film. Was peeled off.

Ionizing radiation-curable fluorine-based resin (KZ: trade name, made by Japan Synthetic Rubber) having a refractive index of 1.43 is formed on the release surface.
Was applied to give a film thickness of 100 nm / dry, and an electron beam was irradiated at 2 Mrad to fully cure the resin layer including the lower resin.

The total light transmittance of the thus-obtained antireflection film was 95.3%, and the reflectance at 550 nm was 0.3%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

Example 4 ZnO having a refractive index of 1.90 was formed on a triacetyl cellulose film having a refractive index of 1.49 (FFUV-80: trade name, manufactured by Fuji Film, thickness 80 μm).
Ultrafine particle dispersion (ZS-300: trade name, made by Sumitomo Cement, particle size 10 nm) and electron beam curable resin with a refractive index of 1.53 (HN-5A: trade name, made by Mitsubishi Yuka) in a weight ratio of 2 :
A solution (refractive index: 1.65) blended at a ratio of 1 was applied to a film thickness of
/ Dry was applied, the electron beam was irradiated with 2 Mrad, and the resin was half-cured.

On this resin layer, an ionizing radiation-curable fluororesin (KZ: trade name, made by Japan Synthetic Rubber) having a refractive index of 1.43 was coated to a film thickness of 100 nm / dry, and an electron beam of 2 Mrad was applied. Irradiation was performed to fully cure the entire resin layer including the lower resin.

The antireflection film thus obtained had a total light transmittance of 94.7% and a reflectance of 550 nm of 1.0%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

Example 5 Zn having a refractive index of 1.90 was formed on a triacetyl cellulose film having a refractive index of 1.49 (FFUV-80: trade name, manufactured by Fuji Film, thickness 80 μm).
O Ultrafine particle dispersion (ZS-300: trade name, made by Sumitomo Cement, particle size 10 nm) and electron beam curable resin with a refractive index of 1.53 (HN-5A: trade name, manufactured by Mitsubishi Yuka) in a weight ratio. A solution (refractive index: 1.65) mixed at a ratio of 2: 1 was applied to a film thickness of 4 μ / dry, and an electron beam was applied at 2 Mrad.
Irradiation was performed to completely cure the resin.

An adhesive (Takelac: trade name, manufactured by Takeda Chemical Co., Ltd., curing agent: 14% added) was added to this resin layer at 4 μ / dry.
And applied a triacetyl cellulose film (FFUV-80: trade name, made by Fuji Film, thickness 80
μ) and aging at 40 ° C. for 3 days, and then the release film was peeled off. A refractive index of 1.
43 ionizing radiation curable fluororesin (KZ: trade name,
(Nippon Synthetic Rubber) was applied to a film thickness of 100 nm / dry, and the resin layer was cured by irradiating an electron beam at 2 Mrad.

The antireflection film thus obtained had a total light transmittance of 94.7% and a reflectance of 550 nm of 1.0%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

Example 6 Release Film (MC-19:
Brand name, made by Reiko, acrylic-melamine treated on the surface) 1.90 ZnO ultrafine particle dispersion liquid with refractive index (ZS-300: trade name, made by Sumitomo Cement, particle size 10n
m) was applied so as to have a film thickness of 100 nm / dry, and the resin was half-cured by irradiation with an electron beam at 2 Mrad.

On this resin layer, a ZnO ultrafine particle dispersion having a refractive index of 1.90 (ZS-300: trade name, manufactured by Sumitomo Cement, particle size 10 nm) and an electron beam curable resin having a refractive index of 1.53 (HN- 5A: product name, manufactured by Mitsubishi Yuka) in a weight ratio of 2:
A resin having a refractive index of 1.65 mixed in a ratio of 1 has a film thickness of 3 μ /
It was coated so as to be dry, and the resin was completely cured by irradiation with an electron beam of 5 Mrad.

An adhesive (Takelac: trade name, manufactured by Takeda Chemical Co., Ltd., curing agent: 14% added) was added to this resin layer at 4 μ / dry.
And a triacetyl cellulose film having a refractive index of 1.49 (FFUV-80: trade name, manufactured by Fuji Film Co., Ltd., film thickness 80 μ), and aged at 40 ° C. for 3 days, and then a release film. Was peeled off.

