JP4319880B2 - Antireflection film, antireflection film and image display device - Google Patents

Description

  The present invention relates to an antireflection film, an antireflection film, and a display device (particularly a liquid crystal display device) using the same.

  In general, an antireflection film is used in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD) to reduce contrast or reduce an image due to reflection of external light. In order to prevent reflection, it is placed on the outermost surface of the display so as to reduce reflectivity using the principle of optical interference.

Such an antireflection film can be produced by forming a high refractive index layer on a support and a low refractive index layer having an appropriate film thickness thereon. From the viewpoint of productivity, it is preferable that each layer can be formed by wet coating.
A fluorine-containing copolymer having a low refractive index is known as a material for a low refractive index layer that can be wet-coated (see, for example, Patent Document 1). However, the fluorine-containing copolymer tends to be negatively charged, and there is a problem that dust tends to adhere to the surface of the antireflection film.

  A technique for improving the antistatic property by adding a positively chargeable silicone component to the fluorine-containing polymer layer is disclosed (for example, see Patent Document 2). According to this technology, it is effective for anti-static as well as water and oil repellency, but depending on the type of fluoropolymer, it is difficult to reach a sufficient level, and if the silicone component is increased to increase the effect, scratch resistance Problems such as lowering of the viscosity and transfer of the silicone component to the contact medium occur.

  On the other hand, although an example using a fluorine-containing copolymer containing an alkylphenol-based polyoxyalkylene chain is disclosed (see Patent Document 3), the refractive index of the film may be increased by an aromatic group, It was not always effective for preventing static electricity.

  From the above, there has been a demand for a technique that exhibits an effect such as antistatic without impairing the refractive index and scratch resistance of the film.

JP-A-8-92323 JP 2002-55205 A Japanese Patent Laid-Open No. 11-228631

  An object of the present invention is to provide an antireflection film having a low reflectance, being hardly scratched, and having excellent antifouling properties and antistatic properties, and secondly, an antireflection film having excellent properties described above. The third object is to provide an anti-reflection film provided on a transparent support, and third, to provide an image display device which is excellent in dust resistance, anti-smudge property and scratch resistance and is prevented from being reflected.

The object of the present invention has been achieved by the present inventions (1) to ( 4 ) shown below .

(1) The antireflection film characterized by containing a fluorine-containing copolymer represented by the following general formula (4).

[In General Formula (4), R ¹ represents a hydrogen atom, a halogen atom or a methyl group. R ¹ represents a hydrogen atom, a halogen atom or a methyl group. Z is -L- _(Y) n -A or ^-L 1 _- to display the _{(CH 2 CH (X) O} ) n -A 1. L represents a divalent linking group not containing an aromatic group, n represents an integer of 2 to 1000, Y represents a polyoxyalkylene chain-containing unit not containing an aromatic group, and A represents an aromatic group Represents no substituent or hydrogen atom. L ¹ represents — (CH ₂ ) _m —O—CH ₂ —CHR ² —O—, —COO—, —COS— , or —CON (R ³ ) —, n represents an integer of 2 to 1000, X represents a hydrogen atom or a methyl group, and A ¹ represents a substituent or a hydrogen atom that does not contain an aromatic group. m represents an integer of 0 to 4, R ² represents a linear, branched, or cyclic alkyl group having 1 to 100 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. L ² represents a linking group having 1 to 10 carbon atoms, and b represents 0 or 1. B represents a polymerization unit of an arbitrary vinyl monomer, and may be a single component or a plurality of components. s, t, u, v represent mass% of each constituent component, and values satisfying 20 ≦ s ≦ 60, 5 ≦ t ≦ 80, 0 ≦ u ≦ 75, 0.001 ≦ v ≦ 20, and s + t + u + v = 100 The polymer is a block polymer, a random polymer, etc., and there is no restriction | limiting in the polymerization form. The same applies hereinafter. ]

( 2 ) The antireflection film as described in (1 ) above, wherein the fluorine-containing copolymer is represented by the following general formula (5).

[In General Formula (5), Z, X, L ² , B, b, and R ¹ represent the same meaning as in General Formula (4) . R ⁴ and R ⁵ represent an alkyl group, a haloalkyl group or an aryl group. R ⁶ represents a hydrogen atom or a substituent having 1 to 10 carbon atoms. L ³ represents a divalent linking group, c represents 0 or 1, and d represents an integer of 10 to 1000. “s”, “t”, “u”, “v”, “w” represent mass% of respective constituent components, and 20 ≦ s ≦ 60, 5 ≦ t ≦ 80, 0 ≦ u ≦ 75, 0.001 ≦ v ≦ 20, 0.001 ≦ It represents a value satisfying w ≦ 20 and s + t + u + v + w = 100, and the polymer is not limited in its polymerization mode, such as a block polymer or a random polymer. The same applies hereinafter. ]
( 3 ) An antireflection film comprising the antireflection film described in (1) or ( 2 ) above on a transparent support.

( 4 ) An image display device comprising the antireflection film according to ( 3 ) above.

The antireflection film of the present invention is a resin film having sufficient film strength and low reflectance, and excellent in antistatic properties and antifouling properties.
Further, the antireflection film and the image display device of the present invention using the antireflection film of the present invention have less dust adhesion, less scratches, good antifouling properties, and little reflection of external light. Excellent visibility.

The antireflection film of the present invention may have a single layer structure composed of only a low refractive index layer, or may have a multilayer structure laminated with a medium / high / low refractive index layer, a hard coat layer, or the like. A multilayer structure is preferable, and a structure in which three or more layers of middle, high, and low refractive index layers are stacked is particularly preferable. The antireflection film may be formed and arranged directly (on the spot) on an image display device or the like, but it is preferable to form the antireflection film in advance and then arrange it on the image display device.
In this specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.

[Typical layer structure of antireflection film]
A typical layer structure of the antireflection film of the present invention will be described below with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing various layer configurations of an antireflection film using the antireflection film of the present invention. The embodiment shown in FIG. 1A has a layer structure in the order of a transparent support 4, a hard coat layer 3, a high refractive index layer 2, and a low refractive index layer 1. As shown in FIG. 1A, an antireflection film having a high refractive index layer 2 and a low refractive index layer 1 has a high refractive index layer as described in JP-A-59-50401. The following formula (I) and the low refractive index layer preferably satisfy the following formula (II).

In the formula, m is a positive integer (generally 1, 2 or 3), n ₁ is the refractive index of the high refractive index layer, and d ₁ is the layer thickness (nm) of the high refractive index layer.

