JP5154772B2 - Antireflection film - Google Patents

Description

  The present invention is an antireflection film. More specifically, it has near infrared absorption performance and antireflection performance, is excellent in scratch resistance and antistatic properties, has a simple layer structure and is low in cost, and is particularly suitable for a plasma display. The present invention relates to an antireflection film.

In an image display device such as a plasma display (PDP), a cathode ray tube (CRT), a liquid crystal display (LCD), etc., light is incident on the screen from the outside, and this light may be reflected to make it difficult to see the displayed image. In recent years, with the increase in the size of displays, it has become increasingly important to solve the above problems.
In order to solve such a problem, various antireflection treatments and antiglare treatments have been taken for various displays so far. As one of them, an antireflection film is used for various displays.
Conventionally, this antireflection film is formed by a method of thinning a low refractive index substance (MgF ₂ ) on a base film by a dry process method such as vapor deposition or sputtering, or a high refractive index substance [ITO (tin-doped Indium oxide), TiO _2, etc.] and a material having a low refractive index (MgF ₂ , SiO _2, etc.) are alternately stacked. However, the antireflection film produced by such a dry process method has a problem that the production cost is unavoidable.
Therefore, in recent years, an attempt has been made to produce an antireflection film by a wet process method, that is, coating. However, the antireflection film produced by the wet process method has a problem that the surface is inferior in scratch resistance as compared with the antireflection film by the dry process method.
Therefore, in order to solve the above problems in the wet process method, a cured layer (hard coat layer) is formed using an ionizing radiation curable resin composition. For example, on a base film, (1) a hard coat layer having a thickness of 2 to 20 μm containing a cured resin by ionizing radiation, a cured resin by ionizing radiation, and at least two kinds of metal oxides containing antimony-doped tin oxide, A high refractive index layer having a refractive index in the range of 1.65 to 1.80 and a thickness of 60 to 160 nm, and a siloxane-based polymer having a refractive index in the range of 1.37 to 1.47. Optical film formed by sequentially laminating low refractive index layers of 180 nm (see, for example, Patent Document 1), (2) hard coat having a thickness of 2 to 20 μm, including a metal oxide and a cured product by heat or ionizing radiation An optical film comprising a layer, and a low refractive index layer having a thickness of 40 to 200 nm and having a refractive index in the range of 1.30 to 1.45, including porous silica and a polysiloxane polymer (for example, , Patent Reference 2) is disclosed.
These optical films are antireflection films that effectively prevent reflection of light on the surface of the image display element and are excellent in scratch resistance.
By the way, the PDP is an apparatus that excites xenon gas molecules enclosed by plasma discharge between electrodes, excites a fluorescent substance with generated ultraviolet rays, emits light in the visible light region, and displays an image. In this PDP, since light emission uses plasma discharge, unnecessary electromagnetic waves having a frequency band of about 30 to 130 MHz leak to the outside, which adversely affects other devices (for example, information processing devices). It is required to suppress electromagnetic waves as much as possible.
Also, it is known that PDP emits near infrared rays. This near-infrared ray may affect peripheral electronic devices such as cordless phones and video decks that use a near-infrared remote control device, and may interfere with normal operation. It is required to block this near-infrared ray as much as possible. .
Furthermore, in the PDP, since the display surface is flat, when outside light is inserted, the light reflected in a wide range may enter the eyes at the same time, making the screen difficult to see, and it is necessary to prevent reflection of outside light. It is. It is also important to transmit the PDP light with a predetermined spectral transmittance to display a good screen and to correct the color tone of the light emission color.
In the PDP, in response to these requirements, a front plate having at least three functional films of (1) an electromagnetic wave shielding film, (2) a near infrared ray absorbing film, and (3) an antireflection film is generally provided on the display screen. Measures have been taken to arrange the antireflection film so as to be the outermost surface (observer side) (see, for example, Patent Document 3). In this case, at least three functional films must be prepared separately and bonded together, which is inevitable in cost.
On the other hand, in recent years, from the viewpoint of cost reduction, in the outermost antireflection film, a near-infrared absorbing layer is provided on the surface opposite to the antireflection layer of the base material, thereby reflecting with one film. Functional films that have both prevention performance and near infrared absorption performance have been developed. When manufacturing such a functional film, two methods of (1) formation of the near-infrared absorption layer on the back surface of the antireflection film and (2) formation of the antireflection layer on the back surface of the near-infrared absorption film However, in any case, film loss occurs, so the cost reduction effect is small.
On the other hand, the antireflection film is required to have antistatic performance with excellent sustainability in order to prevent adhesion of dust and the like.
JP 2002-341103 A JP 2003-139908 A Japanese Patent Laid-Open No. 11-12604

  Under such circumstances, the present invention has near-infrared absorption performance and antireflection performance, is excellent in scratch resistance and antistatic properties, and has a simple layer structure and low cost. The object of the present invention is to provide an antireflection film by a suitable wet process method.

［式（２）中のＲ^１は、炭素数４〜２０の炭化水素基を表し、ヘテロ原子を含んでも良く、Ｒ^２およびＲ^３は、それぞれ独立に水素原子または炭素数１〜１６の炭化水素基を表し、ヘテロ原子を含んでも良い。但し、窒素原子が２重結合を含む場合、Ｒ^３はない。
式（３）中のＲ^４は、炭素数２〜２０の炭化水素基を表し、ヘテロ原子を含んでも良く、Ｒ^５、Ｒ^６、およびＲ^７は、それぞれ独立に水素原子または炭素数１〜１６の炭化水素基を表し、ヘテロ原子を含んでも良い。
式（４）中のＲ^８は、炭素数２〜２０の炭化水素基を表し、ヘテロ原子を含んでも良く、Ｒ^９、Ｒ^１０、およびＲ^１１は、それぞれ独立に水素原子または炭素数１〜１６の炭化水素基を表し、ヘテロ原子を含んでも良い。
式（５）中のＥは、窒素、硫黄、又はリン原子を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４、およびＲ^１５は、それぞれ独立に炭素数１〜２０の炭化水素基を表し、ヘテロ原子を含んでも良い。但しＥが硫黄原子の場合、Ｒ^１５はない。］
で表されるカチオンである上記（１）又は（２）項に記載の反射防止フィルム、
（４）一般式（１）におけるＡ^ｂ−が、（ＣＦ_３ＳＯ_２）_２Ｎ⁻である上記（１）〜（３）項のいずれかに記載の反射防止フィルム、
（５）（Ａ）層及び／又は（Ｂ）層が、さらにイオン性液体と共に、反応性導電剤を含む上記（１）〜（４）項のいずれかに記載の反射防止フィルム、
（６）反応性導電剤が、分子内に、一般式（６）