The total light transmittance of the thus-obtained antireflection film was 94.7%, and the reflectance at 550 nm was 1.0%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

Example 7 Release Film (MC-19:
Product name, made by Reiko, whose surface is treated with acrylic-melamine), and an ionizing radiation-curable fluororesin (KZ: product name, made by Japan Synthetic Rubber) with a refractive index of 1.43 and a film thickness of 10
It is coated so that it becomes 0 nm / dry, and the electron beam is 2 Mra.
The resin was half-cured by irradiation.

On this resin layer, a ZnO ultrafine particle dispersion having a refractive index of 1.90 (ZS-300: trade name, manufactured by Sumitomo Cement, particle size 10 nm) and an electron beam curable resin having a refractive index of 1.53 (HN- 5A: trade name, manufactured by Mitsubishi Yuka) 4 by weight
The solution mixed at a ratio of 5: 1 is applied so as to have a film thickness of 72 nm / dry.

Zn having a refractive index of 1.90 was formed on the ultrafine particle layer.
O Ultrafine particle dispersion (ZS-300: trade name, made by Sumitomo Cement, particle size 10 nm) and electron beam curable resin with a refractive index of 1.53 (HN-5A: trade name, manufactured by Mitsubishi Yuka) in a weight ratio. Resin with a refractive index of 1.65 mixed at a ratio of 2: 1 has a film thickness of 3
The coating was performed so as to be μ / dry, and the resin was completely cured by irradiating with an electron beam of 5 Mrad.

An adhesive agent (Takelac: trade name, manufactured by Takeda Chemical Co., Ltd., hardener: 14% added) was added to this resin layer at 4 μ / dry.
And a triacetyl cellulose film having a refractive index of 1.49 (FFUV-80: trade name, manufactured by Fuji Film Co., Ltd., film thickness 80 μ), and aged at 40 ° C. for 3 days, and then a release film. Was peeled off.

The total light transmittance of the antireflection film thus obtained was 95.8%, and the reflectance at 550 nm was 0.1%. The pencil hardness was 2H, and the result of the steel wool resistance test was that it was not scratched even after rubbing 10 times under a load of 250 g. Regarding the adhesion test,
After putting a 1 mm square grain and rapidly peeling the same portion 5 times with a transparent adhesive tape, there was no peeling of the coating film.

[0161]

The resin composition for the low refractive index layer used in the optical functional film of the present invention has a sufficiently low refractive index and can be formed into a solvent-soluble, sufficiently thin film. Since the thin film has scratch resistance, the optical functional film obtained by the present invention is excellent in antireflection property, excellent in scratch resistance, and furthermore, the optical functional film of the present invention can be formed by coating. , Its manufacture can be done in a simple way.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a type I optically functional film of the present invention.

FIG. 2 is a cross-sectional view of a type II optically functional film of the present invention.

FIG. 3 is a cross-sectional view of a type II optically functional film of the present invention.

FIG. 4 is a flow chart showing a first manufacturing method of the type I optically functional film of the present invention.

FIG. 5 is a flow chart of a second production method of the type I optically functional film of the present invention.

FIG. 6 is a flow chart of a fourth manufacturing method of the type I optically functional film of the present invention.

FIG. 7 is a flow chart of a first manufacturing method of the type II optically functional film of the present invention.

FIG. 8 is a flow chart of the second production method of the type II optically functional film of the present invention.

FIG. 9 is a flow chart of the third production method of the type II optically functional film of the present invention.

FIG. 10 shows an optical functional film of type II of the present invention,
It is a flowchart of the 4th manufacturing method.

FIG. 11 shows the type II optically functional film of the present invention,
It is a flowchart of the 5th manufacturing method.

FIG. 12 shows an example of a polarizing plate in which the optical functional film of the present invention is used.

FIG. 13 shows an example of a liquid crystal display device using the optical functional film of the present invention.