Where n is a positive odd number (generally 1), n ₂ is the refractive index of the low refractive index layer, and d ₂ is the layer thickness (nm) of the low refractive index layer.
The refractive index n ₁ of the high refractive index layer is preferably at least 0.05 higher than that of the transparent support, and the refractive index n ₂ of the low refractive index layer is preferably at least 0.1 higher than the refractive index of the high refractive index layer. Low and at least 0.05 lower than the transparent support. Furthermore, the refractive index n ₁ of the high refractive index layer is preferably in the range of 1.57 to 2.40.

  The embodiment shown in FIG. 1B has a layer structure in the order of a transparent support 4, a hard coat layer 3, a medium refractive index layer 5, a high refractive index layer 2, and a low refractive index layer 1. As shown in FIG. 1B, an antireflection film having a medium refractive index layer 5, a high refractive index layer 2, and a low refractive index layer 1 is disclosed in Japanese Patent Application Laid-Open No. 59-50401. The medium refractive index layer preferably satisfies the following formula (III), the high refractive index layer preferably satisfies the following formula (IV), and the low refractive index layer preferably satisfies the following formula (V).

Where h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer, and d ₃ is the layer thickness (nm) of the medium refractive index layer.

Where j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the layer thickness (nm) of the high refractive index layer.

Where k is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer, and d ₅ is the layer thickness (nm) of the low refractive index layer.

The refractive index n ₃ of the medium refractive index layer is generally in the range of 1.5 to 1.7, and the refractive index n ₄ of the high refractive index layer is generally in the range of 1.7 to 2.2.

Further, λ in the formulas (I) to (V) is the wavelength of visible light, and is a value in the range of 380 to 680 nm. The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers. For example, the medium refractive index layer is produced by a method such as changing the content of the high refractive index inorganic fine particles added to the high refractive index layer.
The low refractive index layer improved according to the present invention is used for the antireflection film having the above layer structure.

[Low refractive index layer]
The low refractive index layer is arranged on the upper layer of the high refractive index layer as shown in FIGS. The upper side of the low refractive index layer is the surface of the antireflection film.

The antireflection film of the present invention contains a fluorine-containing copolymer represented by the following general formula (4), but before the explanation , polymerization of an aliphatic group monomer containing a polyoxyalkylene chain as a reference. The fluorine-containing copolymer containing units will be described. This ^further contain a polysiloxane component having a repeating unit represented by ^{-Si (R 4) (R 5} ) O- (R 4 and ^{R 5} represents an alkyl group, a haloalkyl group or an aryl group) May be . The polysiloxane component may be contained during the fluorine-containing copolymerization, or may be a component other than the fluorine-containing copolymerization.

The aliphatic group monomer containing the polyoxyalkylene chain represented by the following general formula (1) will be described in detail.

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. L represents a divalent linking group containing no aromatic group, Y represents a polyoxyalkylene chain-containing polymer unit containing no aromatic group, and a polyoxyethylene chain-containing polymer unit or polyoxy group containing no aromatic group. A propylene chain-containing polymer unit is more preferred, and a polyoxyethylene chain-containing polymer unit containing no aromatic group is more preferred. n represents an integer of 2 to 1000, more preferably 3 to 100, and still more preferably 5 to 50. A represents a substituent containing no hydrogen atom or aromatic group, and a substituent containing a crosslinking reactive group is more preferred. In addition, two or more kinds of polymerization units of an aliphatic group monomer containing a polyoxyalkylene chain represented by the general formula (1) may be contained as a constituent unit in the fluorine-containing copolymer.

Among aliphatic group monomer having a polyoxyalkylene chain represented by the general formula (1), it is more preferably represented by the following general formula (2).

In General formula (2), R < ¹ > represents a hydrogen atom, a halogen atom, or a methyl group, and a hydrogen atom and a methyl group are more preferable. L ¹ represents — (CH ₂ ) _m —O—CH ₂ —CHR ² —O—, —COO—, —COS—, or —CON (R ³ ) —, and — (CH ₂ ) _m —O—CH ₂ -CHR ² -O-, or -COO- is more preferable. R ² represents a linear, branched or cyclic alkyl group having 1 to 100 carbon atoms, more preferably a linear or branched alkyl group having 1 to 50 carbon atoms. R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. m represents an integer of 0 to 4, and 1 to 3 is more preferable. n represents an integer of 2 to 1000, more preferably 3 to 100, and still more preferably 5 to 50. X represents a hydrogen atom or a methyl group, and a hydrogen atom is more preferable. A ¹ represents a hydrogen atom or a substituent that does not contain an aromatic group, more preferably a hydrogen atom or a substituent that contains a crosslinking reactive group and does not contain an aromatic group, and a hydrogen atom or a (meth) acryloyl group Further preferred. In addition, two or more kinds of polymerization units of an aliphatic group monomer containing a polyoxyalkylene chain represented by the general formula (2) may be contained as a structural unit in the fluorinated copolymer.

  The polymerization unit of the aliphatic group monomer containing the polyoxyalkylene chain represented by the general formula (1) or (2) should be in the range of 0.001 to 20% by mass in the constituent components of the fluorine-containing copolymer. Is preferable, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass.

Specific examples of the aliphatic group monomer containing the polyoxyalkylene chain as the above reference are shown below.

Next , the polysiloxane group as a reference will be described.
The polysiloxane only needs to have a repeating unit represented by —Si (R ⁴ ) (R ⁵ ) O—, and R ⁴ and R ⁵ are preferably an alkyl group (an alkyl group having 1 to 10 carbon atoms. For example, A methyl group, an ethyl group, a hexyl group, etc.), a haloalkyl group (a fluorinated alkyl group having 1 to 10 carbon atoms, for example, a trifluoromethyl group, a pentafluoroethyl group, etc.) or an aryl group (preferably having a carbon number of 6-20). For example, a phenyl group, a naphthyl group, etc., preferably a methyl group or a trifluoromethyl group, particularly preferably a methyl group.
The number of repeating units is preferably in the range of 10 to 1000, more preferably in the range of 20 to 500, and particularly preferably in the range of 30 to 200.
The repeating unit may be a single unit or a plurality of repeating units.

  The polysiloxane component may be contained during the fluorine-containing copolymerization, or may be a component other than the fluorine-containing copolymerization.