［式中、Ｒ^１６及びＲ^１７は、それぞれ同一又は異なる炭素数１〜１０のアルキル基、Ｒ^１８は炭素数１〜１０のアルキル基又は炭素数７〜１０のアラルキル基、Ｒ^１９はラジカル重合性を有する官能基、Ｘ^ｐ−はｐ価の陰イオン、ｐは１〜４の整数を示す。］
で表される四級アンモニウム塩を有するラジカル重合性化合物である上記（５）項に記載の反射防止フィルム、
（７）（Ａ）層が、さらに有機及び／又は無機フィラーを含み、防眩機能が付与されてなる上記（１）〜（６）項のいずれかに記載の反射防止フィルム、
（８）（Ａ）層に含まれる近赤外線吸収剤が、酸化タングステン系化合物である上記（１）〜（７）項のいずれかに記載の反射防止フィルム、
（９）酸化タングステン系化合物が、セシウム含有酸化タングステンである上記（８）項に記載の反射防止フィルム、
（１０）（Ａ）層中の酸化タングステン系化合物の含有量が５〜５０質量％である上記（８）又は（９）項に記載の反射防止フィルム、
（１１）基材フィルムの他方の面に、厚さ５〜５０μｍの粘着剤層を有する上記（１）〜（１０）項のいずれかに記載の反射防止フィルム、及び
（１２）プラズマディスプレイ用である上記（１）〜（１１）項のいずれかに記載の反射防止フィルム、
を提供するものである。
As a result of intensive studies to develop an antireflection film having the above-mentioned preferable properties, the present inventors have conducted a hard coat layer containing a near infrared absorber on one surface of the base film and irradiation with active energy rays. Low-refractive index layers containing a cured resin are sequentially laminated with a predetermined thickness, respectively, and the hard coat layer and / or the low-refractive index layer contains an ionic liquid, and has a wavelength of 800 It has been found that an antireflection film whose spectral transmittance in the entire region of ˜1200 nm is less than a certain value can meet the purpose. The present invention has been completed based on such findings.
That is, the present invention
(1) On one surface of the substrate film, (A) a hard coat layer having a thickness of 2 to 20 μm containing a polyfunctional acrylate not containing fluorine or silicon and a near infrared absorber, and (B) porous silica 60 to An antireflection film comprising a low refractive index layer containing a polyfunctional acrylate containing 75 % by mass and containing no fluorine or silicon and having a refractive index of 1.43 or less and a thickness of 50 to 200 nm. The layer (A) and / or the layer (B) has the general formula (1)
(Z ^{a +} ) _m · (A ^b− ) _n (1)
[In the formula, Z ^{a +} represents a cation, A ^b− represents an anion, a, b, m and n are each an integer of 1 to 3, and satisfy the relationship of a × m = b × n. If Z a ⁺ there are multiple, ⁺ the plurality of Z ^a may be the same or different, if the A ^b-there are multiple, ^b-multiple A may be the same or different. ]
An antireflective film comprising an ionic liquid that is a molten salt that exhibits a liquid state at room temperature and having a spectral transmittance of 20% or less in the entire region of at least a wavelength of 800 to 1200 nm,
(2) The antireflection film as described in (1) above, wherein the surface resistivity is 5 × 10 ¹³ Ω / □ or less,
(3) Z ^{a +} in the general formula (1) is the general formula (2), (3), (4) or (5)

[R ¹ in Formula (2) represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and R ² and R ³ are each independently a hydrogen atom or a carbon atom having 1 to 16 carbon atoms. Represents a hydrogen group and may contain a heteroatom. However, when the nitrogen atom contains a double bond, there is no R ³ .
R ⁴ in the formula (3) represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom or 1 to Represents 16 hydrocarbon groups and may contain heteroatoms.
R ⁸ in the formula (4) represents a hydrocarbon group having 2 to 20 carbon atoms, and may include a hetero atom. R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom or a carbon number 1 to 1 Represents 16 hydrocarbon groups and may contain heteroatoms.
E in Formula (5) represents a nitrogen, sulfur, or phosphorus atom, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and a hetero atom May be included. However, if E is a sulfur ^{atom, R 15} is not. ]
The antireflection film according to (1) or (2), which is a cation represented by:
(4) Formula ^{A b-is} in _{(1), (CF 3 SO} 2) 2 N - is the above (1) to (3) anti-reflection film according to any one of items,
(5) The antireflection film according to any one of (1) to (4) above, wherein the (A) layer and / or the (B) layer further contains a reactive conductive agent together with the ionic liquid.
(6) The reactive conductive agent has a general formula (6) in the molecule.

[Wherein R ¹⁶ and R ¹⁷ are the same or different alkyl groups having 1 to 10 carbon atoms, R ¹⁸ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ¹⁹ is radical polymerization. Functional group, X ^p- represents a p-valent anion, and p represents an integer of 1 to 4. ]
The antireflective film according to (5) above, which is a radically polymerizable compound having a quaternary ammonium salt represented by:
(7) The antireflection film according to any one of (1) to (6) above, wherein the (A) layer further contains an organic and / or inorganic filler and is provided with an antiglare function,
(8) The anti-reflection film according to any one of (1) to (7) above, wherein the near infrared absorber contained in the (A) layer is a tungsten oxide compound.
(9) The antireflection film as described in (8) above, wherein the tungsten oxide compound is cesium-containing tungsten oxide,
(10) The antireflection film as described in (8) or (9) above, wherein the content of the tungsten oxide compound in the layer (A) is 5 to 50% by mass,
(11) The antireflection film according to any one of (1) to (10) above, which has a pressure-sensitive adhesive layer having a thickness of 5 to 50 μm on the other surface of the base film, and (12) for a plasma display. The antireflection film according to any one of (1) to (11) above,
Is to provide.

  According to the present invention, by adding an ionic liquid having high compatibility with the resin of the hard coat layer and / or the low refractive index layer to the hard coat layer and / or the low refractive index layer, the amount of the ionic liquid added Regardless of the amount, the antistatic property is exhibited without impairing the scratch resistance. As a result, it has a near infrared absorption performance and an antireflection performance, is excellent in scratch resistance and antistatic properties, and has a simple layer structure and a low cost. Can be provided.

