JP4815307B2 - Optical film, antireflection film, method for producing the same, polarizing plate using the same, and display device - Google Patents

Description

  The present invention relates to an optical film having improved scratch resistance, an antireflection film having improved scratch resistance while having a low reflectivity, and a method for producing the same, and in particular, an antireflection film used for a display device such as a liquid crystal display device. And a manufacturing method thereof.

  In applications such as adhesives, exterior paints, hard coats, anti-reflection coatings containing organic and inorganic materials, it is possible to improve scratch resistance, strength of cured products, adhesion to other materials in contact It is being considered.

  Among these, in combination with polymerization-curing organic materials, alkoxysilanes containing a polymerization group and / or hydrolysis condensates thereof have attracted attention. For example, Patent Document 1 proposes the combined use of a specific polyalkoxypolysiloxane and a polymerizable silane coupling agent. Patent Document 2 reports a partial cohydrolysis condensate of an alkoxysilane containing an organic functional group and a tetraalkoxysilane.

  On the other hand, an antireflection film is generally used for 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 due to reflection of external light. In order to prevent reflection of images and images, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be produced by forming a high refractive index layer comprising a hard coat layer on a support, and further forming a low refractive index layer having an appropriate film thickness thereon. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display, in many cases, the low refractive index layer which is the uppermost layer of the antireflection film is required to have high scratch resistance. However, in order to realize high scratch resistance in a low refractive index layer which is a thin film having a thickness of about 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  In order to lower the refractive index of the layer, there are means of (1) introducing fluorine atoms, (2) lowering the density (introducing voids), but in any case, film strength and adhesion are impaired and scratch resistance is reduced. This is a decreasing direction, and it has been difficult to achieve both a low refractive index and high scratch resistance.

For example, Patent Documents 3 to 5 describe means for improving scratch resistance by lowering the coefficient of friction on the coating surface by introducing a polysiloxane structure into the fluorine-containing polymer.
JP-A-9-169847 Japanese Patent Laid-Open No. 9-40909 JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A

In the technique of Patent Document 1, since the reaction between the polyalkoxypolysiloxane and the polymerizable silane coupling agent does not proceed sufficiently and the introduction rate of the polymerizable group is low, the scratch resistance and strength of the cured product are not sufficient. Absent. The technique of Patent Document 2 is not sufficient in storage stability of the liquid.

  Although the techniques of Patent Documents 3 to 5 are effective to some extent for improving the scratch resistance, this method alone has sufficient scratch resistance for a film that lacks essential film strength and interfacial adhesion. I can't get it.

  On the other hand, as one means for increasing the film strength, there is a method of introducing an inorganic filler into the low refractive index layer. By using the inorganic fine particles having a low refractive index as a filler, the film strength can be increased without increasing the refractive index of the layer itself. However, with the introduction of the inorganic filler, it is difficult to obtain adhesion to the lower layer, and the scratch resistance is not yet sufficient.

  An object of the present invention is to provide an optical film having improved scratch resistance, an antireflection film having sufficient antireflection performance and further improved scratch resistance, and a method for producing the antireflection film. It is. In particular, an object of the present invention is to provide an inexpensive method for producing such an antireflection film. It is a further object of the present invention to provide a polarizing plate and a display device provided with such an antireflection film.

The present inventors have found that by using an amino compound to which a polymerization initiation site is bonded, it is possible to obtain a great effect that rapid curing and accompanying scratch resistance are improved, and the present invention has been made. .
That is, the present invention achieves the object by the following configuration.

一般式（２）：

（式中、Ｘはアルキル基、または前記重合開始部位を有する置換もしくは無置換のアルキル基もしくはアリール基を表す。但し、Ｘのうち少なくとも１つは、前記重合開始部位を有する置換もしくは無置換のアルキル基もしくはアリール基である。）
＜２＞
透明支持体上に少なくとも反射防止層を有する反射防止フィルムであって、該支持体上に積層された層の少なくとも一層が、光ラジカル重合開始剤または熱ラジカル重合開始剤を基本骨格とする重合開始部位を有する下記一般式（１）または（２）で表されるアミノ化合物の少なくともいずれか１種を含有する組成物を光および／または熱エネルギーにより硬化させてなる層であることを特徴とする反射防止フィルム。
一般式（１）：

一般式（２）：

（式中、Ｘはアルキル基、または前記重合開始部位を有する置換もしくは無置換のアルキル基もしくはアリール基を表す。但し、Ｘのうち少なくとも１つは、前記重合開始部位を有する置換もしくは無置換のアルキル基もしくはアリール基である。）
＜３＞
透明支持体上に、少なくともハードコート層および、バインダーポリマーを含む組成物により形成される低屈折率層を有する反射防止フィルムであって、いずれかの層形成用組成物に、前記一般式（１）または（２）で表されるアミノ化合物の少なくともいずれか１種を含む上記＜２＞に記載の反射防止フィルム。
＜４＞
低屈折率層が、シリカ、中空シリカおよびフッ化マグネシウムより選ばれる無機フィラーを含有する上記＜３＞に記載の反射防止フィルム。
＜５＞
低屈折率層のバインダーポリマーが含フッ素ポリマーである上記＜３＞または＜４＞に記載の反射防止フィルム。
＜６＞
ハードコート層が、ジルコニウム、チタン、アルミニウム、インジウム、亜鉛、錫、アンチモン、および珪素のうちより選ばれる少なくとも１種の酸化物からなる無機フィラーを含有する上記＜３＞〜＜５＞のいずれかに記載の反射防止フィルム。
＜７＞
上記＜１＞に記載の光学フィルムの製造方法であって、該塗布された層を透明支持体上にダイコート法により塗布して形成することを特徴とする製造方法。
＜８＞
上記＜２＞〜＜６＞のいずれかに記載の反射防止フィルムの製造方法であって、該反射防止フィルムが有する少なくとも１層を透明支持体上にダイコート法により塗布して形成することを特徴とする製造方法。
＜９＞
低屈折率層を、塗布し、乾燥した後、酸素濃度３％以下の雰囲気下で、電離放射線照射して硬化して形成する上記＜３＞〜＜６＞のいずれかに記載の反射防止フィルムの製造方法。
＜１０＞
低屈折率層を、塗布し、乾燥した後、加熱硬化し、さらに３％以下の雰囲気下で電離放射線照射して硬化して形成する上記＜３＞〜＜６＞のいずれかに記載の反射防止フィルムの製造方法、または上記＜９＞に記載の反射防止フィルムの製造方法。
＜１１＞
上記＜２＞〜＜６＞のいずれかに記載の反射防止フィルム、または上記＜８＞〜＜１０＞のいずれかに記載の製造方法で製造された反射防止フィルムを、偏光板における偏光層の２枚の保護フィルムのうちの少なくとも一方に用いたことを特徴とする偏光板。
＜１２＞
上記＜２＞〜＜６＞のいずれかに記載の反射防止フィルム、もしくは上記＜８＞〜＜１０＞のいずれかに記載の製造方法で製造された反射防止フィルム、または上記＜１１＞に記載の偏光板を有するディスプレイ装置であって、反射防止層または低屈折率層が視認側になるように配置されていることを特徴とするディスプレイ装置。
本発明は上記＜１＞〜＜１２＞に関するものであるが、参考のためその他の事項（例えば下記（１）〜（２０）に記載の事項など）についても記載した。
（１）透明支持体上に塗布された層が、少なくとも１種の重合開始部位を有するアミノ化合物を含有する組成物の硬化物を含むことを特徴とする光学フィルム。 The present invention is as follows.
<1>
The layer coated on the transparent support has at least an amino compound represented by the following general formula (1) or (2) having a polymerization initiation site having a photo-radical polymerization initiator or a thermal radical polymerization initiator as a basic skeleton. The optical film characterized by including the hardened | cured material of the composition containing any 1 type.
General formula (1):