[Explanation of symbols]

 1 Transparent Substrate Film 2 Other Layer 3, 10 Low Refractive Index Layer 4 Fine Particle Layer 5 Process Paper 6 Adhesive Layer 7 Fine Particles 8 TAC Film 9 High Refractive Index Hard Coat Layer 11 Polarizing Element 12 TAC Film 13 Liquid Crystal Display Element 14 Optical Functional film

Claims (25)

[Claims] 1. A transparent substrate film, (1) through (2) another layer consisting of one or more layers, (3) 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing OH, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. A low refractive index layer having a refractive index of less than 1.60, which is a thin film having a thickness of 200 nm or less and is provided with scratch resistance, is formed by using the resin composition. (4) Among the other layers The layer directly in contact with the low refractive index layer has a refractive index higher than that of the low refractive index layer. 2. The optical function according to claim 1, wherein among the other layers, a layer that is in direct contact with the low refractive index layer is mainly made of a thermosetting resin and / or an ionizing radiation curable resin. Sex film. 3. The optical element according to claim 1, wherein a layer of the other layers that is in direct contact with the low refractive index layer has a refractive index higher than that of the transparent substrate film. Functional film. 4. The layer which is in direct contact with the low refractive index layer among the other layers contains fine particles and a binder resin, and the refractive index of the layer is 1.60 or more. 2. The optically functional film according to 2 or 3. 5. Among the other layers, the layer which is in direct contact with the low refractive index layer has fine particles having a refractive index of 1.60 or more from the interface with the low refractive index layer to the inside of the other layer. It is fixed by being made into a solid, The claim 1, 2, 3 or 4 characterized by the above-mentioned.
The optically functional film described. 6. Among the other layers, the layer which is in direct contact with the low refractive index layer has fine particles having a refractive index of 1.60 or more from the interface with the low refractive index layer to the inside of the other layer. The optical functional film according to claim 5, wherein the refractive index of the other layer in the portion where the fine particles are fixed and in which the fine particles are not present is less than 1.60. 7. Among the other layers, the layer which is in direct contact with the low refractive index layer has fine particles having a refractive index of 1.60 or more from the interface with the low refractive index layer to the inside of the other layer. 7. The refractive index of the other layer in the portion where the fine particles are fixed and in which the fine particles are not present is higher than the refractive index of the transparent substrate film. Optical functional film. 8. The fine particles having a refractive index of 1.60 or more, which are localized and fixed from the interface with the low refractive index layer to the inside of another layer, have an optical film thickness of λ / 4 or λ / 2 (4
The optical functional film according to claim 5, 6 or 7, wherein a fine particle layer of 50 nm <λ <600 nm) is formed. 9. One of the other layers is an adhesive layer which is in contact with the transparent substrate film, and is one of the layers 1, 2, 3, 4, 5, 6, 7 or 8. The optically functional film described. 10. The optical function of the optical functional film is an antireflection function.
The optical functional film as described in 4, 5, 6, 7, 8 or 9. 11. The optical functional film according to claim 1, wherein fine irregularities are formed on the outermost surface of the optical functional film.
The optical functional film according to 2, 3, 4, 5, 6, 7, 8, 9 or 10. 12. (1) On the transparent substrate film, directly or through another layer, (2) the refractive index of the resin composition is the resin composition in the layer structure of the optical functional film as a final product. The resin composition having a higher refractive index than the layer directly in contact with the lower layer of the layer is used to form a coating film, and (3) the obtained coating film is subjected to heat treatment and / or ionizing radiation treatment. Then, the coating film is fully cured or half cured, and (4) the obtained fully cured or half cured coating film contains 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. The content of fluorine formed by copolymerizing the monomer composition is 60 to 7
A solvent mixture of a resin composition comprising 100 parts by weight of a fluorine-containing copolymer, which is 0% by weight, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group is applied, and the solvent is dried to form a film thickness of 200 nm. A coating film having the following thin film and having a refractive index of less than 1.60 is formed, and (5) the coating film obtained by drying the solvent is subjected to heat treatment and / or ionizing radiation treatment to give another coating film. A method for producing an optical functional film, which comprises performing full cure including a coating film. 13. The refractive index of the resin composition on the step (1) paper is more than the refractive index of the layer directly in contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as a final product. Also, a high resin composition is applied to form a coating film, and (2) the coating film obtained in the above step is subjected to heat treatment and / or ionizing radiation treatment to be half-cured or full-cured. (3) An adhesive layer is formed on either the obtained half-cured or fully-cured coating film or on the transparent substrate film, and (4) coating on the process paper via the adhesive layer. After laminating the process paper and the transparent substrate film with the membrane side inside,