The antireflective film of the present invention is a hard coat layer having a thickness of 2 to 20 μm (hereinafter referred to as “A”) containing a cured resin and near-infrared absorber by irradiation with active energy rays on one surface of a base film by a wet process method. , (A) layer), and (B) a low refractive index layer (hereinafter referred to as (B) layer) having a refractive index of 1.43 or less and a thickness of 50 to 200 nm, including a cured resin by irradiation with active energy rays. ) Are sequentially stacked.
There is no restriction | limiting in particular about the base film in the antireflection film of this invention, It can select suitably from well-known plastic films as a base material of a conventional antireflection film, and can use it. Examples of such plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, acetyl cellulose butyrate films, and polychlorinated. Vinyl film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide film , Polyimide film, fluororesin film, Li amide film, acrylic resin film, norbornene resin film, a cycloolefin resin film.

These base films may be either transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application.
The thickness of these substrate films is not particularly limited and is appropriately selected, but is usually 15 to 250 μm, preferably 30 to 200 μm. Moreover, this base film can be surface-treated by an oxidation method, a concavo-convex method, or the like on one side or both sides as desired for the purpose of improving adhesion to a layer provided on the surface. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and examples of the unevenness method include a sand blast method, a solvent, and the like. Treatment methods and the like. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, what gave the primer process to the single side | surface or both surfaces can also be used.

式（２）中のＲ¹は、炭素数４〜２０の炭化水素基を表し、ヘテロ原子を含んでも良く、Ｒ²およびＲ³は、それぞれ独立に水素原子または炭素数１〜１６の炭化水素基を表し、ヘテロ原子を含んでも良い。但し、窒素原子が２重結合を含む場合、Ｒ³はない。
式（３）中のＲ⁴は、炭素数２〜２０の炭化水素基を表し、ヘテロ原子を含んでも良く、Ｒ⁵、Ｒ⁶、およびＲ⁷は、それぞれ独立に水素原子または炭素数１〜１６の炭化水素基を表し、ヘテロ原子を含んでも良い。
式（４）中のＲ⁸は、炭素数２〜２０の炭化水素基を表し、ヘテロ原子を含んでも良く、Ｒ⁹、Ｒ¹⁰、およびＲ¹¹は、それぞれ独立に水素原子または炭素数１〜１６の炭化水素基を表し、ヘテロ原子を含んでも良い。 In the antireflection film of the present invention, an ionic liquid is contained in one or both of the (A) layer and the (B) layer sequentially provided on one surface of the base film, As a result, excellent antistatic performance is imparted.
In the present invention, the ionic liquid refers to a molten salt that exhibits a liquid state at room temperature (25 ° C.).
(Z ^{a +} ) _m · (A ^b− ) _n (1)
The compound represented by these is used.
In the general formula (1), Z ^{a +} represents a cation, A ^b− represents an anion, a, b, m, and n are each an integer of 1 to 3, and satisfy the relationship of a × m = b × n. . If Z a ⁺ there are multiple, ⁺ the plurality of Z ^a may be the same or different, if the A ^b-there are multiple, ^b-multiple A may be the same or different.
There is no restriction | limiting in particular as a cation represented by said Za ^<+> , Arbitrary things can be suitably selected from cations known as a cation of a conventional ionic liquid. Examples of the cation include cations represented by the following formulas (2) to (5).

R ¹ in formula (2) represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and R ² and R ³ are each independently a hydrogen atom or a hydrocarbon having 1 to 16 carbon atoms. Represents a group and may contain heteroatoms. However, when the nitrogen atom contains a double bond, there is no R ³ .
R ⁴ in formula (3) represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom or 1 to Represents 16 hydrocarbon groups and may contain heteroatoms.
R ⁸ in the formula (4) represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom or a C ¹ to C 1 carbon atom. Represents 16 hydrocarbon groups and may contain heteroatoms.

E in Formula (5) represents a nitrogen, sulfur, or phosphorus atom, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and a hetero atom May be included. However, when E is a sulfur atom, there is no R ¹⁵ .
Examples of the cation represented by the formula (2) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton. Specific examples include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3. -Methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1,2-dimethylindole cation, 1-ethylcarbazole cation and the like.
Examples of the cation represented by the formula (3) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation. Specific examples include 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl- 3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethyl Imidazolium cation, 1,3-dimethyl-1,4,5,6-teto Lahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyri Midinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl 1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2 1,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like.

Examples of the cation represented by the formula (4) include a pyrazolium cation and a pyrazolinium cation. Specific examples include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation and the like.
Examples of the cation represented by the formula (5) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and those in which a part of the alkyl group is substituted with an alkenyl group, an alkoxyl group, or an epoxy group. Is mentioned.
Specific examples include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrahexylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylhexylammonium cation, trimethyldecylammonium cation, N, N-diethyl- N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, N , N-dipropyl-N, N-dihexylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributyl Rufonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, triethylmethylphosphonium cation, tributylethyl Examples thereof include a phosphonium cation, a trimethyldecylphosphonium cation, and a diallyldimethylammonium cation.

［式中、Ｒ¹⁶及びＲ¹⁷は、それぞれ同一又は異なる炭素数１〜１０のアルキル基、Ｒ¹⁸は炭素数１〜１０のアルキル基又は炭素数７〜１０のアラルキル基、Ｒ¹⁹はラジカル重合性を有する官能基、Ｘ^p-はｐ価の陰イオン、ｐは１〜４の整数を示す。］
で表される四級アンモニウム塩を有するラジカル重合性化合物を好ましく挙げることができる。 On the other hand, in the general formula (1), the anion represented by A ^b- is not particularly limited as long as it can ionically bond with the cation to form an ionic liquid. For example, Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , F (HF) _n ⁻ , (CN) ₂ N ⁻ , C ₄ F ₉ SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , C ₃ F ₇ COO ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ^{− and the} like are used. Among these, an anion containing a fluorine atom is preferable because it gives an ionic compound having a low melting point, and (CF ₃ SO ₂ ) ₂ N ⁻ is particularly preferable.
Such an ionic liquid has high compatibility with the resin constituting the (A) layer and / or (B) layer, and when blended in the (A) layer and / or (B) layer, (A ) Layer and / or (B) layer without lowering the scratch resistance and exhibiting excellent antistatic properties.
In the present invention, the layer (A) and / or the layer (B) can contain a reactive conductive agent together with the ionic liquid. By using the ionic liquid and the reactive conductive agent in combination, a further excellent antistatic effect is exhibited by the synergistic effect.
This reactive conductive agent is irradiated with active energy rays at the time of forming the (A) layer or the (B) layer to cure the active energy ray polymerizable compound to form a cured resin. It is not particularly limited as long as it is copolymerized with the resin and incorporated into the cured resin, and any one of conventionally known reactive conductive agents can be appropriately selected and used.
Specifically, in the molecule, the general formula (6)

[Wherein R ¹⁶ and R ¹⁷ are the same or different alkyl groups having 1 to 10 carbon atoms, R ¹⁸ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ¹⁹ is radical polymerization. Functional group, X ^p- represents a p-valent anion, and p represents an integer of 1 to 4. ]
The radically polymerizable compound which has the quaternary ammonium salt represented by these can be mentioned preferably.