一般式（３）において、Ｒ^１は水素原子、ハロゲン原子またはメチル基を表し、水素原子、メチル基がより好ましい。Ｒ^４およびＲ^５はアルキル基（炭素数１〜１０のアルキル基が好ましい。例えば、メチル基、エチル基、ヘキシル基等）、ハロアルキル基（炭素数１〜１０のフッ素化アルキル基が好ましい。例えばトリフルオロメチル基、ペンタフルオロエチル基等）またはアリール基（炭素数６〜２０が好ましい。例えばフェニル基、ナフチル基等）を表わし、好ましくはメチル基、またはトリフルオロメチル基、特に好ましくはメチル基である。Ｒ^６は水素原子または炭素数１〜１０の置換基を表し、水素原子、または炭素数１〜５の置換基がより好ましく、水素原子、トリメチルシリル基及び炭素数１〜５のアルキル基が特に好ましい。Ｌ^３は２価の連結基を表し、−ＣＯＯ−、−ＣＯＳ−、または−ＣＯＮ（Ｒ^３）−の結合を有することがより好ましく、−ＣＯＯ−の結合を有することが更に好ましい。Ｒ^３は水素原子、または炭素数１〜８のアルキル基を表し、水素原子、または炭素数１〜４のアルキル基がより好ましく、水素原子、またはメチル基が更に好ましい。ｃは０または１を表す。ｄは１０〜１０００の整数を表し、２０〜５００の整数がより好ましく、５０〜２００の整数が特に好ましい。
The monomer containing the polysiloxane chain represented by the following general formula (3) will be described in detail.

In the general formula (3), R ¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. R ⁴ and R ⁵ are preferably an alkyl group (an alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, a hexyl group, etc.) or a haloalkyl group (a fluorinated alkyl group having 1 to 10 carbon atoms) Represents a trifluoromethyl group, a pentafluoroethyl group or the like) or an aryl group (preferably having 6 to 20 carbon atoms, such as a phenyl group or a naphthyl group), preferably a methyl group or a trifluoromethyl group, particularly preferably a methyl group. It is. R ⁶ represents a hydrogen atom or a substituent having 1 to 10 carbon atoms, more preferably a hydrogen atom or a substituent having 1 to 5 carbon atoms, particularly preferably a hydrogen atom, a trimethylsilyl group, or an alkyl group having 1 to 5 carbon atoms. . L ³ represents a divalent linking group, more preferably has a —COO—, —COS—, or —CON (R ³ ) — bond, and more preferably has a —COO— bond. R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group. c represents 0 or 1; d represents an integer of 10 to 1000, more preferably an integer of 20 to 500, and particularly preferably an integer of 50 to 200.

  The polymerization unit of the monomer containing the polysiloxane chain represented by the general formula (3) is preferably in the range of 0.001 to 20% by mass in the constituent components of the fluorine-containing copolymer, and more preferably is in the range of 0.001. 01 to 10% by mass.

Hereinafter , specific examples of the monomer containing a polysiloxane chain as the reference will be shown . Contact name in embodiments, Ph represents a phenyl group.

  The polysiloxane component other than the fluorine-containing copolymer preferably has a polyoxyalkylene chain in the molecule so as to be compatible with the low refractive index layer film. As polysiloxanes containing polyoxyalkylene chains, commercially available KF-351 to 355, 615, 618, 945, 6004, 6011, 6015 (above trade names, manufactured by Shin-Etsu Silicone Co., Ltd.) ), SH3746M, 3773- 1773M, 3775M (above trade names, manufactured by Toray Dow Corning Silicone Co., Ltd.), and the like.

  Further, the polysiloxane component preferably contains a crosslinking reactive group so that it can be immobilized on the low refractive index layer film, and has a group capable of forming a bond with the crosslinking reactive group of the fluorine-containing copolymer. It is more preferable from the viewpoint of durability.

  Commercially available polysiloxanes having crosslinking reactive groups include KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-164C, X-22- 5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above (Trade name, manufactured by Toa Gosei Co., Ltd.), Silaplane FM0725, Silaplane FM0721 (above, trade name, manufactured by Chisso Corporation), and the like, which are useful in the present invention.

  More preferably, the polysiloxane component has both a polyoxyalkylene chain and a crosslinking reactive group.

  The polysiloxane component is preferably used (added) in the low refractive index layer in a range of 0.1 to 10% by mass of the polysiloxane moiety, more preferably in the range of 0.5 to 7% by mass. Especially preferred is 1 to 5% by mass.

Although the specific example of polysiloxane components other than the fluorine-containing copolymer as a reference is shown below, this invention is not limited to these. In the following exemplary compounds, the suffix of each unit indicates the number of units.

Examples of the fluorine-containing copolymer as the reference include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane) and the like, and fluorine-containing monomer units ( For example, a fluorine-containing vinyl monomer, a ring-opening polymerizable monomer, etc.) and a crosslinkable group-containing monomer unit (for example, a vinyl monomer containing a radical polymerizable group, a cationic polymerizable group, a hydroxyl group, etc., a ring-opening polymerizable monomer), Examples thereof include a copolymer comprising an aliphatic monomer unit containing an oxyalkylene chain and a monomer unit containing a polysiloxane chain, preferably a fluorine-containing vinyl monomer unit, a crosslinkable vinyl monomer unit, or a polyoxyalkylene chain. Aliphatic monomer unit containing, and monomer unit containing polysiloxane chain It is Li Cheng copolymer. In addition, said polysiloxane component may be contained during fluorine-containing copolymerization, or components other than fluorine-containing copolymerization may be sufficient.

The fluorine-containing vinyl monomer may have fluorine at the position of the main chain or at the position of the side chain when polymerized, but it is preferable that the main chain has fluorine.
Examples of fluorine-containing vinyl monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (For example, Biscoat 6FM (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), M-2020 (trade name, manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, and the like can be mentioned. From the viewpoint of rate, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, it is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 40 to 55%. This is a case of mass%.

The copolymer as a reference is a radical polymerizable group (for example, (meth) acryloyl group, allyl group, vinyl group, vinyloxy group, etc.) or a cationic polymerizable group (for example, epoxy group, oxetanyl group, oxazolyl group) in the side chain. Etc.), more preferably a radical polymerizable group, and particularly preferably a (meth) acryloyl group.

  The method for introducing these polymerizable groups into the copolymer is not particularly limited, but contains two types of reactive groups having different reactivity, such as glycidyl (meth) acrylate and allyl (meth) acrylate. A method in which only one polymerizable group is polymerized by a radical polymerization method or an ionic polymerization method, or a method in which a polymerizable group-containing copolymer such as a hydroxyl group is synthesized in advance and then a polymerizable group is introduced by a polymer reaction Is mentioned.