General formula (2):

(In the formula, X represents an alkyl group or a substituted or unsubstituted alkyl group or aryl group having the polymerization initiation site, provided that at least one of X is a substituted or unsubstituted group having the polymerization initiation site. An alkyl group or an aryl group.)
<2>
An antireflection film having at least an antireflection layer on a transparent support, wherein at least one of the layers laminated on the support is a polymerization initiator having a radical radical polymerization initiator or a thermal radical polymerization initiator as a basic skeleton. It is a layer formed by curing a composition containing at least one of amino compounds represented by the following general formula (1) or (2) having a moiety with light and / or heat energy Antireflection film.
General formula (1):

General formula (2):

(In the formula, X represents an alkyl group or a substituted or unsubstituted alkyl group or aryl group having the polymerization initiation site, provided that at least one of X is a substituted or unsubstituted group having the polymerization initiation site. An alkyl group or an aryl group.)
<3>
An antireflective film having a low refractive index layer formed of a composition containing at least a hard coat layer and a binder polymer on a transparent support, wherein any one of the layer forming compositions has the general formula (1) ) Or the antireflection film according to <2>, which contains at least one of the amino compounds represented by (2).
<4>
The antireflection film according to <3>, wherein the low refractive index layer contains an inorganic filler selected from silica, hollow silica, and magnesium fluoride.
<5>
The antireflection film according to <3> or <4>, wherein the binder polymer of the low refractive index layer is a fluorine-containing polymer.
<6>
Any of the above <3> to <5>, wherein the hard coat layer contains an inorganic filler composed of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and silicon. The antireflection film as described in 1.
<7>
The method for producing an optical film as described in <1> above, wherein the applied layer is formed on a transparent support by a die coating method.
<8>
The method for producing an antireflection film according to any one of the above <2> to <6>, wherein at least one layer of the antireflection film is applied on a transparent support by a die coating method. Manufacturing method.
<9>
The antireflective film according to any one of <3> to <6>, wherein the low refractive index layer is applied and dried, and then cured by irradiation with ionizing radiation in an atmosphere having an oxygen concentration of 3% or less. Manufacturing method.
<10>
The reflection according to any one of <3> to <6>, wherein the low refractive index layer is applied, dried, heat-cured, and then cured by irradiation with ionizing radiation in an atmosphere of 3% or less. The manufacturing method of an antireflection film as described in said <9>, or the manufacturing method of an antireflection film.
<11>
The antireflection film according to any one of <2> to <6> above or the antireflection film produced by the production method according to any one of <8> to <10> above, A polarizing plate used for at least one of two protective films.
<12>
The antireflection film according to any one of <2> to <6> above, the antireflection film produced by the production method according to any one of <8> to <10> above, or the above <11> A display device having the above polarizing plate, wherein the antireflection layer or the low refractive index layer is arranged on the viewing side.
The present invention relates to the above <1> to <12>, but other matters (for example, the matters described in the following (1) to (20)) are also described for reference.
(1) The optical film characterized in that the layer coated on the transparent support contains a cured product of a composition containing an amino compound having at least one polymerization initiation site.

(2) An antireflection film having at least an antireflection layer on a transparent support, wherein at least one layer laminated on the support contains an amino compound having at least one polymerization initiation site. An antireflection film, which is a layer obtained by curing an object with light and / or heat energy.

(3) An antireflective film having a low refractive index layer formed of a composition containing at least a hard coat layer and a binder polymer on a transparent support, and polymerization is started in any of the layer forming compositions The antireflection film as described in (2) above, which contains at least one of amino compounds represented by the following general formula (1) or (2) having a moiety.
General formula (1):

  General formula (2):

(In the formula, X represents an alkyl group or a substituted or unsubstituted alkyl group or aryl group having a polymerization initiation site, provided that at least one of X is a substituted or unsubstituted alkyl group having a polymerization initiation site. Or an aryl group.)

(4) The antireflection film as described in (3) above, wherein the low refractive index layer contains an inorganic filler selected from silica, hollow silica and magnesium fluoride.
(5) The antireflection film as described in (4) above, wherein the inorganic filler has an average particle size of 0.001 to 0.2 μm.
(6) The antireflection film as described in any one of (3) to (5) above, wherein the binder polymer of the low refractive index layer is a fluorine-containing polymer.

(7) The above (3) to (6), wherein the hard coat layer contains an inorganic filler composed of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and silicon. The antireflection film according to any one of the above.

(8) The antireflection film according to any one of (3) to (7), wherein at least one of the hard coat layers is an antiglare hard coat layer.
(9) The antireflection film as described in (8) above, further having a hard coat layer having no antiglare property in the lower layer of the antiglare hard coat layer.
(10) The above (8) or (8), wherein the antiglare hard coat layer is formed from a binder and matte particles having an average particle size of 1.0 to 10.0 μm, and the refractive index of the binder is 1.40 to 2.2. The antireflection film as described in (9).
(11) The antireflection film according to any one of (8) to (10), wherein the antiglare hard coat layer contains a fluorine-based and / or silicone-based surfactant.

(12) The optical film according to (1) or the antireflection film according to any one of (2) to (11), wherein the transparent support is triacetylcellulose, polyethylene terephthalate, or polyethylene naphthalate.
(13) The antireflection film as described in any one of (2) to (12), wherein the haze is from 0 to 80.0%, and the average reflectance for light having a wavelength of from 450 to 650 nm is 2.5% or less. .

(14) The method for producing an optical film as described in (1) above, wherein the coating solution is formed on a transparent support by a die coating method.

(15) The method for producing an antireflection film as described in any one of (2) to (13) above, wherein at least one layer of the antireflection film is applied on a transparent support by a die coating method. The manufacturing method characterized by the above-mentioned.

(16) The transparent support is in the form of a roll, the transparent support is continuously unwound, and at least one of a hard coat layer and a low refractive index layer is provided on one side of the unwound support, The method for producing an antireflection film according to (15), which is formed by coating by a die coating method.

(17) The method for producing an antireflection film according to (16), wherein the low refractive index layer is applied and dried, and then cured by irradiation with ionizing radiation in an atmosphere having an oxygen concentration of 3% or less.
(18) The reflection according to (16) or (17) above, wherein the low refractive index layer is applied, dried, heat-cured, and further cured by irradiation with ionizing radiation in an atmosphere of 3% or less. The manufacturing method of a prevention film.

(19) Polarizing an antireflection film according to any one of (2) to (13) or an antireflection film produced by the production method according to any one of (15) to (18) in a polarizing plate A polarizing plate used for at least one of two protective films of a layer.

(20) The antireflection film according to any one of (2) to (13) above, the antireflection film produced by the production method according to any one of (15) to (18), or (19) A display device comprising: a polarizing plate, wherein the low refractive index layer is disposed on the viewing side.

  According to the present invention, it is possible to manufacture an optical film with improved scratch resistance and an antireflection film with improved scratch resistance while having sufficient antireflection performance by an inexpensive manufacturing method. Moreover, according to the manufacturing method of this invention, such an antireflection film can be stably obtained with high productivity. Furthermore, the display device provided with the antireflection film or the polarizing plate manufactured according to the present invention has a feature of extremely high visibility with little reflection of external light and reflection of the background.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . The term “polymerization” as used in the present invention is intended to include copolymerization. Furthermore, “on the support” as used in the present invention includes both the case where it refers to the direct surface of the support and the case where it refers to the surface where some layer (film) is provided on the support. is there.