［式中、Ｒ²⁰は水素原子又はメチル基、Ｒ²¹はエチレン基又はトリメチレン基を示す。］
で表されるラジカル重合性四級アンモニウム塩系化合物などを挙げることができる。具体的には、アクリロキシエチルトリメチルアンモニウムクロライドなどを挙げることができる。
（Ａ）層及び／又は（Ｂ）層中の前記イオン性液体の含有量及び所望によりイオン性液体と併用される前記反応性導電剤の含有量は、用いるイオン性液体や反応性導電剤の種類により異なるが、本発明の反射防止フィルムの表面抵抗率が、通常５×１０¹³Ω／□以下になるように選定される。（Ａ）層及び（Ｂ）層に使用した全成分中におけるイオン性液体の全含有量は、通常２〜２０質量％、好ましくは３〜１５質量％、より好ましくは５〜１２質量％である。一方、反応性導電剤の全含有量は、（Ａ）層及び（Ｂ）層の合計量に基づき、通常０〜２０質量％、好ましくは２〜１５質量％、より好ましくは４〜１２質量％である。 In the general formula (6), the alkyl group represented by R ¹⁶ and R ¹⁷ and the alkyl group of R ¹⁸ are preferably an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms, The aralkyl group in R ¹⁸ is preferably a benzyl group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
R ¹⁹ is not particularly limited as long as it is a functional group having radical polymerizability, and examples of the functional group include a (meth) acryloyl group and a vinyl group.
On the other hand, X ^p− may be either an inorganic anion or an organic anion. Examples thereof include halogen ions of F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ and BF _{4. ^{-, CO 3 2-, SO 4}} 2- , etc. of the inorganic ^{_{anion, CH 3 OSO 3 -, C}} 2 H 5 OSO 3 -, more acetic acid, malonic acid, succinic acid, maleic acid, fumaric acid, p- toluene Examples include organic anions composed of residues of organic acids such as sulfonic acid and trifluoroacetic acid.
As such a reactive conductive agent, for example, the general formula (6-a)

[Wherein, R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ represents an ethylene group or a trimethylene group. ]
And a radically polymerizable quaternary ammonium salt compound represented by the formula: Specific examples include acryloxyethyl trimethyl ammonium chloride.
The content of the ionic liquid in the layer (A) and / or the layer (B) and the content of the reactive conductive agent used in combination with the ionic liquid as desired are the ionic liquid and reactive conductive agent used. Although it depends on the type, the surface resistivity of the antireflection film of the present invention is usually selected to be 5 × 10 ¹³ Ω / □ or less. The total content of the ionic liquid in all components used in the (A) layer and the (B) layer is usually 2 to 20% by mass, preferably 3 to 15% by mass, and more preferably 5 to 12% by mass. . On the other hand, the total content of the reactive conductive agent is usually 0 to 20% by mass, preferably 2 to 15% by mass, more preferably 4 to 12% by mass based on the total amount of the (A) layer and the (B) layer. It is.

In the antireflection film of the present invention, a hard coat layer having a thickness of 2 to 20 μm is first provided on at least one surface of the substrate film, which includes (A) a cured resin by irradiation with active energy rays and a near infrared absorber. It is done.
The (A) layer containing the curable resin and the near-infrared absorber by this active energy ray irradiation is, for example, an active energy ray-curable compound, the near-infrared absorber, and the ionic liquid or the ionic liquid. A coating film is formed by coating one side of the base film with a coating liquid for layer (A) containing the above-mentioned reactive conductive agent and optionally containing a photopolymerization initiator, etc. It can be formed by irradiating a line to cure the coating film.
Here, the active energy ray-curable compound refers to a compound having energy quanta in an electromagnetic wave or a charged particle beam, that is, a compound that is crosslinked and cured by irradiation with ultraviolet rays or electron beams.
Examples of such active energy ray-curable compounds include radical polymerization type and cationic polymerization type. The radical polymerization type of the active energy ray-curable compound includes an energy ray polymerizable prepolymer and an energy ray polymerizable monomer. Examples of the radical polymerization type active energy ray polymerizable prepolymer include polyester acrylate and epoxy acrylate. , Urethane acrylate and polyol acrylate. Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid.

The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. The urethane acrylate-based prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Furthermore, the polyol acrylate-based prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. One of these radical polymerization type active energy ray polymerizable prepolymers may be used, or two or more thereof may be used in combination.
Examples of radical polymerization type active energy ray polymerizable monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene. Glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, Di (meth) acrylate modified with ethylene oxide, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate Propionate modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol Examples thereof include polyfunctional acrylates such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These radical polymerization type active energy ray polymerizable monomers may be used singly or in combination of two or more, and may be used in combination with radical polymerization type active energy ray polymerizable prepolymers. Good.
On the other hand, as a cationic polymerization type active energy ray polymerizable prepolymer, an epoxy resin is usually used. Examples of the epoxy resins include compounds obtained by epoxidizing polyphenols such as bisphenol resins and novolak resins with epichlorohydrin, etc., and compounds obtained by oxidizing a linear olefin compound or a cyclic olefin compound with a peroxide or the like. Etc.

  As photopolymerization initiators used as desired, for radical polymerization type active energy ray polymerizable prepolymers and active energy ray polymerizable monomers, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -N-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 Roxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2- Examples include methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like. Examples of the photopolymerization initiator for the cationic polymerization type active energy ray polymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions and aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, Examples thereof include compounds composed of anions such as hexafluoroantimonate and hexafluoroarsenate. These may be used alone or in combination of two or more thereof, and the blending amount thereof is based on 100 parts by mass of the active energy ray polymerizable prepolymer and / or the active energy ray polymerizable monomer. In general, it is selected in the range of 0.2 to 10 parts by mass.