  In particular, the following methods (1) to (6) are preferred as the method for introducing the (meth) acryloyl group into the copolymer. (1) After synthesizing a polymer having a nucleophilic group such as a hydroxyl group and an amino group, (meth) acrylic acid chloride, (meth) acrylic anhydride, (meth) acrylic acid and methanesulfonic acid mixed acid anhydride, etc. (2) A method in which (meth) acrylic acid is allowed to act on the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid. (3) A methacryloyloxypropyl isocyanate etc. in the polymer having the nucleophilic group (4) A method in which (meth) acrylic acid is allowed to act after synthesizing a polymer having an epoxy group, (5) A glycidyl methacrylate on a polymer having a carboxyl group A method of allowing a compound having both an epoxy group and a (meth) acryloyl group to act, (6) 3-chloro Method of performing dehydrochlorination after obtained by polymerizing a vinyl monomer having a propionic acid ester moiety. Among these, it is particularly preferable to introduce a (meth) acryloyl group by the method (1) or (2) for a polymer containing a hydroxyl group.

  Although it varies depending on the type of the fluorine-containing vinyl monomer polymerization unit, the polymerizable group-containing polymerization unit preferably accounts for 5 to 80% by mass and more preferably 10 to 75% by mass in the constituent components of the copolymer. It is particularly preferable to occupy 20 to 60% by mass.

In the copolymer as a reference , in addition to the fluorine-containing vinyl monomer polymerization unit and the polymerization unit having a radical or cation polymerizable group, adhesion to a substrate, polymer Tg (contributes to film hardness), solvent Other vinyl monomers may be appropriately copolymerized from various viewpoints such as solubility and transparency. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 75% by mass in the copolymer, and in the range of 0 to 40% by mass. More preferably, the range of 0 to 30% by mass is particularly preferable.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p -Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate) Vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tertbutylacrylamide, N- Cyclohexyl acrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

Fluorine-containing copolymer used in the present invention are those represented by the general formula (4) is preferably one represented by the Among these general formulas (5).

In the general formula (4), Z -L- (Y) _n -A or -L ¹ - represents a _{(CH 2 CH (X) O} ) n -A 1. R ¹ , L, Y, n, and A represent the same meaning as in general formula (1). L ¹ , X and A ¹ represent the same meaning as in general formula (2). L ² represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms. May have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred _{examples, - (CH 2) 2 -O} -, - (CH 2) 2 -NH -, - (CH 2) 4 -O -, - (CH 2) 6 -O -, - (CH 2) ₂ -O- (CH) ₂ -O-, -CONH- (CH ₂ ) ₃ -O-, -CH ₂ CH (OH) CH ₂ -O-, -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O -Etc. are mentioned. b represents 0 or 1;

  In the general formula (4), B represents a polymerization unit of an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid While the unsaturated carboxylic acid and derivatives thereof may be mentioned by way of example, preferably a vinyl ether derivatives and vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  s, t, u, v represent mass% of each constituent component, and values satisfying 20 ≦ s ≦ 60, 5 ≦ t ≦ 80, 0 ≦ u ≦ 75, 0.001 ≦ v ≦ 20, s + t + u + v = 100 Represents. Preferably, 25 ≦ s ≦ 55, 10 ≦ t ≦ 75, 0 ≦ u ≦ 40, 0.01 ≦ v ≦ 10, particularly preferably 40 ≦ s ≦ 55, 20 ≦ t ≦ 60, 0 ≦. This is the case when u ≦ 30 and 0.1 ≦ v ≦ 5.

Next, in the general formula (5), R ¹ and X represent the same meaning as in the general formula (2), Z, L ² , b and B represent the same meaning as in the general formula (4), and L ³ and R ⁴ , R ⁵ , R ⁶ , c, d represent the same meaning as in general formula (3).
“s”, “t”, “u”, “v”, and “w” represent mass% of each constituent component, and 20 ≦ s ≦ 60, 5 ≦ t ≦ 80, 0 ≦ u ≦ 75, 0.001 ≦ v ≦ 20, 0.001 ≦ The value satisfies w ≦ 20 and s + t + u + v + w = 100. Preferably, 25 ≦ s ≦ 55, 10 ≦ t ≦ 75, 0 ≦ u ≦ 40, 0.01 ≦ v ≦ 10, 0.01 ≦ w ≦ 10, particularly preferably 40 ≦ s ≦ 55, This is the case of 20 ≦ t ≦ 60, 0 ≦ u ≦ 30, 0.1 ≦ v ≦ 5, and 0.01 ≦ w ≦ 10.

  Preferred examples of the fluorine-containing copolymer useful in the present invention are shown below, but the present invention is not limited thereto. In addition, in the following exemplary compounds, the subscript of each unit shows the mass% of each structural component.

  The fluorine-containing copolymer is preferably used in the range of 50% to less than 100% of the total solid content of the low refractive index layer film, more preferably in the range of 70% by mass to less than 99%, and particularly preferably 80%. This is the case when the content is not less than 95% by mass.

  The copolymer used in the present invention can be synthesized by various polymerization methods such as solution polymerization, suspension polymerization, intelligent precipitation polymerization, bulk polymerization, emulsion polymerization and the like. Alternatively, after synthesizing a precursor such as a hydroxyl group-containing polymer by these methods, it can be synthesized by introducing a (meth) acryloyl group or the like by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to carry out the polymerization in the range of 50 to 100 ° C.

The reaction pressure can be selected as appropriate, but it is usually 1-100 kg / cm ² , particularly about 1-30 kg / cm ² . The reaction time is usually about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

  The composition for forming a low refractive index layer used in the present invention is usually in the form of a liquid, the fluorine-containing copolymer and the polysiloxane component as essential constituent components, and various additives and polymerization initiators as necessary. Is dissolved in a suitable solvent. At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

  Further, a small amount of a curing agent such as a polyfunctional (meth) acrylate compound, a polyfunctional epoxy compound, a polyisocyanate compound, an aminoplast, a polybasic acid or an anhydride thereof is added to the low refractive index layer in the antireflection film of the present invention. You can also. When adding these, it is preferable that it is the range of 0-30 mass% with respect to the total solid of a low refractive index layer membrane | film | coat, It is more preferable that it is the range of 0-20 mass%, 0-10 mass % Range is particularly preferred.

The polymerization initiator is appropriately selected according to the type of the curing reactive group.
For example, when the fluorine-containing copolymer has an unsaturated double bond (acryloyl group, methacryloyl group, etc.) capable of radical polymerization, it is preferable to add a radical polymerization initiator.

  The radical polymerization initiator may be in any form of generating radicals by the action of heat or generating radicals by the action of light.

As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p-nitrobenzenediazonium Etc.

  When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays.

  Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be preferably used in combination with these photoradical polymerization initiators.