<Antireflection film>
[Layer structure of antireflection film]
The antireflection film of the present invention has a hard coat layer to be described later on a transparent support (hereinafter also referred to as a base material or a base film), and the reflectance is reduced by optical interference thereon. And an antireflection layer laminated in consideration of the refractive index, film thickness, number of layers, layer order, and the like. The simplest structure of the antireflection layer is one in which only a low refractive index layer is applied. In order to further reduce the reflectance, the antireflection layer is preferably constituted by combining a high refractive index layer having a higher refractive index than that of the base material and a low refractive index layer having a lower refractive index than that of the base material. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a refractive index lower than that of the high refractive index layer) / a high refractive index layer / a low refractive index layer, and the like, and more antireflection layers may be laminated. Among these, in view of durability, optical characteristics, cost, productivity, and the like, those laminated in the order of medium refractive index layer / high refractive index layer / low refractive index layer on a substrate having a hard coat layer are preferable. The antireflection film of the present invention may have a functional layer such as an antiglare layer or an antistatic layer.

The example of the preferable structure of the antireflection film of this invention is shown below. A schematic diagram is shown in FIGS.
Base film / antiglare layer / low refractive index layer,
Base film / hard coat layer / antiglare layer / low refractive index layer,
Base film / hard coat layer / high refractive index layer / low refractive index layer,
Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer.

The antireflection film of the present invention is not particularly limited to these layer configurations as long as the reflectance can be reduced by optical interference.
The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[Amino compound having a polymerization initiation site]
At least one of the hard coat layer and the low refractive index layer included in the antireflection film of the present invention is formed of a layer forming composition containing an amino compound having a polymerization initiation site.
The amino compound having the polymerization initiation site is represented by the general formula (1) or (2), and the layer forming composition preferably contains at least one of the amino compounds. By using an amino compound in which a polymerization initiation site is linked, it functions as an initiator at the time of photopolymerization, and the progress of curing can be promoted due to the radical polymerization chain transfer effect of the amino group. Moreover, since the polymerization by light and heat is also advanced and cured, the crosslinking in the layer can be effectively strengthened, so that the scratch resistance can be further improved.

  General formula (1):

  General formula (2):

  In the formula, X represents an alkyl group or a substituted or unsubstituted alkyl group or aryl group having a polymerization initiation site. However, at least one of X is a substituted or unsubstituted alkyl group or aryl group having a polymerization initiation site. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, s-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

  The substituent contained in X is not particularly limited, but may be a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (for example, methyl, ethyl, i-). Propyl, propyl, t-butyl etc.), aryl group (eg phenyl, naphthyl etc.), aromatic heterocyclic group (eg furyl, pyrazolyl, pyridyl etc.), alkoxy group (eg methoxy, ethoxy, i-propoxy, hexyloxy etc.) ), Aryloxy (eg phenoxy, etc.), alkylthio group (eg methylthio, ethylthio etc.), arylthio group (eg phenylthio etc.), alkenyl group (eg vinyl, 1-propenyl etc.), alkoxysilyl group (eg trimethoxysilyl, tri Ethoxysilyl, etc.), acyloxy groups (eg a Toxyl, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl groups (eg phenoxycarbonyl etc.), carbamoyl groups (eg carbamoyl, N-methylcarbamoyl, N, N-dimethyl) Carbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (for example, acetylamino, benzoylamino, acrylamino, methacrylamino, etc.) and the like. These substituents may be further substituted.

  Of these, a halogen atom, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group are preferable, and an epoxy group, a (meth) acryloyloxy group, and a (meth) acrylic group are more preferable. An amino group.

[Polymerization start site]
As the polymerization initiation site, those having the following photoradical polymerization initiator, thermal radical polymerization initiator or the like as a basic skeleton can be used by linking and synthesizing with a melamine site or uril site. As a synthesis example, K.K. Dietericker's “A Compilation of
Photoinitiators Commercially available for UV today "{SITA Technology Limited (2002)}, p25-28.

[Photo radical polymerization initiator]
As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP 2001-139663 A), Examples include 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, onium salts, and active halogen compounds.

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, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.

Examples of the benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone.
Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like. Specifically, compounds described in Examples in JP-A No. 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

  A borate salt may be used as a radical photopolymerization initiator. For example, it is described in Japanese Patent Nos. 2764769 and 2002-116539, and in “Rad. Tech'98. Proceeding” by Kunz, Martin et al., April, 19-22, 1998 (Chicago). And the compounds described in paragraphs [0022] to [0027] of JP-A No. 2002-116539. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

Furthermore, as the active halogens, specifically, “Bull Chem. Soc of Wakabayashi et al.
Japan ", 42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-A-5-27830," Jurnal of Heterocyclic Chemistry "by MP Hutt, 1 (3 No.), (1970), etc., and in particular, oxazole compounds and s-triazine compounds substituted with a trihalomethyl group, more preferably at least one mono-, di- or tri S-triazine derivatives in which a halogen-substituted methyl group is bonded to the s-triazine ring, specifically, p14-30 of JP-A-58-15503, p6-10 of JP-A-55-77742 No. 1-8 described on p287 of JP-B-60-27673, p4 of JP-A-60-239736 No.1~17 of 3-444, compounds such No.1~19 U.S. Pat. No. 4,701,399 are particularly preferred.

An inorganic complex may be used as a photo radical polymerization initiator. Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis {2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl} titanium. . Examples of coumarins include 3-ketocoumarin.
These initiators may be used alone or in combination.

  “Latest UV Curing Technology” {Publisher: Kazuhiro Takasato, Publisher; Technical Information Association, 1991}, p. 159 and “UV Curing System” (Kyoto Kato, published by the General Technology Center in 1989), pages 65 to 148 also describe examples of various radical photopolymerization initiators, which are useful for the present invention. is there.

  As a commercially available photocleavable photoradical polymerization initiator, “Irgacure {651,184,819,907,1870 (CGI-403 / Irg184 = 7/3 mixed initiator)” manufactured by Ciba Specialty Chemicals Co., Ltd. , 500, 369, 1173, 2959, 4265, 4263, etc.}, OXE01), etc .; “Kayacure (DETX-S, BP-100, BDK, CTX, BMS, 2-EAQ, ABQ, manufactured by Nippon Kayaku Co., Ltd.) CPTX, EPD, ITX, QTX, BTC, MCA, etc.); “Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT)” manufactured by Sartomer, and combinations thereof are also given as preferable examples. It is done.

[Thermal radical initiator]
As the thermal radical initiator, 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. Diazo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

[Specific examples of amino compounds]
Specific examples of the synthesis of the amino compounds represented by the general formulas (1) and (2) are shown below, but the present invention is not limited thereto.
The compound represented by the general formula (1) is, for example, K.I. Dietliker's “A Compilation of Photoinitiators Communityly
It can be synthesized by the scheme described in “available for UV today” (published by SITA Technology Limited, 2002), p.

  Although there is no restriction | limiting in particular in the usage-amount of these amino compounds which have a polymerization start part, It is preferable to use in the range of 0.1-20 mass parts with respect to 100 mass parts of polymerizable compounds used together, More preferably, it is 1-10 mass parts. These amino compounds may be used alone or in combination of other photosensitizers or the like. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

[Hard coat layer]
The antireflection film of the present invention preferably has a hard coat layer on a transparent support, and further has a low refractive index layer thereon. Furthermore, according to the performance requested | required, it can also be set as the antireflection film which used this hard-coat layer as the glare-proof hard coat layer. In the antireflection film of the present invention, for the purpose of improving the film strength, a hard coat layer that is not antiglare can be further provided under the antiglare hard coat layer.