The process paper is peeled off, and (5) 30 to 90% by weight of vinylidene fluoride and 5 to hexafluoropropylene are placed on the half-cured or fully-cured coating film formed on the transparent substrate film.
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 50% by weight, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. Part of the resin composition is applied, and the solvent is dried to a film thickness of 200 nm.
A coating film having the following thin film and a refractive index of less than 1.60 is formed, and (6) the coating film obtained by drying the solvent is subjected to a heat treatment and / or an ionizing radiation treatment to give another coating film. A method for producing an optical functional film, which comprises performing full cure including a coating film. 14. The refractive index of the resin composition on the step (1) paper is more than the refractive index of the layer directly in contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product. Also, a high resin composition is applied to form a coating film. (2) On the other hand, a transparent substrate film is prepared, and the process paper and the transparent substrate film are laminated with the coating film side on the process paper inside. (3) After the obtained laminate is half-cured or full-cured, the process paper is peeled off. (4) On the half-cured or fully-cured coating film formed on the transparent substrate film. , Vinylidene fluoride 30 to 90% by weight and hexafluoropropylene 5 to
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 50% by weight, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. Part of the resin composition is applied, and the solvent is dried to a film thickness of 200 nm.
A coating film having the following thin film and having a refractive index of less than 1.60 is formed, and (5) the coating film obtained by drying the solvent is subjected to heat treatment and / or ionizing radiation treatment to give another coating film. A method for producing an optical functional film, which comprises performing full cure including a coating film. 15. A vinylidene fluoride (30-90% by weight) and hexafluoropropylene (5-5) on (1) step paper.
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 0% by weight, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. Part of the resin composition is applied, and the solvent is dried to form a coating film having a film thickness of 200 nm or less and a refractive index of less than 1.60. In the uncured state, or by subjecting the coating film to a heat treatment and / or an ionizing radiation treatment to perform full cure or half cure, (3) the refractive index of the resin composition on the obtained coating film A coating film is formed by applying a resin composition having a higher refractive index than a layer directly in contact with a layer below the layer using the resin composition in the layer structure of the optical functional film as a final product, ) Heating the coating film obtained in the above process (5) Fully-cured process including curing of other coatings by performing physical treatment and / or ionizing radiation treatment, and (5) fully-cured coating film formed on paper or a transparent substrate prepared separately. An adhesive layer is formed on either one of the films, and (6) after the process paper and the transparent substrate film are laminated with the coating film side on the process paper inside through the adhesive layer,
A process for producing an optical functional film, which comprises peeling a process paper. 16. The (1) step paper has 30 to 90% by weight of vinylidene fluoride and 5 to 5 of hexafluoropropylene.
100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 0% by weight, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. Part of the resin composition is applied, and the solvent is dried to form a coating film having a film thickness of 200 nm or less and a refractive index of less than 1.60. In the uncured state, or by subjecting the coating film to a heat treatment and / or an ionizing radiation treatment to perform full cure or half cure, (3) the refractive index of the resin composition is A resin composition having a higher refractive index than the layer directly in contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product is applied to form a coating film. , Prepare a transparent substrate film, The serial process paper and the transparent substrate film to a coating process paper inside laminated, with respect to (5) resulting laminate was heat-treated and /