  The amount of the compound that initiates radical polymerization by the action of heat or light may be any amount that can initiate the polymerization of the carbon-carbon double bond, but generally the total amount in the low refractive index layer forming composition is not limited. 0.1-15 mass% is preferable with respect to solid content, More preferably, it is 0.5-10 mass%, Most preferably, it is a case of 2-5 mass%.

  When the cross-linking reactive site of the polymer has a group capable of cationic polymerization (epoxy group, oxetanyl group, oxazolyl group, vinyloxy group, etc.), it is preferable to add a polymerization initiator that generates an acid catalyst by the action of light.

Various examples of compounds that generate an acid by the action of light are described in, for example, “Organic Materials for Imaging” p187-198, JP-A-10-282644, edited by the Society for Organic Electronics Materials (Bunshin Publishing). These known compounds can be used. Specifically, RSO ₃ ^- (R is an alkyl group, an aryl ^{_{group), AsF 6 -, SbF 6}} -, PF 6 -, BF 4 - diazonium salt and the counter ion or the like, ammonium salts, phosphonium salts, Various onium salts such as iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halides such as oxadiazole derivatives and S-triazine derivatives substituted with a trihalomethyl group, o-nitrobenzyl esters of organic acids, benzoin esters, Examples thereof include iminoesters and disulfone compounds, preferably onium salts, particularly preferably sulfonium salts and iodonium salts.

  A sensitizing dye can also be preferably used in combination with a compound that generates an acid by the action of light. In the present invention, the addition amount of the compound that accelerates the curing reaction by the action of light is preferably 0.1 to 15% by mass, more preferably 0.5%, based on the total solid content in the low refractive index layer forming composition. -10 mass%, particularly preferably 2-5 mass%.

  The solvent contained in the low refractive index layer coating liquid composition is not particularly limited as long as the composition containing the fluorine-containing copolymer is uniformly dissolved or dispersed without causing precipitation, and two or more kinds These solvents can also be used in combination. Preferred examples include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, isopropyl). Alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

  In addition, additives such as fine particles such as silica, various silane coupling agents or hydrolyzed partial condensates thereof, surfactants, thickeners, leveling agents, and the like are appropriately added to the low refractive index layer forming composition as necessary. May be.

The refractive index of the low refractive index layer is preferably 1.20 to 1.49, more preferably 1.20 to 1.45, and particularly preferably 1.20 to 1.44.
The thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 1 kg load.

[High / Medium Refractive Index Layer]
When the antireflection film of the present invention takes the form of a multilayer film, generally, the low refractive index layer has at least one layer having a higher refractive index than the low refractive index layer (that is, the high refractive index layer, the medium refractive index). Rate layer).

  As an organic material for forming a layer having a higher refractive index than the above low refractive index layer, a thermoplastic film (eg, polystyrene, polystyrene copolymer, polycarbonate, aromatic ring other than polystyrene, heterocyclic ring, alicyclic ring) A polymer having a group or a halogen group other than fluorine); a composition for forming a thermal film (eg, a composition for forming a film using a melamine film, a phenol film, or an epoxy film as a curing agent); urethane forming property Compositions (eg, combinations of alicyclic or aromatic isocyanates and polyols); and radical polymerizable compositions (modified films capable of radical curing by introducing double bonds into the above compounds (polymers, etc.)) Or a composition containing a prepolymer). A material having high film-forming properties is preferred. For the layer having a higher refractive index, inorganic fine particles dispersed in an organic material can also be used. As the organic material to be used above, those having a refractive index lower than that in the case where the organic fine particles are used alone because inorganic fine particles generally have a high refractive index can be used. As such materials, in addition to the above-mentioned organic materials, acrylic copolymers, vinyl copolymers, polyesters, alkyd coatings, fibrous polymers, urethane coatings, various curing agents that cure these, and curability Examples thereof include various organic materials that are transparent and stably disperse inorganic fine particles, such as a composition having a functional group.

Further organically substituted silicon-based compounds can be included therein. These silicon-based compounds are compounds represented by the following general formula or hydrolysis products thereof.
: R ^a _m R ^b _n SiZ _(4-m-n) (where R ^a and R ^b are each substituted with an alkyl group, an alkenyl group, an aryl group, or halogen, epoxy, amino, mercapto, methacryloyl or cyano. Z represents a hydrolyzable group selected from the group consisting of an alkoxyl group, an alkoxyalkoxyl group, a halogen atom and an acyloxy group, m + n is 1 or 2, and m and n are 0, 1 or 2 respectively)

  Preferable inorganic compounds of inorganic fine particles dispersed in these include oxides of metal elements such as aluminum, titanium, zirconium and antimony. These compounds are commercially available in particulate form, ie as a colloidal dispersion in powder or water and / or other solvents. These are further mixed and dispersed in the above organic material or organosilicon compound.

  As a material for forming a layer having a higher refractive index than the above, an inorganic material (eg, alkoxides of various elements, salts of organic acids, coordinating properties) that can be dispersed in a solvent with film-forming properties or are themselves liquid. And coordination compounds (eg, chelate compounds) and inorganic polymers bonded to the compound. Suitable examples of these include titanium tetraethoxide, titanium tetra-i-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-butoxide, titanium tetra-tert-butoxide, Aluminum triethoxide, aluminum tri-i-propoxide, aluminum tributoxide, antimony triethoxide, antimony riboxide, zirconium tetraethoxide, zirconium tetra-i-propoxide, zirconium tetra-n-propoxide, zirconium tetra- metal alcoholate compounds such as n-butoxide, zirconium tetra-sec-butoxide and zirconium tetra-tert-butoxide; diisopropoxytitanium bis (acetylacetonate), dibutoxy titani Um bis (acetylacetonate), diethoxytitanium bis (acetylacetonate), bis (acetylacetonezirconium), aluminum acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-propoxide monomethylacetoacetate and Examples include chelate compounds such as tri-n-butoxide zirconium monoethyl acetoacetate; and inorganic polymers mainly composed of carbon zirconyl ammonium or zirconium. In addition to those described above, various alkyl silicates or hydrolysates thereof, particularly particulate silica, particularly silica gel dispersed in a colloidal form can be used as a compound having a relatively low refractive index but can be used in combination with the above compound. .

  The refractive index of the high refractive index layer is generally 1.55 to 2.40. The refractive index can be obtained by measurement using an Abbe refractometer or estimation from the reflectance of light from the layer surface. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 0.5 μm. The haze of the high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The specific strength of the high refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70.
It is particularly preferable that inorganic fine particles and a polymer are used for the high refractive index layer, and the middle refractive index layer is formed by adjusting the refractive index to be lower than that of the high refractive index layer. The haze of the medium refractive index layer is preferably 3% or less.