On the other hand, the near-infrared absorber to be contained in the layer (A) is not particularly limited as long as it can provide an antireflection film having a spectral transmittance of 30% or less in at least a wavelength range of 800 to 1200 nm. Instead, various types can be appropriately selected and used.
The near infrared absorber can be broadly classified into an organic near infrared absorber and an inorganic near infrared absorber. Here, examples of the organic near-infrared absorber include cyanine compounds, squarylium compounds, thiol nickel complex compounds, naphthalocyanine compounds, phthalocyanine compounds, triallylmethane compounds, naphthoquinone compounds, anthraquinone compounds, Furthermore, N, N, N ′, N′-tetrakis (p-di-n-butylaminophenyl) -p-phenylenediaminium perchlorate, phenylenediaminium chloride, phenylenedianium hexafluoroantimony Amino compounds such as acid salts, fluorinated boronates of phenylene diaminium, fluorine salts of phenylene diaminium, perchlorates of phenylene diaminium, copper compounds and bisthiourea compounds, phosphorus compounds and copper compounds, phosphate ester compounds Obtained by reaction of copper with copper compounds Examples include phosphate ester copper compounds.
Among these, a thiol nickel complex salt compound (JP-A-9-230134, etc.) and a phthalocyanine compound are preferable. In particular, a fluorine-containing phthalocyanine compound disclosed in JP-A-2000-26748 is an organic compound. Among near-infrared absorbers, it is preferable because it has a high visible light spectral transmittance and excellent properties such as heat resistance, light resistance, and weather resistance.

Examples of inorganic near infrared absorbers include tungsten oxide compounds, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, zinc oxide, indium oxide, tin-doped indium oxide (ITO), tin oxide, and antimony-doped oxide. Tin (ATO), cesium oxide, zinc sulfide, LaB ₆ , CeB ₆ , PrB ₆ , NdB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , HoB ₆ , YB ₆ , SmB ₆ , EuB ₆ , ErB ₆ , TmB ₆ , hexaboride such as YbB ₆ , LuB ₆ , SrB ₆ , CaB ₆ , (La, Ce) B ₆ and the like. Of these, tungsten oxide compounds are preferred because they have a high near-infrared absorptivity and a high visible light spectral transmittance.
Cs _0.2-0.4 WO ₃ (7)
The cesium containing tungsten oxide represented by these is suitable.
In general, when comparing organic near-infrared absorbers with inorganic near-infrared absorbers, the near-infrared absorption capacity is superior to organic ones, but inorganic ones are far superior in terms of light resistance and weather resistance. Is excellent. In addition, organic materials have a drawback that they are easily colored, and from the viewpoint of practicality, inorganic near infrared absorbers are preferred, and the use of cesium-containing tungsten oxide is particularly preferred. In order to form a transparent coat layer with a small absorption in the visible light region, this inorganic infrared absorber preferably has a particle size of preferably 0.5 μm or less, more preferably 0.1 μm or less. is there.
In the present invention, one kind of inorganic near infrared absorber may be used, or two or more kinds may be used in combination, and an inorganic near infrared absorber and an organic near infrared absorber are used in combination. You can also.
In addition, when the near infrared absorber is used alone, even if there is a portion where the spectral transmittance exceeds 30% in the wavelength range of 800 to 1200 nm, the total wavelength of 800 to 1200 nm can be obtained by using two or more types in combination. The spectral transmittance in the region may be 30% or less.
The amount of the near infrared absorber used depends on the film thickness of the layer (A), but when a tungsten oxide compound, for example, a cesium-containing tungsten oxide represented by the formula (7) is used, The content thereof is usually 5 to 50% by mass, preferably 10 to 40% by mass.

In the present invention, the layer (A) can contain an organic and / or inorganic filler as an antiglare property-imparting agent. Examples of the organic filler include melamine resin particles, acrylic resin particles, acrylic-styrene copolymer particles, polycarbonate particles, polyethylene particles, polystyrene particles, and benzoguanamine resin particles. These organic fillers usually have an average particle size of about 2 to 10 μm.
Examples of the inorganic filler include silica particles and aggregates of amine particles of colloidal silica particles having an average particle diameter of about 0.5 to 10 μm.
These antiglare imparting agents may be used alone or in combination of two or more, and the content thereof in the layer (A) is usually 2 to 15% by mass, preferably 3 to 8% by mass. When the antiglare imparting agent is contained in the layer (A), the 60 ° gloss value of the antireflection film of the present invention is usually about 30 to 120.
The coating liquid for layer (A) used in the present invention, if necessary, in an appropriate solvent, the active energy ray-curable compound, the near infrared absorber, the ionic liquid or the ionic liquid described above. In addition to the liquid and the above-mentioned reactive conductive agent, the above-mentioned photopolymerization initiator, anti-glare agent, and various additives used as desired, for example, antioxidants, ultraviolet absorbers, light stabilizers, It can be prepared by adding a leveling agent, an antifoaming agent and the like at a predetermined ratio and dissolving or dispersing them.
Examples of the solvent used in this case include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Examples include alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, and isophorone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.

The concentration and viscosity of the coating solution thus prepared are not particularly limited as long as the concentration and viscosity can be coated, and can be appropriately selected depending on the situation.
Next, the coating liquid is applied to one surface of the base film using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. By coating, a coating film is formed, and after drying, the coating film is cured by irradiating the active energy ray to form the layer (A).
Examples of the active energy rays include ultraviolet rays and electron beams. The ultraviolet rays can be obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like. On the other hand, the electron beam is obtained by an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. In addition, when using an electron beam, a cured film can be obtained, without adding a photoinitiator.
In the present invention, the thickness of the layer (A) is in the range of 2 to 20 μm. If the thickness is less than 2 μm, the resulting antireflection film may not exhibit sufficient scratch resistance, and if it exceeds 20 μm, cracks may occur in the hard coat layer. (A) The preferable thickness of a layer is the range of 3-15 micrometers, and the range of 5-10 micrometers is especially suitable.
In the antireflection film of the present invention, the refractive index of the layer (A) is usually 1.47 to 1.60, preferably 1.49 to 1.55.