[Inorganic filler]
Moreover, it is preferable to add an inorganic filler to each layer on the support. The inorganic filler added to each layer may be the same or different, and the type and amount added are preferably adjusted according to the required performance such as the refractive index, film strength, film thickness, and coatability of each layer.

  The shape of the inorganic filler used in the present invention is not particularly limited, and for example, any of spherical, plate-like, fiber-like, rod-like, amorphous, hollow and the like is preferably used, but from the viewpoint of good dispersibility. A spherical shape is more preferable.

  Further, the kind of the inorganic filler is not particularly limited, but an amorphous one is preferably used, and is preferably made of a metal oxide, nitride, sulfide or halide. Particularly preferred. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb, Ni and the like.

In order to obtain a transparent cured film, the average particle diameter of the inorganic filler is preferably set to a value within the range of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, and still more preferably. 0.001 to 0.06 μm. Here, the average particle diameter of the particles is measured by a Coulter counter.

  The method of using the inorganic filler in the present invention is not particularly limited, and for example, it can be used in a dry state, or can be used in a state dispersed in water or an organic solvent.

[Dispersion stabilizer]
In the present invention, it is also preferable to use a dispersion stabilizer in combination for the purpose of suppressing aggregation and sedimentation of the inorganic filler. Examples of the dispersion stabilizer include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives, polyamides, phosphate esters, polyethers, surfactants, hydrolysates of organosilane compounds and / or partial condensates thereof, silane coupling agents, A titanium coupling agent or the like can be used. In particular, a silane coupling agent is preferable because the film after curing is strong.

  Although the addition amount of the silane coupling agent as a dispersion stabilizer is not particularly limited, for example, the value is preferably 1 part by mass or more with respect to 100 parts by mass of the inorganic filler. Further, the addition method of the silane coupling agent as a dispersion stabilizer is not particularly limited, but a hydrolyzed one can be added, and the silane coupling agent which is a dispersion stabilizer and A method of further hydrolysis and condensation after mixing with the inorganic filler can be employed, but the latter is more preferable.

  Further, the hydrolyzate of organosilane compound and / or its partial condensate may be used as a dispersion stabilizer for inorganic fillers, as a part of the binder component of each layer, and as an additive for preparing a coating solution. It is preferable to use it.

  The inorganic filler suitable for each layer will be described later.

[Anti-glare hard coat layer]
The antiglare hard coat layer used in the present invention will be described below.
The antiglare hard coat layer is a binder for imparting hard coat properties, matte particles for imparting antiglare properties, and more preferably an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength. Formed from.

[Binder polymer]
The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, and more preferably a polymer having a saturated hydrocarbon chain as the main chain. The binder polymer preferably has a crosslinked structure.

(Binder polymer having a saturated hydrocarbon chain as the main chain)
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.

  In order to make the layer have a high refractive index, it is preferable that the monomer structure contains at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. .

Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid {for example, ethylene glycol di (meth) acrylate, 1,4
-Cyclohexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetriol tri (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate }, Vinylbenzene and its derivatives (for example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ester) Glycol ester, 1,4-divinyl cyclohexanone), vinyl sulfones (e.g., divinyl sulfone), acrylamides (e.g., methylenebisacrylamide) and methacrylamides. Two or more of these monomers may be used in combination.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

  Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. It can harden | cure by the polymerization reaction by and can form the anti-glare hard-coat layer of an antireflection film.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And 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.

  “Latest UV Curing Technology” {Publisher: Kazuhiro Takasato, Publisher; Technical Information Association, 1991}, p. Various examples are also described in 159 and are useful in the present invention.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

  In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, 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, diazoamino Examples thereof include benzene and p-nitrobenzenediazonium.

(Binder polymer with polyether as main chain)
The binder polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

  Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form an antireflective film.

  Instead of, or in addition to, a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and this crosslinkable functional group reacts. A crosslinked structure may be introduced into the binder polymer.

  Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.

  These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

[Matte particles]
For the purpose of imparting antiglare properties, the antiglare hard coat layer has matte particles having an average particle size of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, such as inorganic compounds, larger than the filler particles. Particles or resin particles.

Specific examples of the mat particles preferably include inorganic particles such as silica particles and TiO ₂ particles; resin particles such as crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Of these, crosslinked styrene particles are preferred.
As the shape of the matte particle, either a true sphere or an amorphous shape can be used. Further, two or more different kinds of mat particles may be used in combination.

The mat particles are formed on the anti-glare hard coat layer so that the amount of the mat particles in the formed anti-glare hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ^2. Contained.

Further, in a particularly preferred embodiment, cross-linked styrene particles are used as the matte particles, and the cross-linked styrene particles having a particle size larger than a half of the film thickness of the antiglare hard coat layer are 40 to 100 of the entire cross-linked styrene particles. %.
Here, the particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

Two or more kinds of mat particles having different particle diameters may be used in combination.
It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 dpi or more, it is required that there is no problem in optical performance called glare. This is because the pixels are enlarged or reduced due to unevenness present on the film surface and the uniformity of display performance is lost, but this is 5 to 50% more than the matte particles that impart antiglare properties. It can be greatly improved by using mat particles having a small diameter.

  Furthermore, the particle size distribution of the mat particles is preferably monodispersed, and the particle size of all particles is preferably as close as possible. For example, when particles having a particle size different from the average particle size by 20% or more are defined as coarse particles, the ratio of the coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. % Or less, more preferably 0.01% or less. The mat particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and mat particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

[Inorganic filler]
In order to increase the refractive index of the antiglare hard coat layer, in addition to the above mat particles, at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin and antimony is used. It is preferable to contain an inorganic filler made of an oxide and having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.

  Conversely, in the antiglare hard coat layer using the high refractive index mat particles in order to increase the refractive index difference from the mat particles, silicon oxide is used to keep the refractive index of the layer low. It is also preferable. The preferred particle size is the same as that of the inorganic filler.

Specific examples of the inorganic filler used in the antiglare hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, SiO _{2 and the} like. It is done. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index.

  The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.

  The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the antiglare hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.

  Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The total refractive index of the mixture of binder and inorganic filler in the antiglare hard coat layer in the antireflection film of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.50. 80. In order to set the refractive index within the above range, the type and amount ratio of the binder and the inorganic filler may be selected. It can be known experimentally in advance how to select.

  The antiglare hard coat layer in the present invention has a surface activity of either fluorine or silicone, particularly in order to prevent surface failure such as coating unevenness, drying unevenness, point defects and the like to ensure surface uniformity. It is preferable to contain the agent or both in the coating composition for forming the antiglare hard coat layer. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears in a smaller addition amount.

  Preferable examples of the fluorosurfactant include “Megafac F-171”, “Megafac F-172”, “Megafac F-173”, “Megafac F-176” manufactured by Dainippon Ink, Inc. (All are trade names) and other perfluoroalkyl group-containing oligomers. Examples of the silicone-based surfactant include polydimethylsiloxane in which a side chain or a main chain terminal is modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.

  In addition, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.40 or less, and / or a peak derived from a silicon atom and a peak derived from a carbon atom It is preferable that the ratio Si / C is 0.30 or less.

  The film thickness of the antiglare hard coat layer is preferably 1 to 10 μm, and more preferably 1.2 to 6 μm.