[Other layers]
The antireflection film may further be provided with a hard coat layer, a moisture proof layer, an antistatic layer, an undercoat layer or a protective layer. The hard coat layer is provided for imparting scratch resistance to the transparent support. The hard coat layer also has a function of strengthening the adhesion between the transparent support and the layer thereon. The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer, or a silica compound. A pigment may be added to the hard coat layer. The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Two or more kinds of polymers may be used in combination. As the silica compound, colloidal silica is preferably used. The strength of the hard coat layer is preferably a pencil hardness of 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. An adhesive layer and a shield layer may be provided on the transparent support in addition to the hard coat layer. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Transparent support]
Except when the antireflection film is directly provided on the CRT image display surface or the lens surface, the antireflection film may be formed on a transparent support and used as an antireflection film. As the transparent support, a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose acylates (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). Phthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, , Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl Methacrylate and polyether ketone are included. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred. The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. The film thickness of the transparent support is preferably 50 to 200 μm.
About manufacturing a cellulose acylate film using a non-chlorinated solvent, it is described in detail in JIII Journal of Technical Disclosure No. 2001-1745, and the cellulose acylate film described therein is also preferably used in the present invention. it can.

An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass. As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. A surface treatment may be performed on the transparent support.

  Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

[Formation of antireflection film]
When the antireflection film has a single layer or a multi-layer structure as described above, each layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrinsic. It can be formed by coating by a rouge coating method (described in US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

Curing of each layer of the antireflection film of the present invention is performed by the action of ionizing radiation and / or heat. The irradiation with ionizing radiation is preferably performed using a high-pressure mercury lamp. At this time, it is preferable to perform the ultraviolet irradiation under an oxygen concentration of 0.5% or less, more preferably an oxygen concentration of 0.3% or less, particularly preferably 0.2% or less. Preferably the irradiation energy in the range of ^{300mJ / cm 2 ~1500mJ / cm 2} , more preferably in the range of ^{400mJ / cm 2 ~1000mJ / cm 2} , particularly preferably of 500mJ / cm ² ~800mJ / cm ² It is a range.

  In the case of heating, a temperature range of about 30 to 200 ° C is preferable, more preferably 80 to 180 ° C, and particularly preferably 100 to 150 ° C. The heating time is preferably in the range of 30 seconds to 100 hours, more preferably 1 minute to 1 hour, and particularly preferably 2 minutes to 15 minutes.

The ease of charging of the surface of the antireflection film of the present invention can be measured by a vertical peeling charging test. For the vertical peel charge test, the measurement sample is left in advance for 2 hours or more in an environment of measurement temperature and humidity. The measuring device is composed of a table on which a measurement sample is placed and a head that holds a counterpart film and repeats pressing and peeling on the measurement sample from above. An electrometer for measuring the amount of charge is connected to the head. Place the anti-reflection film to be measured on the table and attach polyethylene terephthalate to the head. After neutralizing the measurement part, repeatedly pressing and peeling the head to the measurement sample, reading the charge values at the first and fifth peeling, and the difference between the first and fifth peeling charge values. In the case of ± 100 pC (picocoulomb) / cm ² , the value of the fifth charge is defined as vertical peeling charge.

The antireflection film of the present invention preferably has a vertical peel charge of ± 200 pC / cm ^{2 or} less measured at room temperature and normal humidity (23 to 26 ° C., 50 to 70% RH) with respect to polyethylene terephthalate. More preferably, it is within ± 150 pC / cm ² , and further preferably within ± 100 pC / cm ² . The vertical peel charge value may be positively charged or negatively charged depending on the type of the counterpart film or measurement sample, but the problem is the magnitude of the absolute value. In general, the absolute value of charging becomes larger under low humidity. In the present invention, it is desirable that this value is small. In particular, when used in a display device that is easily charged, such as PDP and CRT, the vertical peeling charge is preferably within ± 100 pC / cm ² . In the present invention, it is also preferable to reduce the surface resistance value of the film provided with the antireflection layer in order to remove the generated charges. A preferable surface resistance value is 1 × 10 ¹² Ω / sq or less, more preferably 1 × 10 ¹⁰ Ω / sq or less, and further preferably 1 × 10 ⁸ Ω / sq or less. The surface resistance can be measured by a four probe method.

  The lower the reflectance of the antireflection film, the better. Specifically, the specular average reflectance in the wavelength region of 450 to 650 nm is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less. The haze of the antireflection film (when it has no anti-glare function described below) is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The strength of the antireflection film is preferably 1 H or higher, more preferably 2 H or higher, and most preferably 3 H or higher, with a pencil hardness of 1 kg. The antireflection film may have an antiglare function that scatters external light. The antiglare function is obtained by forming irregularities on the surface of the antireflection film. In a low refractive index layer using fine particles, irregularities can be formed on the surface of the antireflection film by the fine particles. When the antiglare function obtained by the fine particles is insufficient, relatively small particles (particle size: 50 nm to 200 nm in a small amount (0.1 to 0.1) are added to the low refractive index layer, the high refractive index layer, the middle refractive index layer or the hard coat layer. When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 30%, more preferably 5 to 20%, Most preferably, it is 20%.

  The antireflection film is applied to an image display device such as a polarizing plate or a display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). . The antireflection film is disposed so that the high refractive index layer is on the image display surface side of the image display device. When the antireflection film is provided on the transparent support and used as an antireflection film, the transparent support side is adhered to the image display surface of the image display device. Further, the antireflection film can be used for a case cover, an optical lens, a spectacle lens, a window shield, a light cover, and a helmet shield.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

<Synthesis example>
Synthesis of fluorinated copolymer (P-1) 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, Adekari Soap ER-30 (trade name, Asahi Denka Kogyo Co., Ltd.) Co.) 3.5 g and dilauroyl peroxide 0.55 g were charged, the inside of the system was deaerated and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of a fluorinated copolymer (P-1). The number average molecular weight of the obtained polymer was 31,000.

Synthesis of fluorinated copolymer (P-5) 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, Bremer AP-400 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) 3.5 g and 0.55 g of dilauroyl peroxide were charged, and 18 g of a fluorinated copolymer (P-5) was obtained in the same manner as P-1.

Synthesis of fluorine-containing copolymer (P-21) In an autoclave with a stainless steel stirrer having an internal volume of 100 ml, ethyl acetate 40 ml, hydroxyethyl vinyl ether 14.7 g, Adekari Soap ER-30 (trade name, Asahi Denka Kogyo Co., Ltd.) 3.5 g, Silaplane FM-0721 (trade name, manufactured by Chisso Co., Ltd.) 1.47 g and dilauroyl peroxide 0.55 g were charged, and a fluorine-containing copolymer ( 20 g of P-21) was obtained.