Alternatively, a method for producing an optical functional film, which comprises performing ionizing radiation treatment to perform full cure including other coating films, and then peeling the process paper. 17. A resin composition, wherein the refractive index of the resin composition is higher than the refractive index of a layer directly in contact with a lower layer of a layer using the resin composition in the layer structure of an optical functional film as a final product, 13. A resin composition comprising a binder resin and high refractive index fine particles having a refractive index higher than that of the binder resin.
A method for producing an optically functional film according to 3, 14, 15 or 16. 18. A thin film having a film thickness of 200 nm or less and having a refractive index of less than 1.60, which is obtained by applying a low refractive index resin composition diluted with a solvent onto a step (1) step paper and drying the solvent. A low refractive index layer is formed, (2) the obtained low refractive index layer is left in an uncured state, or the low refractive index layer is subjected to heat treatment and / or ionizing radiation treatment to be half-cured or full-cured, 3) On the obtained low-refractive index layer, a fine particle layer having a refractive index of 1.60 or more is formed to have an optical film thickness of λ / 4 or λ / 2 (450 <λ <
600 nm), and (4) a coating film mainly composed of a resin is formed on the obtained fine particle layer, and heat treatment and / or ionizing radiation treatment is performed,
This coating film is fully cured including curing of other coating films, and (5) an adhesive layer is formed on the fully cured resin layer formed on the obtained process paper, or a transparent film prepared separately. An adhesive layer is formed on the base film, and (6) the process paper and the transparent base film are laminated with the resin layer formed on the process paper inside through the adhesive layer, and then the process A method for producing an optical functional film, which comprises peeling paper. 19. A low-refractive-index resin composition diluted with a solvent is applied onto step (1) paper, and the solvent is dried to obtain a film thickness of 20.
A low refractive index layer having a refractive index of less than 1.60, which is a thin film having a thickness of 0 nm or less, is formed, and (2) the obtained low refractive index layer remains in an uncured state, or the low refractive index layer is subjected to heat treatment and / or Alternatively, it is subjected to ionizing radiation treatment to be half-cured or full-cured, and (3) a fine particle layer having a refractive index of 1.60 or more is formed on the obtained low refractive index layer with an optical film thickness of λ / 4 or λ / 2 (450). <Λ <
(4) On the other hand, (4) on the other hand, a coating film mainly composed of a resin is formed on the transparent substrate film, (5) a low refractive index layer and a fine particle layer formed on the process paper, By laminating by pressing both the process paper and the transparent substrate film so that the resin layer on the transparent substrate film is in contact, the fine particle layer is embedded in the resin layer or a part of the fine particle layer is embedded, (6) The obtained laminate is subjected to heat treatment and / or ionizing radiation treatment to be fully cured including curing of other coating films, and then the process paper is peeled off to form a low refractive index layer and a high refractive index. A method for producing an optical functional film, which comprises transferring a fine particle layer. 20. The low refractive index resin composition diluted with a solvent is applied onto step (1) paper, and the solvent is dried to obtain a film thickness of 20.
A low refractive index layer having a refractive index of less than 1.60, which is a thin film having a thickness of 0 nm or less, is formed, and (2) the obtained low refractive index layer remains in an uncured state, or the low refractive index layer is subjected to heat treatment and / or Alternatively, it is subjected to ionizing radiation treatment to be half-cured or full-cured, and (3) a fine particle layer having a refractive index of 1.60 or more is formed on the obtained low refractive index layer with an optical film thickness of λ / 4 or λ / 2 (450). <Λ <
600 nm), (4) a coating film composed mainly of a resin is formed on the obtained fine particle layer, and (5) a transparent substrate film is separately prepared, and the process paper and the transparent substrate are prepared. The material film is laminated with the resin layer formed on the process paper inside, and (6) heat treatment and / or
Alternatively, a method for producing an optical functional film, which comprises performing full curing including curing of other coating films by performing ionizing radiation treatment, and then peeling the process paper. 21. The low refractive index resin composition has a fluorine content ratio of 60 to 70 obtained by copolymerizing a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. 21. A resin composition comprising 100 parts by weight of a fluorine-containing copolymer (weight%) and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group.
A method for producing the optically functional film described. 22. A fine particle layer having a refractive index of 1.60 or more is formed on a paper of step (1) and has an optical film thickness of λ / 4 or λ / 2 (450 <