[Smooth hard coat layer]
In the antireflection film of the present invention, a so-called smooth hard coat layer that is not antiglare is also preferably used for the purpose of improving the film strength, and is coated between the transparent support and the antiglare hard coat layer.

  The material used for the smooth hard coat layer is the same as that mentioned in the anti-glare hard coat layer except that the matte particles for imparting anti-glare properties are not used. From the binder and preferably the inorganic filler It is formed.

  In the smooth hard coat layer in the present invention, as the inorganic filler, silica and alumina are preferable in terms of strength and versatility, and silica is particularly preferable. The inorganic filler is preferably subjected to silane coupling treatment on the surface, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.

  The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the smooth hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%. The film thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

(Low refractive index layer)
The low refractive index layer of the present invention will be described below.
The refractive index of the low refractive index layer in the antireflection film of the present invention is preferably 1.38 to 1.49, more preferably 1.38 to 1.44.

Further, the low refractive index layer preferably satisfies the following formula (1) from the viewpoint of reducing the reflectance.
Formula (1): (jλ / 4) × 0.7 <n ₁ d ₁ <(jλ / 4) × 1.3
In the formula, j is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm. The film thickness (d ₁ ) of the low refractive index layer is preferably 70 nm to 150 nm, more preferably 80 nm to 120 nm, and most preferably 85 nm to 115 nm.

  In addition, satisfy | filling said Numerical formula (1) means that j (positive odd number, usually 1) which satisfy | fills Numerical formula (1) exists in the said wavelength range.

  The material for forming the low refractive index layer in the present invention will be described below.

[Fluoropolymer]
In the present invention, the binder polymer used for forming the low refractive index layer is preferably a fluorine-containing polymer. The structure of the fluorinated vinyl monomer polymerized units contained in the fluorinated polymer is not particularly limited, and examples thereof include polymerized units based on fluorinated olefins, perfluoroalkyl vinyl ethers, vinyl ethers having a fluorinated alkyl group, and (meth) acrylates. be able to. The fluorine-containing polymer is preferably a copolymer of a fluorine-containing olefin and a vinyl ether because of suitability for production and properties required for a low refractive index layer such as a refractive index and film strength. More preferably, it is a copolymer. Further, as a copolymer component, perfluoroalkyl vinyl ether, vinyl ether having a fluorine-containing alkyl group, (meth) acrylate, or the like may be included for the purpose of reducing the refractive index.

  In the present invention, it is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content of the fluorine-containing polymer is 20 to 60% by mass, more preferably 25 to 55% by mass, particularly preferably 30 to 50%. This is a case of mass%.

(Perfluoroolefin)
As the perfluoroolefin, those having 3 to 7 carbon atoms are preferable, and from the viewpoint of polymerization reactivity, perfluoropropylene or perfluorobutylene is preferable, and from the viewpoint of refractive index, solubility, transparency, availability, etc., perfluoropropylene Is particularly preferred.

  The content of perfluoroolefin in the polymer is 25 to 75 mol%. In order to lower the refractive index of the material, it is desired to increase the introduction rate of perfluoroolefin, but in terms of polymerization reactivity, introduction of about 50 to 70 mol% is a limit in general solution-based radical polymerization reaction. This is difficult. In the present invention, the content is preferably 30 to 70 mol%, more preferably 30 to 60 mol%, still more preferably 35 to 60 mol%, and more preferably 40 to 60 mol%. It is particularly preferred.

(Perfluorovinyl ether)
In the present invention, a perfluorovinyl ether represented by the following general formula M2 may be copolymerized in order to reduce the refractive index. The copolymer component may be introduced into the polymer in a co-range of 0 to 40 mol%, preferably 0 to 30 mol%, more preferably 0 to 20 mol%, particularly preferably. It is a case of 0-15 mol%.

In the Formula M2, Rf ¹² represents a fluorine-containing alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, particularly preferably containing fluorinated alkyl group having 1 to 10 carbon atoms, 1 to carbon atoms More preferably, it is 10 perfluoroalkyl groups. The fluorinated alkyl group may have a substituent. Specific examples of Rf ¹² include -CF ₃ {M2- (1)}, -CF ₂ CF ₃ {M2- (2)}, -CF ₂ CF ₂ CF ₃ {M2- (3)}, -CF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₃ {M2- (4)} and the like.

(Vinyl ether having a fluorine-containing alkyl group)
In the present invention, a fluorine-containing vinyl ether represented by M1 shown below may be copolymerized in order to reduce the refractive index. The copolymer component may be introduced into the polymer in a co-range of 0 to 40 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%.

In the general formula M1, Rf ¹¹ represents a fluorine-containing alkyl group having 1 to 30 carbon atoms, preferably a fluorine-containing alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 15 carbon atoms, _{CF 2 CF 3, -CH 2 (} CF 2) q1 H, -CH 2 CH 2 (CF 2) q1 F: even (q1 2 to 12 integer) such}, branched structure {e.g. CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.} It may have a formula structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these), and an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ (CF _{2 ) Q2 H, -CH 2 CH 2} OCH 2 (CF 2) q2 F (q2: 2~12 integer), CH like _{2 CH 2 OCF 2 CF 2 OCF} 2 CF 2 H) may have. The substituent represented by Rf ¹¹ is not limited to the substituent described here.

  Examples of the monomer represented by the general formula M1 include “Macromolecules”, Vol. 32 (21), p. 7122 (1999), a method in which a fluorine-containing alcohol is allowed to act on a leaving group-substituted alkyl vinyl ether such as vinyloxyalkyl sulfonate and vinyloxyalkyl chloride as described in JP-A-2-721. A method of exchanging vinyl groups by mixing a fluorine-containing alcohol and a vinyl ether such as butyl vinyl ether in the presence of a palladium catalyst as described in International Patent Application No. 92/05135; as described in US Pat. No. 3,420,793. , A method in which a fluorine-containing ketone and dibromoethane are reacted in the presence of a potassium fluoride catalyst, followed by a de-HBr reaction with an alkali catalyst;

(Other fluorine-containing monomer polymerization units)
Specific examples of other fluorine-containing monomer polymerization units other than the fluorine-containing monomer polymerization units described above include, for example, fluoroolefins other than those described above (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, etc.), perfluoro-2, 2-dimethyl-1,3-dioxole, a part of (meth) acrylic acid or a fully fluorinated alkyl ester derivative {for example, “Biscoat 6FM” (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd., “M-2020 "(Trade name), manufactured by Daikin Industries, Ltd., etc.}.

(Hydroxyl group-containing vinyl monomer polymerization unit)
The fluorine-containing polymer preferably used in the present invention preferably contains a hydroxyl group-containing vinyl monomer polymerization unit, but the content is not particularly limited. Since the hydroxyl group has a function of curing by reacting with the crosslinking agent, the higher the hydroxyl group content, the harder the film can be formed. The content is preferably 10 mol% or more and 70 mol% or less, % Is more preferably 60 mol% or less, and further preferably 25 mol% or more and 55 mol% or less.

  As the hydroxyl group-containing vinyl monomer, any vinyl ethers, (meth) acrylates, styrenes and the like can be used as long as they are copolymerizable with the above-described fluorine-containing vinyl monomer polymerization unit. For example, when a perfluoroolefin (such as hexafluoropropylene) is used as the fluorine-containing vinyl monomer, it is preferable to use a hydroxyl group-containing vinyl ether having good copolymerization properties, specifically 2-hydroxyethyl vinyl ether, 4-hydroxybutyl. Examples thereof include, but are not limited to, vinyl ether, 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, 4- (hydroxymethyl) cyclohexyl methyl vinyl ether, and the like.