Fluorine-containing copolymers (P-2), (P-4), (P-6), (P-22), (P-24), (P-25), (P-26 ) in a similar manner It was synthesized.

[Example 1]
Mixing the components shown in the preparation Table 1 of the low refractive index layer coating solution, it was dissolved in methyl isobutyl ketone, and filtered through a pore size of 1μm polypropylene filter, a coating liquid Ln1～Ln1 7 for the low refractive index layer Prepared.
Ln 18 was prepared in the same manner as the coating solution for low refractive index layer described in Example 1 of JP-A No. 11-228631 (R-3 contains a polysiloxane component).

In the table, PE-600 represents a polyethylene oxide PE-600 (trade name) containing both terminal acryloyl groups manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and does not contain a polysiloxane component. X-22-164B and X-22-164C represent the polydimethylsiloxane containing both terminal methacryloyl groups manufactured by Shin-Etsu Silicone Co., Ltd.
IRG907 represents Irgacure 907 (trade name) manufactured by Ciba Geigy Co., Ltd. UVI6990 represents a cationic photopolymerization initiator UVI6990 (trade name) manufactured by Union Carbide Japan. The value in () represents the mass part of the solid content of each component.

Fluorine-containing copolymer (R-3) (Comparative Example)
A fluoropolymer A1 (R-3) described in JP-A No. 11-228631 was used.

Preparation of coating solution for first layer (hard coat layer) 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) and urethane acrylate oligomer (UV-6300B) 125 g (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was dissolved in 439 g of industrially modified ethanol. In the obtained solution, 7.5 g of photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba-Geigy) and photosensitizer (Kayacure-DETX (trade name), manufactured by Nippon Kayaku Co., Ltd.) 5 A solution of 0.0 g in 49 g of methyl ethyl ketone was added. After the mixture was stirred, it was filtered with a filter having a pore size of 1 μm to prepare a coating solution for a hard coat layer.

Preparation of titanium dioxide dispersion Titanium dioxide fine particles having a core / shell structure (TTO-55B (trade name), manufactured by Ishihara Sangyo Co., Ltd.), anionic diacrylate monomer (PM21 (trade name), Nippon Kayaku ( Co., Ltd.) 4.5 parts by weight, cationic methacrylate monomer (DMAEA (trade name), manufactured by Kojin Co., Ltd.) 0.3 parts by weight and methyl ethyl ketone 65.2 parts by weight are dispersed with a sand grinder, and titanium dioxide. A dispersion was prepared.

Preparation of coating solution for second layer (medium refractive index layer) 151.9 g of cyclohexanone and 37.0 g of methyl ethyl ketone, 0.14 g of photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba-Geigy) and photosensitization 0.04 g of an agent (Kayacure-DETX (trade name), manufactured by Nippon Kayaku Co., Ltd.) was dissolved. Further, 6.1 g of the above titanium dioxide dispersion and 2.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. Then, it filtered with the filter with a hole diameter of 1 micrometer, and prepared the coating liquid for middle refractive index layers.

Preparation of coating solution for third layer (high refractive index layer) 152.8 g of cyclohexanone and 37.2 g of methyl ethyl ketone, 0.06 g of photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba-Geigy) and photosensitization 0.02 g of an agent (Kayacure-DETX (trade name), manufactured by Nippon Kayaku Co., Ltd.) was dissolved. Further, 13.13 g of titanium dioxide dispersion and 0.76 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. Then, it filtered with the filter with a hole diameter of 1 micrometer, and prepared the coating liquid for high refractive index layers.

Preparation of antireflection film A 80 μm-thick triacetylcellulose film (TAC-TD80U (trade name), manufactured by Fuji Photo Film Co., Ltd.) is provided with a gelatin undercoat layer, and the above hard coat is formed on the gelatin undercoat layer. The layer coating solution was applied using a bar coater and dried at 120 ° C. Next, the coating layer was cured by irradiating ultraviolet rays with an energy of 500 mJ / cm ² under an oxygen concentration of 0.1% under a nitrogen atmosphere to form a hard coat layer having a thickness of 7.5 μm.

Subsequently, the coating solution for the medium refractive index layer was applied onto the hard coat layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays in a nitrogen atmosphere to cure the coating layer. A layer (refractive index: 1.60, thickness: 81 nm) was formed. Subsequently, the above high refractive index layer coating solution was applied onto the middle refractive index layer using a bar coater, dried at 120 ° C., and then adjusted to an oxygen concentration of 0.1% in a nitrogen atmosphere, and 500 mJ / cm ² . The coating layer was cured by irradiating ultraviolet rays with energy to form a high refractive index layer (refractive index: 1.92, thickness: 53 nm). Further, the coating solution for the low refractive index layer shown in Table 1 (the present invention Ln1 to Ln1 3 and comparative examples Ln1 4 to 1 7 ) was applied on the high refractive index layer so as to have a thickness of 85 nm using a bar coater. And an oxygen concentration of 0.
The antireflective films 1 to 17 were prepared by irradiating ultraviolet rays with an energy of 750 mJ / cm ² to form a low refractive index layer. With respect to the antireflection film 18 , a low refractive index layer was formed by the method described in Example 1 of JP-A-11-228631 to prepare the antireflection film 18 .

Preparation of saponification sample The following saponification treatment was performed on the above sample in order to impart the suitability to a polarizing plate.

A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 50 ° C. After antireflection film prepared (the present invention 1 to 1 3 and Comparative Examples 1 4-18) were respectively immersed for 2 minutes in an aqueous solution of sodium hydroxide above, dipped to thoroughly wash out the aqueous sodium hydroxide solution in water.
Next, after being immersed in a 0.01N dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Further the antireflection film was sufficiently dried at 100 ° C. was prepared saponified sample 1K~ 18 K. In the following examples, the letter K is marked on the saponification sample.

Evaluation of performance of coated film Antireflection film coated with the first to fourth layers thus obtained (Invention 1 to 1 3 , 1K to 1)
3 K, and Examples 1 4-18, for 1 to 4 K ~ 18 K) comparison was carried out following performance evaluation.
The obtained results are shown in Tables 2 and 3.

(1) Pencil Hardness Evaluation After the antireflection film was conditioned for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, the pencil hardness evaluation described in JIS K 5400 was performed.