(2) On the other hand, a coating film mainly composed of a resin is formed on the transparent substrate film, and (3) the fine particle layer formed on the process paper, and By laminating by pressing the process paper and the transparent substrate film so that the resin layer formed on the transparent substrate film is in contact, the fine particle layer is embedded in the resin layer or a part of the fine particle layer is formed. (4) Fully cure or half cure this coating by subjecting the obtained laminate to heat treatment and / or ionizing radiation treatment, (5) Obtained full cure or half cured laminate The process paper is peeled from the object to transfer the fine particle layer to the transparent substrate film, and (6) vinylidene fluoride 30 to 90 is formed on the transferred layer.
A fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing 5% to 50% by weight of hexafluoropropylene.
0 parts by weight and a solvent mixture of a resin composition consisting of 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group are applied, and the solvent is dried to form a thin film having a film thickness of 200 nm or less and a refractive index of 1 Forming a coating film of less than 60. (7) subjecting the coating film obtained by drying the solvent to a heat treatment and / or an ionizing radiation treatment so that the coating film including other coating films is fully cured. A method for producing a featured optical functional film. 23. A fine particle layer having a refractive index of 1.60 or more and an optical film thickness of λ / 4 or λ / 2 (450 <1.
λ <600 nm), and (2) a coating film composed mainly of a resin is formed on the fine particle layer formed on the obtained process paper so as to have a thickness not less than that of the fine particle layer. Then, the fine particle layer is embedded in the coating film or a part of the fine particle layer is embedded, and (3) the obtained coating film is subjected to a heat treatment and / or an ionizing radiation treatment to obtain a half cure or a full cure. (4) An adhesive layer is formed on the obtained half-cured or fully-cured coating film, or an adhesive layer is formed on a separately prepared transparent substrate film, (5) the adhesive layer Through the process paper and the transparent substrate film laminated with the resin layer formed on the process paper inside, and then the process paper is peeled off to transfer the resin layer and the fine particle layer to the transparent substrate film. , (6) Vinyl fluoride is provided on the transferred layer. Reden 30-90
Fluorine-containing copolymer 10 having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 5% by weight and hexafluoropropylene 5 to 50% by weight.
0 parts by weight and a solvent mixture of a resin composition consisting of 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group are applied and the solvent is dried to form a thin film having a thickness of 200 nm or less and a refractive index of 1.60. A method for producing an optical functional film, comprising forming a coating film having a thickness of less than 1 and performing a heat treatment and / or an ionizing radiation treatment to allow the coating film to be fully cured including other coating films. 24. A fine particle layer having a refractive index of 1.60 or more is formed on a paper having the optical film thickness of λ / 4 or λ / 2 (450 <1.
λ <600 nm), and (2) a coating film composed mainly of a resin is formed on the fine particle layer formed on the obtained process paper so as to have a thickness not less than that of the fine particle layer. Then, the fine particle layer is embedded in the coating film, or a part of the fine particle layer is embedded. (3) Separately prepare a transparent substrate film, and coat the process paper and the transparent substrate film on the process paper. The film is laminated with the film inside, and (4) the laminate is subjected to heat treatment and / or ionizing radiation treatment to half-cure or full-cure the coating film, and then the process paper is peeled off to separate the resin layer and the fine particles. The layer is transferred onto a transparent substrate film, and (5) vinylidene fluoride 30 to 90 is transferred onto the transferred layer.
A fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing a monomer composition containing 5% to 50% by weight of hexafluoropropylene.
0 parts by weight and a solvent mixture of a resin composition consisting of 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group are applied and the solvent is dried to form a thin film having a thickness of 200 nm or less and a refractive index of 1.60. A method for producing an optical functional film, which comprises forming a coating film having a thickness of less than 1 and performing a heat treatment and / or an ionizing radiation treatment to fully cure the coating film including other coating films. 25. The resin-based coating film is a resin composition containing a binder resin and high refractive index fine particles having a refractive index higher than that of the binder resin. It is characterized in that the refractive index of the product is made of a resin composition higher than the refractive index of the layer directly in contact with the lower layer of the layer using the resin composition in the layer structure of the optical functional film as the final product. Claim 18, 1
The method for producing an optically functional film according to 9, 20, 21, 22, 23 or 24.