(Constitutional unit for imparting crosslinking reactivity)
As the structural unit for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, Polymerization of monomers having amino groups, sulfo groups, etc. {eg (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.} A structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into the structural unit by a polymer reaction (for example, by introducing an acrylic acid chloride on a hydroxy group) Can) It is below.

  The fluorine-containing polymer used in the present invention preferably has a repeating unit having a (meth) acryloyl group in the side chain as an essential constituent component. If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. Generally, the (meth) acryloyl group-containing repeating unit preferably accounts for 5 to 90% by mass, more preferably 30 to 70% by mass, although it varies depending on the type of repeating unit derived from the fluorine-containing vinyl monomer. It is particularly preferred to account for ~ 60% by weight.

  In the fluorine-containing polymer useful in the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, the adhesion to the substrate, the Tg of the polymer (on the film hardness) In addition, other vinyl monomers can be appropriately copolymerized from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

(Other vinyl monomer units)
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, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene) P-hydroxymethylstyrene, p-methoxystyrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, Droxyethyl 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.), Examples include acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile, and the like.

In the present invention, a fluorine-containing polymer described by the following general formula (3) is preferably used.
General formula (3):

In General Formula (3), L ¹¹ 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, which is linear. It may have a branched structure, may have a ring structure, or may have a heteroatom selected from O, N, and S. Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, - (CH} 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH 2 CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side) For example). s1 represents 0 or 1.

In general formula (3), R ¹¹ represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable. A ¹¹ represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., and can be selected as appropriate, and is composed of single or multiple vinyl monomers depending on the purpose. It may be.

Preferred examples of the vinyl monomer constituting A ¹¹ include vinyl ethers such as 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, and allyl vinyl ether. Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyl (Meth) acrylates such as trimethoxysilane, styrene derivatives such as styrene and p-hydroxymethylstyrene, Phosphate, maleate, there may be mentioned unsaturated carboxylic acids and derivatives thereof such as itaconic acid, more preferably a vinyl ether derivative, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z = 100.

As a particularly preferred form of the fluorine-containing polymer used in the present invention, general formulas (3-1) and (3-2) may be mentioned.
General formula (3-1):

In General Formula (3-1), R ¹¹ , x, and y have the same meaning as in General Formula (3), and the preferred range is also the same. t1 represents an integer of 2 ≦ t1 ≦ 10, preferably 2 ≦ t1 ≦ 6, and particularly preferably 2 ≦ t1 ≦ 4. B ¹¹ represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Examples include those described as examples of A ¹¹ in the general formula (3) applies. z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.

  The fluorine-containing polymer represented by the general formula (3) or (3-1) can be obtained, for example, by introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component. Can be synthesized.

  Formula (3-2):

In the general formula (3-2), R ¹² represents an alkyl group having 1 to 10 carbon atoms or a group containing an ethylenically unsaturated group such as the general formula (3-1) {—O—C (═O) C (-R ¹¹⁾ = CH _2} may be. t2 represents an integer of 1 ≦ t2 ≦ 10, preferably 1 ≦ t2 ≦ 6, and particularly preferably 1 ≦ t2 ≦ 4. t3 represents an integer of 2 ≦ t3 ≦ 10, preferably 2 ≦ t3 ≦ 6, and particularly preferably 2 ≦ t3 ≦ 4.

B ¹¹ represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Moreover, the silicone site | part may be included. x, y, z1 and z2 represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 0 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦ 55. 0 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 0 ≦ y ≦ 55. z1 and z2 preferably satisfy 1 ≦ z1 ≦ 65 and 1 ≦ z2 ≦ 65, more preferably 1 ≦ z1 ≦ 40, and 1 ≦ z2 ≦ 10, preferably 1 ≦ z1 ≦ 30, It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.

  The fluorine-containing polymer useful in the present invention is preferably those shown in [0043] to [0047] of JP-A No. 2004-45462.

  The fluorine-containing polymer used in the present invention can be synthesized by the method described in JP-A-2004-45462. Further, the synthesis of the fluorine-containing polymer used in the present invention was carried out by synthesizing precursors such as a hydroxyl group-containing polymer by various polymerization methods other than those described above, for example, solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Then, it can also carry out by introduce | transducing a (meth) acryloyl group by the said 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 ionizing radiation, and the like. These polymerization methods and polymerization initiation methods are described in, for example, the revised version of “Polymer Synthesis Method” written by Tsuruta Junji (Nikkan Kogyo Shimbun) (1971), and Takayuki Otsu and Masaaki Kinoshita “Experimental Methods for Polymer Synthesis” (Chemical Doujin) (Showa 47), pages 124-154.

  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 (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, Benzene, toluene, acetonitrile, methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more organic solvents such as water or water A mixed solvent 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, and the like, and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform the polymerization in the range of 50 to 100 ° C.

  The reaction pressure can be selected as appropriate, but usually 1 to 100 kPa, particularly about 1 to 30 kPa is desirable. The reaction time is about 5 to 30 hours.

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

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of a perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing crosslinking reaction alone {a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group}. These crosslinkable group-containing polymerized units preferably occupy 5 to 90% by mass of the total polymerized units of the polymer, and particularly preferably 40 to 60% by mass.

  Moreover, it is preferable that the polysiloxane structure is introduce | transduced into the fluorine-containing polymer of this invention for the purpose of providing antifouling property. The method for introducing the polysiloxane structure is not limited. For example, as described in JP-A-11-189621, JP-A-11-228631, and JP-A-2000-313709, polysiloxane can be introduced using a silicone macroazo initiator. A method of introducing a block copolymer component; a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806 is preferable. These polysiloxane components are preferably 0.5 to 10% by mass, particularly preferably 1 to 5% by mass in the polymer.

  For imparting antifouling properties, reactive group-containing polysiloxanes other than the above (for example, “KF-100T”, “X-22-169AS”, “KF-102”, “X-22-3701IE”, “ "X-22-164B", "X-22-5002", "X-22-173B", "X-22-174D", "X-22-167B", "X-22-161AS" "AK-5", "AK-30", "AK-32" {above trade name, manufactured by Toa Gosei Co., Ltd.}; "Silaplane FM0725", "Silaplane FM0721" It is also preferable to add {the above-mentioned trade name, manufactured by Chisso Corporation}, etc. In this case, these polysiloxanes may be added in the range of 0.5 to 10% by mass of the total solid content of the low refractive index layer. Preferably, particularly preferably 1 to 5% by mass This is the case.

[Inorganic filler]
As the inorganic filler used in the low refractive index layer, those having a low refractive index are preferably used. Preferred inorganic fillers are silica, hollow silica, and magnesium fluoride, and hollow silica is particularly preferable. The average particle size of the inorganic filler is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.05 μm. The particle diameter of the filler is preferably as uniform (monodispersed) as possible.

(Magnesium fluoride)
The particle diameter of magnesium fluoride is preferably as fine as possible in the dispersion medium, and the weight average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. By miniaturizing the magnesium fluoride particles to 100 nm or less, a film that does not impair the transparency can be formed. The particle size of magnesium fluoride can be measured by a light scattering method or an electron micrograph.

(Silica fine particles)
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm. If the particle size of the silica fine particles is not less than the lower limit value, the effect of improving the scratch resistance is exhibited. If the particle size is not more than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening or This is preferable because it does not cause problems such as poor integrated reflectance.