(2) Scratch resistance test The film surface was rubbed 10 times under a load of 200 g using steel wool # 0000, and then the level of scratching was confirmed. The determination was in accordance with the following criteria.
Not scratched at all: ◎
Slightly scratched: ○
Fine scratches stand out: △
Scratch is remarkable: ×

(3) Refractive Index of Low Refractive Index Layer A cured film having a thickness of about 10 μm is prepared from a concentrated solution of the low refractive index layer composition, and the refractive index of the cured film is measured at an Abbe refractometer (Atago Co., Ltd.). Manufactured).

(4) Measurement of vertical peeling charge amount The antireflection film was allowed to stand at 25 ° C. and 55% RH for 2 hours, and then placed on a measurement stand of a vertical peeling charge amount measuring apparatus connected to an electrometer. After neutralizing the measurement part of the antireflection film, the crimping and peeling are repeated between the head equipped with polyethylene terephthalate and the antireflection film, and the difference in charge value between the first and fifth peeling is ± 100 pC / cm ^In the case of ² , the value of the fifth charge was taken as the peel charge amount value. The measurement was performed under conditions of 25 ° C. and 55% RH.

(5) Adherence to dust After the measurement film is applied to a glass plate and neutralized, it is rubbed back and forth 10 times using Toraysee (trade name, manufactured by Toray Industries, Inc.). Here, fine tissue paper powder was used as pseudo garbage, and the film was put up after being applied to the entire film, and evaluated as follows.
A: Almost all the pseudo dust falls. ○: The pseudo dust falls by 80% or more. Δ: The pseudo dust falls by 50% or more. X: The pseudo dust remains on the film surface by 50% or more.
This dust adhesion test was performed on samples immediately after sample preparation and with a roll after application of the sample, with the antireflection layer application surface and the opposite surface being in contact with each other for 2 weeks.

(6) Fingerprint adhesion evaluation After the antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, a fingerprint was attached to the sample surface, and then it was made into Ben Cotton (trade name, manufactured by Asahi Kasei Corporation). ) Was observed, and the fingerprint adhesion was evaluated as follows.
◎: Fingerprints can be easily wiped off ○: Fingerprints can be wiped off by wiping normally △: Fingerprints can be wiped off by rubbing firmly ×: Fingerprints remain without being wiped off

(7) Magic adhesion evaluation After the anti-reflection film was conditioned for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, magic (Macchi-Extra Fine (trade name; manufactured by ZEBRA)) was attached to the sample surface. Then, the state when the cloth was wiped with Ben Cotton (manufactured by Asahi Kasei Co., Ltd.) was observed, and the magic adhesion was evaluated as follows.
A: The magic can be easily wiped off. ○: The magic can be wiped off normally. Δ: The magic can be wiped off by rubbing firmly. X: The magic remains without being wiped off. Tables 2 and 3 show the obtained results.

As is apparent from this embodiment, the antireflection film 1 to 1 3 and 1K～1 3 K or without saponification treatment, very low surface reflectance in a wide wavelength region, sufficiently tough film strength of the present invention It has, and dust resistance (dust with), stain resistance (fingerprint wiping and resistance, wiping with magic) whereas also has excellent anti-reflection film 1 4 - Comparative example 18 and 1 4 K ~ It can be seen that 18 K cannot satisfy all of scratch resistance, dust resistance and antifouling properties.

[Creation of display device with anti-reflection film]
On the surface of the liquid crystal display of the personal computer PC9821NS / 340W obtained from NEC Corporation, the antireflection film (1K to 1 3 K) of the present invention prepared above and the antireflection film of the comparative example (1 4 K to 18 K) were obtained. A surface device sample was prepared by pasting. The display device provided with the antireflection film (1K to 1 3 K) of the present invention has almost no reflection of the surrounding scenery, has almost no dust, has a comfortable visibility, and has a sufficient surface strength. contrast there was the display device in which the film was installed in Comparative example (1 4 K~ 18 K) was found to be included around the reflection is easily attaches dust which can reduce.

It is a cross-sectional schematic diagram which shows the layer structure at the time of using the antireflection film of this invention as a composite film and an antireflection film, (a) shows a 4 layer structure, (b) shows the example of a 5 layer structure.

Explanation of symbols

1 Low Refractive Index Layer 2 High Refractive Index Layer 3 Hard Coat Layer 4 Transparent Support 5 Medium Refractive Index Layer

Claims (4)

An antireflection film comprising a fluorine-containing copolymer represented by the following general formula (4) .

[In General Formula (4), R ¹ represents a hydrogen atom, a halogen atom or a methyl group. Z is -L- _(Y) n -A or ^-L 1 _- represents a _{(CH 2 CH (X) O} ) n -A 1. L represents a divalent linking group not containing an aromatic group, n represents an integer of 2 to 1000, Y represents a polyoxyalkylene chain-containing unit not containing an aromatic group, and A represents an aromatic group Represents no substituent or hydrogen atom. L ¹ represents — (CH ₂ ) _m —O—CH ₂ —CHR ² —O—, —COO—, —COS— , or —CON (R ³ ) —, n represents an integer of 2 to 1000, X represents a hydrogen atom or a methyl group, and A ¹ represents a substituent or a hydrogen atom that does not contain an aromatic group. m represents an integer of 0 to 4, R ² represents a linear, branched, or cyclic alkyl group having 1 to 100 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. L ² represents a linking group having 1 to 10 carbon atoms, and b represents 0 or 1. B represents a polymerized unit of an arbitrary vinyl monomer. s, t, u, and v represent mass% of each constituent component, and satisfy 20 ≦ s ≦ 60, 5 ≦ t ≦ 80, 0 ≦ u ≦ 75, 0.001 ≦ v ≦ 20, and s + t + u + v = 100. Represents a value. ] The antireflection film according to claim 1, wherein the fluorine-containing copolymer is represented by the following general formula (5) .

[In General Formula (5), Z, X, L ² , B, b, and R ¹ represent the same meaning as in General Formula (4). R ⁴ and R ⁵ represent an alkyl group, a haloalkyl group or an aryl group. R ⁶ represents a hydrogen atom or a substituent having 1 to 10 carbon atoms. L ³ represents a divalent linking group, c represents 0 or 1, and d represents an integer of 10 to 1000. “s”, “t”, “u”, “v”, and “w” represent mass% of each constituent component, and 20 ≦ s ≦ 60, 5 ≦ t ≦ 80, 0 ≦ u ≦ 75, 0.001 ≦ v ≦ 20, 0.001. It represents a value satisfying ≦ w ≦ 20 and s + t + u + v + w = 100. ] An antireflection film comprising the antireflection film according to claim 1 or 2 on a transparent support. An image display device comprising the antireflection film according to claim 3 .

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