In the antireflection film of the present invention, on the (A) layer, (B) a low refractive index layer having a thickness of 50 to 200 nm having a refractive index of 1.43 or less containing a cured resin by active energy ray irradiation is provided.
The layer (B) is formed on the layer containing, for example, the active energy ray-curable compound, preferably porous silica particles, the ionic liquid or the ionic liquid and the reactive conductive agent, as desired. Formed by coating the (B) layer coating solution containing a photopolymerization initiator on the (A) layer to form a coating film, irradiating active energy rays and curing the coating film. can do.
About the kind and compounding quantity of the said active energy ray hardening compound and the photoinitiator used depending on necessity, it can select from what was shown in description of (A) layer.
As the porous silica particles contained in the layer (B), those having a specific gravity of 1.7 to 1.9, a refractive index of 1.25 to 1.36 and an average particle size of 20 to 100 nm are preferably used. It is done. By using porous silica particles having such properties, an antireflection film having a single layer type antireflection layer having excellent antireflection performance can be obtained.
In the present invention, the content of the porous silica particles in the layer (B) is preferably selected in the range of 30 to 80% by mass. If content of this porous silica particle exists in the said range, a (B) layer will become a layer which has a desired low refractive index, and the obtained antireflection film will be excellent in antireflection property. The preferable content of the porous silica particles is 50 to 80% by mass, and particularly preferably 60 to 75% by mass.
The (B) layer has a thickness of 50 to 200 nm and a refractive index in the range of 1.43 or less. If the thickness and refractive index of the (B) layer are in the above ranges, an antireflection film excellent in antireflection performance and scratch resistance can be obtained. The thickness of the (B) layer is preferably 70 to 130 nm, and the refractive index is preferably 1.30 to 1.42, more preferably 1.35 to 1.40.

The coating liquid for layer (B) used in the present invention, if necessary, in an appropriate solvent, the active energy ray-curable compound, preferably porous silica particles, the ionic liquid or the above-mentioned ionic liquid. In addition to the ionic liquid and the above-mentioned reactive conductive agent, the above-mentioned photopolymerization initiator used as desired, and various additives such as antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, quenching agents, etc. It can be prepared by adding a foaming agent or the like at a predetermined ratio and dissolving or dispersing them.
About the solvent used in this case, it can select from what was shown in description of (A) layer.
The concentration and viscosity of the coating solution thus prepared are not particularly limited as long as the concentration and viscosity can be coated, and can be appropriately selected depending on the situation.
(A) This coating liquid is coated on the layer using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. A film is formed, dried, and then irradiated with active energy rays to cure the coating film, thereby forming the layer (B).
About an active energy ray, it can select from what was shown in description of (A) layer.
In the present invention, the formation of the (A) layer and the (B) layer is advantageously performed by the following method.
First, the coating liquid for (A) layer is formed on one surface of the substrate film to form a coating film, and then irradiated with active energy rays to be cured in a half-cured state. In this case, when irradiating with ultraviolet rays, the amount of light is usually about 50 to 150 mJ / cm ² . Next, a coating film is formed by coating the coating liquid for layer (B) on the half-cured cured layer formed in this way, and the active energy ray is sufficiently irradiated to form the half-cured state. Completely cured with cured layer. Under the present circumstances, when irradiating an ultraviolet-ray, a light quantity is about 400-1000mJ / cm < ² > normally. When the (A) layer and / or the (B) layer are completely cured, active energy rays can be irradiated in an atmosphere such as nitrogen gas in order to prevent curing inhibition by oxygen. In this case, the oxygen concentration is preferably low and is preferably 2% by volume or less.
On the base film, the (A) layer is half-cured, the (B) layer is applied, and finally the (A) layer and the (B) layer are completely cured, whereby the (A) layer and the (B ) The adhesion of the layer can be increased.
In the antireflection film of the present invention thus produced, it is necessary that the spectral transmittance in the entire region of at least a wavelength of 800 to 1200 nm is 30% or less. If the spectral transmittance is 30% or less, when the antireflection film of the present invention is used for the front plate of the PDP, peripheral electronic devices using near infrared rays generated from the PDP (for example, cordless phones, near infrared remote control devices) Malfunctions of video decks that use). The spectral transmittance is preferably 20% or less.
The reflectance at a wavelength of 500 to 700 nm is usually 3% or less, and the total light transmittance is usually 40% or more, preferably 50% or more. Further, the haze value is usually less than 3%, and is about 3 to 30% when the antiglare imparting agent is contained in the layer (A).

In the antireflection film of the present invention, the surface resistivity is usually 5 × 10 ¹³ Ω / □ or less. If this surface resistivity is 5 × 10 ¹³ Ω / □ or less, good antistatic performance is exhibited. A preferable surface resistivity is 2 × 10 ¹³ Ω / □ or less, and a more preferable surface resistivity is 8 × 10 ¹² Ω / □ or less. The lower limit of the surface resistivity is not particularly limited, but is usually about 2 × 10 ¹⁰ Ω / □.
In the antireflection film of the present invention, an antifouling coating layer can be provided on the (B) layer. This antifouling coating layer is generally obtained by applying a coating solution containing a fluororesin using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. (B) It can form by coating on a layer, forming a coating film, and drying-processing.
The thickness of the antifouling coating layer is usually in the range of 1 to 10 nm, preferably 3 to 8 nm. By providing the antifouling coating layer, the resulting antireflection film has improved surface slipperiness and is less likely to become dirty.
In this way, an antireflection film having both near-infrared absorption performance and antireflection performance, excellent scratch resistance and antistatic properties, and a simple layer structure and low cost can be obtained. This antireflection film is particularly suitably used for the front plate of a PDP.