  The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

(Hollow silica fine particles)
In order to lower the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles. The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, if the radius of the cavity in the particle is r _i and the radius of the particle outer shell is r _o , the porosity x is expressed by the following formula (2). The porosity x of the hollow silica particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.
Equation (2): x = (4πr i 3/3) / (4πr o 3/3) × 100
Since the thickness of the outer shell is sufficiently thick and the strength of the particles is increased, particles having a refractive index of 1.15 or more are preferable from the viewpoint of scratch resistance.

  A method for producing hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably from 1 to 100 mg / m ^2, more preferably 5-80 mg / m ^2, more preferably from 10~60mg / m ^2. If the coating amount of the hollow silica is equal to or greater than the lower limit value, the effect of lowering the refractive index and the effect of improving scratch resistance are exhibited. If the coating amount is equal to or smaller than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer. This is preferable because it does not cause defects such as black appearance and poor integrated reflectance.

  The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm. If the particle size of the silica fine particles is equal to or greater than the lower limit value, the ratio of the cavities is not excessively small, so that an effect of lowering the refractive index is exhibited. This is preferable because irregularities are formed and appearance such as black tightening and inconveniences such as deterioration in integrated reflectance do not occur.

  The hollow silica may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.

In the present invention, the specific surface area of the hollow silica is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be determined by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

  In addition, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “silica fine particles with small size particle size”) is used as silica fine particles with the above particle size (“large size particles”). It can also be used in combination with "silica fine particles having a diameter".

  Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.

  The average particle diameter of the silica fine particles having a small size is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

  Silica fine particles are treated by physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to increase the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred.

  As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent, a silane coupling agent, etc.) is preferably used. Of these, treatment with an organosilane compound or a silane coupling agent having an acryloyl group or a methacryloyl group is particularly effective.

  The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.

The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment. Specific examples of the surface treatment agent and the catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in International Publication No. 04/017105 pamphlet.

  As the inorganic filler used for the low refractive index layer, two types of fillers having different particle diameters may be used in combination. In particular, by using an inorganic filler having a particle diameter of 0.02 to 0.08 μm and an inorganic filler having a particle diameter of 0.02 μm or less in combination, both reflectance and scratch resistance can be achieved. The ratio of the added amount of each of the two types of inorganic fillers having different particle diameters can be freely changed between 0 and 1 depending on the desired balance between reflectivity and scratch resistance. When it is desired to reduce the reflectance, it is preferable that the inorganic filler having a small particle diameter occupies the majority, and when it is desired to enhance the scratch resistance, it is preferable to increase the ratio of the inorganic filler having a large particle diameter.

  The addition amount of the inorganic filler is preferably 5 to 90% by mass of the total mass of the low refractive index layer, more preferably 10 to 70% by mass, and particularly preferably 10 to 50% by mass.

[Solvent of coating liquid for layer formation]
The solvent composition of the coating solution used for forming the hard coat layer and the low refractive index layer according to the present invention may be either single or mixed. When mixed, the solvent has a boiling point of 100 ° C. or less in all the solvents. Is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 100% by mass. If the solvent having a boiling point of 100 ° C. or lower is equal to or higher than the lower limit, the drying rate will not be too slow, the coated surface shape will not be deteriorated, and the coating film thickness will not be uneven, the reflectance, etc. This is preferable because problems such as deterioration of the optical properties of the film do not occur. In the present invention, these problems can be solved by using a coating liquid containing a large amount of a solvent having a boiling point of 100 ° C. or less.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hexane (boiling point 68.7 ° C., hereinafter “° C.” is omitted), heptane (98.4), cyclohexane (80.7), benzene (80.1), and the like. Hydrocarbons; halogenated carbonization such as dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87.2), etc. Hydrogens; for example, ethers such as diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), tetrahydrofuran (66); for example ethyl formate (54.2), methyl acetate ( 57.8), ethyl acetate (77.1), esters such as isopropyl acetate (89); for example, acetone (56.1), 2-butanone ( Ketones such as methyl ethyl ketone, 79.6); alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2); (81.6), cyano compounds such as propionitrile (97.4); carbon disulfide (46.2). Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or higher include octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), chlorobenzene (131.7), and dioxane (101.3). , Dibutyl ether (142.4), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (methyl isobutyl ketone = MIBK, 115.9), 1-butanol (117.7), N, N-dimethylformamide (153), N, N-dimethylacetamide (166), dimethyl sulfoxide (189), and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

By diluting the hard coat layer and the low refractive index layer component according to the present invention with the solvent having the above composition, coating solutions for forming these layers are prepared. The concentration of the coating solution is preferably adjusted in consideration of the viscosity of the coating solution and the specific gravity of the layer material, but is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass.

(Transparent support)
As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. As a polymer for forming a plastic film, cellulose ester {for example, triacetyl cellulose, diacetyl cellulose, typically “TAC-TD80U”, “TAC-TD80U”, “TAC-TD80UF” (manufactured by Fuji Photo Film Co., Ltd.) ( Etc.], polyamide, polycarbonate, polyester (for example, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, norbornene resin {“Arton” (trade name), manufactured by JSR Corporation}, amorphous Polyolefin {“ZEONEX” (trade name), manufactured by Nippon Zeon Co., Ltd.} and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.

  The triacetyl cellulose film is composed of a single layer or a plurality of layers. A single-layer triacetyl cellulose film is produced by drum casting or band casting disclosed in JP-A No. 7-11055 and the like. It is produced by the so-called co-casting method disclosed in JP-A-61-94725 and JP-B-62-43846.

  That is, raw material flakes such as halogenated hydrocarbons (dichloromethane, etc.), alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. Dissolve in a solvent, and add a solution (called a dope) to which various additives such as plasticizer, ultraviolet absorber, deterioration inhibitor, slipping agent, peeling accelerator and the like are added as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support and peeled off from the support. A process comprising passed through a drying unit to remove the solvent by various transport means.

  A typical solvent for dissolving triacetylcellulose as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). In preparing a triacetyl cellulose dope using a solvent substantially free of dichloromethane or the like, the following special dissolution method is essential.

The first dissolution method is called a cooling dissolution method and will be described below.
First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (−10 to 40 ° C.) while stirring. The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this manner, the mixture of triacetyl cellulose and solvent solidifies. Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), a solution in which triacetyl cellulose flows in the solvent is obtained. The temperature may be increased by simply leaving it at room temperature or in a warm bath.

The second method is called a high temperature dissolution method and will be described below.
First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (−10 to 40 ° C.) while stirring. The triacetyl cellulose solution used in the present invention is preferably swollen beforehand by adding triacetyl cellulose to a mixed solvent containing various solvents. In this method, the dissolution concentration of triacetyl cellulose is preferably 30% by mass or less, but is preferably as high as possible from the viewpoint of drying efficiency during film formation. Next, the organic solvent mixed solution is heated to 70 to 240 ° C. under a pressure of 0.2 MPa to 30 MPa (preferably 80 to 220 ° C., more preferably 100 to 200 ° C., most preferably 100 to 190 ° C.). Next, since these heated solutions cannot be applied as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to -10-50 degreeC and to return to a normal pressure. For cooling, the high-pressure and high-temperature vessel or line containing the triacetylcellulose solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water.

  A cellulose acetate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter published Technical Report 2001- No. 1745).

[Use of antireflection film]
When the antireflection film of the present invention (also referred to as an antireflection film) is used in a liquid crystal display device, it can be disposed on the outermost surface of the display by providing an adhesive layer on one side. Further, since a triacetyl cellulose film is often used as a protective film for protecting a polarizing layer (also referred to as a polarizing film) of a polarizing plate, when the transparent support of the antireflection film of the present invention is a triacetyl cellulose film, the antireflection It is preferable in terms of cost to use the film as it is for the protective film.