In the antireflection film of this invention, the adhesive layer for making it adhere to the to-be-adhered body in a front plate can be formed in the surface on the opposite side to the hard-coat layer of a base film. As an adhesive which comprises this adhesive layer, the thing for optical uses, for example, an acrylic adhesive, a urethane type adhesive, and a silicone type adhesive, are used preferably. The thickness of this pressure-sensitive adhesive layer is usually in the range of 5 to 50 μm. When the antireflection film of the present invention is used as an antireflection film for PDP, this pressure-sensitive adhesive layer can contain a dye or a pigment in order to correct the color tone of the display device.
Furthermore, a release film can be provided on this pressure-sensitive adhesive layer. Examples of the release film include paper such as glassine paper, coated paper, and laminate paper, and various plastic films coated with a release agent such as silicone resin. Although there is no restriction | limiting in particular about the thickness of this peeling film, Usually, it is about 20-150 micrometers.
The antireflection film of the present invention produced in this way has both near-infrared absorption performance and antireflection performance, is excellent in scratch resistance and antistatic properties, and has a simple layer structure and low cost. have. This antireflection film is suitably used for the front plate of PDP, particularly as an antireflection film for PDP.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the physical property of the antireflection film obtained in each example was measured according to the method shown below.
(1) Reflectance at wavelengths of 500 nm, 600 nm, and 700 nm The reflectance at wavelengths of 500 nm, 600 nm, and 700 nm was measured with a spectrophotometer [manufactured by Shimadzu Corporation “UV-3101PC”].
(2) Spectral transmittance at a wavelength of 800 to 1200 nm Using a spectrophotometer [“UV-3101PC” manufactured by Shimadzu Corporation], the spectral transmittance at a wavelength of 800 nm to 1200 nm was measured, and the wavelengths of 800 nm, 850 nm, 900 nm, 1000 nm, The measured values at 1100 nm and 1200 nm were obtained.
(3) Total light transmittance and haze value A haze meter “NDH 2000” manufactured by Nippon Denshoku Industries Co., Ltd. was used and measured according to JIS K 6714.
(4) 60 ° gloss value A gloss meter “VG 2000” manufactured by Nippon Denshoku Industries Co., Ltd. was used and measured according to JIS K 7105.
(5) Scratch resistance Steel wool # 0000 was used, and after rubbed 5 times with a load of 9.8 × 10 ⁻³ N / mm ² , visual observation was performed, and evaluation was performed according to the following criteria.
○: Not scratched.
×: Scratched.
(6) Refractive index Measured with an Abbe refractometer [manufactured by Atago Co., Ltd., product name “Abbe refractometer 4T”, Na light source, wavelength: about 590 nm].
(7) Thickness of each layer It measured using "Filmetrics F-20" by Matsushita Intertechno.
(8) Surface resistivity After the sample was conditioned for 24 hours under the conditions of 23 ° C. and 50% humidity, the surface resistivity of the surface layer was measured with “High Lester” manufactured by Mitsubishi Chemical Corporation at an applied voltage of 100V.

Example 1
(1) Preparation of coating liquid for (A) layer Tris (acryloxyethyl) isocyanurate [trade name “Aronix M-315” manufactured by Toagosei Co., Ltd., solid concentration 100%] as an active energy ray-curable compound 40 parts by mass and pentaerythritol triacrylate [manufactured by Toagosei Chemical Co., Ltd., trade name “Aronix M-305”, solid concentration 100%] and polyethylene glycol diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK ester” A photopolymerization initiator (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) was added to a mixture consisting of 30 parts by mass of “A-400”, solid content concentration 100%]. [Product name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.] 2 parts by mass were added, and then a near infrared absorber [Sumitomo Metal Mining ( ), Trade name “YMF-01”, cesium-containing tungsten oxide having an average particle diameter of 23 nm (molar ratio Cs: W: O = 0.33: 1: 3) content 10 mass% suspension, total solid content Concentration 14% by mass] 270 parts by mass and ionic liquid [manufactured by Guangei Chemical Co., Ltd., trade name “IL-A5” (cation species: [Chemical Formula 1] (5), anion species: (CF ₃ SO ₂ ) ₂ N ⁻ ), Solid content concentration of 100% by mass] After mixing 10 parts by mass, dilute with methyl isobutyl ketone (MIBK) so that the total solid content concentration becomes 30% by mass. Prepared.
(2) Preparation of (B) layer coating liquid Multifunctional acrylate mixture (polyurethane acrylate) [Arakawa Chemical Co., Ltd., trade name “Beamset 577CB”, solid content concentration 100%] 5 parts by mass of an initiator [trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.] was added, and then a methyl isobutyl ketone (MIBK) dispersion of porous silica particles [manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name] “ELCOM RT-1002SIV”, solid content concentration 21% by mass, porous silica particles: specific gravity 1.8, refractive index 1.30, average particle size 60 nm] After mixing 1200 parts by mass, the total solid content concentration is 2 It diluted with MIBK so that it might become a mass%, and prepared the coating liquid for (B) layers.
(3) Production of antireflection film Obtained on (1) above on the surface of a 100 μm thick double-sided easy-adhesion-treated polyethylene terephthalate (PET) film [trade name “A4300” manufactured by Toyobo Co., Ltd.] as a base film. (A) The Meyer bar No. was adjusted so that the thickness of the coating solution for layer after curing was 6 μm. 16 was applied. Next, after drying at 90 ° C. for 1 minute, ultraviolet rays were irradiated at a light amount of 100 mJ / cm ² to be cured in a half-cured state.
Next, on the half-cured coat surface, the Meyer bar No. 1 was applied so that the thickness after curing of the coating solution for layer (B) obtained in (2) was 100 nm. 4 was applied. Next, after drying at 80 ° C. for 1 minute, ultraviolet rays were irradiated at a light amount of 500 mJ / cm ² in a nitrogen gas atmosphere (oxygen concentration 0.5% by volume) to completely cure, and a refractive index of 1. An antireflection film was prepared by sequentially forming a 54 near-infrared absorbing hard coat layer and a low refractive index layer having a refractive index of 1.38.
Table 1 shows the physical properties of the antireflection film thus prepared. The spectral transmittance of this antireflection film in the entire range of wavelengths from 800 to 1200 nm was 30% or less.
Example 2
In the preparation of the coating liquid for (B) layer in Example 1 (2), the coating for (B) layer was performed in the same manner as in Example 1 except that 10 parts by mass of the same ionic liquid as in Example 1 was added. A liquid was prepared, and an antireflection film was further produced. That is, in this example, the ionic liquid was added to both the (A) layer and the (B) layer. Table 1 shows the physical properties of this antireflection film.
Example 3
In the preparation of the coating solution for the layer (A) in Example 1 (1), except that 5 parts by mass of silica gel [manufactured by Tosoh Silica Co., Ltd., trade name “Nip Seal E-200”, average particle size 3 μm] was added, A coating solution for layer (A) was prepared in the same manner as in Example 1, and an antireflection film was produced. Table 1 shows the physical properties of this antireflection film.
Example 4
In the preparation of the coating solution for the layer (A) in Example 1 (1), the ionic liquid was changed to a product name “IL-C3” (cation type: [Chemical Formula 1] (2), anion manufactured by Guangei Chemical Co., Ltd.] Except for changing to Species: (CF ₃ SO ₂ ) ₂ N ⁻ )], a coating solution for layer (A) was prepared in the same manner as in Example 1, and an antireflection film was further produced. Table 1 shows the physical properties of this antireflection film.
Example 5
An antireflection film was produced in the same manner as in Example 1 except that the preparation of the coating solution for layer (A) in Example 1 (1) was changed as follows. Table 1 shows the physical properties of this antireflection film.
<(A) Preparation of coating liquid for layer>
40 parts by mass of tris (acryloxyethyl) isocyanurate [trade name “Aronix M-315”, solid content concentration 100%] manufactured by Toagosei Co., Ltd.) and pentaerythritol triacrylate [Toagosei Co., Ltd.] Product name “Aronix M-305”, solid content concentration 100%] 30 parts by mass and polyethylene glycol diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., product name “NK Ester A-400”, solid content concentration 100%] 30 mass 2 parts by weight of a photopolymerization initiator [manufactured by Ciba Specialty Chemicals, trade name “Irgacure 907”] is added to the mixture consisting of parts, and then a near infrared absorber [manufactured by Sumitomo Metal Mining Co., Ltd., trade name] “YMF-04”, cesium-containing tungsten oxide having an average particle diameter of 23 nm (Cs: W: O = 0.33 by molar ratio: : 3) Content 17.5% by mass suspension, total solid concentration 28% by mass] 160 parts by mass and ionic liquid [manufactured by Guangei Chemical Co., Ltd., trade name “IL-A5”, solid content concentration 100% by mass] After mixing 10 parts by mass and further adding 12 parts by mass of an aqueous acryloxyethyltrimethylammonium chloride solution (trade name “DMAEA-Q”, solid concentration 79% by mass, manufactured by Kojin Co., Ltd.) as a reactive conductive agent, It diluted with MIBK so that solid content concentration might be 30 mass%, and the coating liquid for (A) layers was prepared.
Comparative Example 1
In the preparation of the coating liquid for (A) layer in Example 1 (1), except that the ionic liquid was not added, the coating liquid for (A) layer was prepared in the same manner as in Example 1, Further, an antireflection film was produced. Table 1 shows the physical properties of this antireflection film.

From Table 1, the antireflection films of the present invention (Examples 1 to 5) all have excellent antireflection properties, excellent near infrared absorptivity, excellent scratch resistance, and surface resistivity. Low and has excellent antistatic properties. In Example 3, since the hard coat layer contains an antiglare property-imparting agent, the 60 ° gloss value is 80.
On the other hand, in Comparative Example 1, since neither the ionic liquid nor the reactive conductive agent is contained in either the hard coat layer or the low refractive index layer, the surface resistivity is high and the antistatic property is poor.

  The antireflection film of the present invention has near-infrared absorption performance and antireflection performance, is excellent in scratch resistance and antistatic properties, has a simple layer structure and is low in cost, and is particularly suitable for PDP use.

Claims (12)

On one surface of the base film, (A) a hard coat layer having a thickness of 2 to 20 μm containing a polyfunctional acrylate not containing fluorine or silicon and a near infrared absorber, and (B) porous silica 60 to 75 % by mass A low-refractive index layer having a refractive index of 1.43 or less and a thickness of 50 to 200 nm, which contains a polyfunctional acrylate containing no fluorine or silicon .
The layer (A) and / or the layer (B) is represented by the general formula (1)
(Z ^{a +} ) _m · (A ^b− ) _n (1)
[In the formula, Z ^{a +} represents a cation, A ^b− represents an anion, a, b, m and n are each an integer of 1 to 3, and satisfy the relationship of a × m = b × n. If Z a ⁺ there are multiple, ⁺ the plurality of Z ^a may be the same or different, if the A ^b-there are multiple, ^b-multiple A may be the same or different. ]
An antireflective film comprising an ionic liquid that is a molten salt that exhibits a liquid state at room temperature and having a spectral transmittance of 20% or less in the entire region at a wavelength of 800 to 1200 nm. The antireflection film according to claim 1, wherein the surface resistivity is 5 × 10 ¹³ Ω / □ or less. Z ^{a +} in the general formula (1) is the general formula (2), (3), (4) or (5).

[R ¹ in Formula (2) represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and R ² and R ³ are each independently a hydrogen atom or a carbon atom having 1 to 16 carbon atoms. Represents a hydrogen group and may contain a heteroatom. However, when the nitrogen atom contains a double bond, there is no R ³ .
R ⁴ in the formula (3) represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom or 1 to Represents 16 hydrocarbon groups and may contain heteroatoms.
R ⁸ in the formula (4) represents a hydrocarbon group having 2 to 20 carbon atoms, and may include a hetero atom. R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom or a carbon number 1 to 1 Represents 16 hydrocarbon groups and may contain heteroatoms.
E in Formula (5) represents a nitrogen, sulfur, or phosphorus atom, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and a hetero atom May be included. However, if E is a sulfur ^{atom, R 15} is not. ]
The antireflection film according to claim 1, which is a cation represented by the formula: Formula ^{A b-is} in _{(1), (CF 3 SO} 2) 2 N - antireflection film according to any of claims 1 to 3.  The antireflection film according to claim 1, wherein the (A) layer and / or the (B) layer further contains a reactive conductive agent together with the ionic liquid. The reactive conductive agent has a general formula (6) in the molecule.

[Wherein R ¹⁶ and R ¹⁷ are the same or different alkyl groups having 1 to 10 carbon atoms, R ¹⁸ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ¹⁹ is radical polymerization. Functional group, X ^p- represents a p-valent anion, and p represents an integer of 1 to 4. ]
The antireflection film according to claim 5, which is a radically polymerizable compound having a quaternary ammonium salt represented by the formula:  The antireflection film according to claim 1, wherein the layer (A) further contains an organic and / or inorganic filler and has an antiglare function.  The near-infrared absorber contained in (A) layer is a tungsten oxide type compound, The antireflection film in any one of Claims 1-7.  The antireflection film according to claim 8, wherein the tungsten oxide compound is cesium-containing tungsten oxide.  The antireflection film according to claim 8 or 9, wherein the content of the tungsten oxide compound in the layer (A) is 5 to 50% by mass.  The antireflection film according to any one of claims 1 to 10, which has a pressure-sensitive adhesive layer having a thickness of 5 to 50 µm on the other surface of the base film.  It is an object for plasma displays, The antireflection film in any one of Claims 1-11.