[Saponification]
When the antireflection film of the present invention is disposed on the outermost surface of the display or used as it is as a protective film for a polarizing plate, the fluoropolymer is mainly used on the transparent support in order to improve adhesion. It is preferable to perform a saponification treatment after forming the outermost layer.

  The saponification treatment is performed by a known method, for example, by immersing the antireflection film in an alkali solution for an appropriate time. After being immersed in the alkali solution, it is preferable to wash the substrate sufficiently with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the film. By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.

  The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so when adhering to the polarizing film, it is difficult for dust to enter between the polarizing film and the antireflective film, thus preventing point defects due to dust. It is effective for.

  The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two. The following (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the saponification treatment is performed up to the antireflection layer surface, the surface is alkali-hydrolyzed and the film is deteriorated. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, the following (2) is excellent.

(1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after forming the antireflection layer on the transparent support, an alkaline solution is applied to the surface of the antireflection film opposite to the surface on which the antireflection layer is formed, and heating, washing and / or in By summing, only the back surface of the film is saponified.

(Formation of antireflection layer)
Each layer of the antireflection film having a multilayer structure is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, a gravure coating method, an extrusion coating method (US Pat. No. 2,681,294) Can be formed by coating, but is preferably coated by a die coating method, and more preferably by using a new die coater described later. 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, 3,526,528 and Yuji Harasaki, “Coating Engineering”, Asakura Shoten (1973), page 253. .

  In order to continuously produce the antireflection film of the present invention, the base film is preferably in the form of a roll. For example, a step of continuously unwinding (also referred to as “feeding out”) a roll-shaped base film, a step of applying and drying a coating liquid on one side of the unrolled base film, and curing the coating film The process and the process of winding up the base film which has a hardened layer are performed.

Specifically, it can be performed as follows.
The substrate film is continuously sent from the roll-shaped substrate film to the clean room. In the clean room, the static electricity charged in the substrate film is removed by the electrostatic charge-removing device, and then adheres onto the substrate film. Remove the foreign material that has been removed with a dust remover. Next, the coating liquid is applied onto the base film in the coating section installed in the clean room, and the coated base film is sent to the drying room and dried.

  The substrate film having the dried coating layer is sent from the drying chamber to the thermosetting section, heated and cured, and then sent to the radiation curing chamber, where the monomer contained in the coating layer is polymerized by irradiation with radiation. Harden. In some cases, the film is sent directly to the radiation curing chamber, irradiated with radiation, the monomer contained in the coating layer is polymerized to complete the curing, and the base film having the cured layer is wound up into a roll shape. Become.

  In the present invention, a die coating method is preferably used as a coating method from the viewpoint of a higher production rate. The die coating method is preferably used because it can achieve a high level of productivity and a surface shape without coating unevenness. As a manufacturing method of the antireflection film of the present invention, the following coating method using such a die coating method is preferable.

  That is, the manufacturing method includes a coating step of applying a coating liquid from the slot of the tip lip by bringing the land of the tip lip of the slot die close to the surface of the web supported continuously by the backup roll. The slot die has a slot die whose land length in the web traveling direction of the tip lip on the web traveling direction side of the slot die is 30 μm or more and 100 μm or less, and is opposite to the web traveling direction when the slot die is set at the coating position. The gap between the tip lip on the side and the web is larger by 30 μm or more and 120 μm or less than the gap between the tip lip on the web traveling direction side and the web (hereinafter, this numerical limitation is referred to as “over bit length”). It is preferable to apply | coat using the coating device installed so that it might become.

In particular, a die coater that can be preferably used in the production method of the present invention will be described below with reference to the drawings. The die coater can be used when the wet coating amount is small (20 mL / m ² or less), which is preferable.

[Configuration of die coater]
FIG. 6 is a cross-sectional view of an example of a coater (coating device) using a slot die that can suitably implement the present invention.
The coater 10 includes a backup roll 11 and a slot die 13, and the coating liquid 14 is discharged from the slot die 13 in a bead shape 14 a and applied to the web W that is continuously supported by the backup roll 11. Thus, the coating film 14b is formed on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular or semicircular. The pocket 15 is extended with its cross-sectional shape in the width direction of the slot die 13 (where the width direction of the slot die 13 refers to the front side or the back side toward the drawing shown in FIG. 6). In general, the effective extension length of the coating liquid reservoir space is equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper (not shown) that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a thing such as a width regulating plate (not shown), the length is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the running direction of the web W of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat part 18 called a land. The upstream side of the land 18 in the traveling direction of the web W with respect to the slot 16 (the traveling direction, that is, the direction opposite to the arrow direction in the drawing) is the upstream lip land 18a, and the downstream side (the traveling direction side) is downstream. This is called side lip land 18b.

  The shape of the tip lip 17 is extended on the downstream side compared to the upstream side (over bite shape), and the gap between the upstream lip land 18a and the web W is correspondingly larger than the gap between the downstream lip land 18b and the web W. Large in the above range. The length of the downstream lip land land 18b is in the above-described range.

Referring to FIG. 7A, the part relating to the numerical limitation described above will be described. The land length on the web traveling direction side (downstream side) is a portion indicated by I _LO in FIG. The length of the overbyte is a portion indicated by LO in FIG.

Next, the overall coating process will be described with reference to FIG.
FIG. 8 is a perspective view showing the slot die 13 and its periphery in the coating process for carrying out the manufacturing method of the present invention. A decompression chamber 40 is installed on the slot die 13 on the opposite side of the web W in the direction of travel (that is, on the upstream side of the bead 14a) at a position where the decompression chamber 40 is not in contact with the slot die 13 so as to perform sufficient decompression adjustment on the bead 14a. Vacuum chamber 40, the gap between its operating efficiency has a back plate 40a and side plates 40b for holding a gap between the back plate 40a and the web W G _B, the side plate 40b and the web W G _S exists.

  The relationship between the decompression chamber 40 and the web W will be described with reference to FIG. FIG. 9 is a cross-sectional view showing the vacuum chamber 40 and the web W that are close to each other.

The side plate 40b and the back plate 40a may be integrated with the chamber 40 main body as shown in FIG. In any structure, the portions that are actually vacant between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W of the decompression chamber 40, when the vacuum chamber 40 is placed under the web W and the slot die 13 as shown in FIG. 8, the uppermost end of the back plate 40a to the web W Indicates the gap.

The back plate 40a and the gap G _B of the web W is preferably installed to be larger than the gap G _L [FIG 7 (A) Reference to the end lip 17 and the web W of the slot die 13, thereby backup A change in the degree of reduced pressure near the bead due to the eccentricity of the roll 11 can be suppressed. For example, when the gap G _L between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

[Coating method]
In the present invention, it may be cured by irradiation with ionizing radiation directly after drying, or may be cured by heating after drying and further irradiation with ionizing radiation. In any case, when curing by irradiating with ionizing radiation, it is preferable to irradiate with ionizing radiation in an atmosphere having an oxygen concentration of 3% by volume or less, and further, for 0.5 second or more from the start of ionizing radiation irradiation. It is preferable to harden by the process of maintaining the atmosphere at a concentration of 3% by volume or less. By supplying inert gas to the ionizing radiation irradiation chamber and slightly blowing out to the web entrance side of the irradiation chamber, it is possible to eliminate the carry air accompanying the web conveyance and effectively reduce the oxygen concentration in the reaction chamber Thus, the substantial oxygen concentration on the pole surface, which is largely inhibited by curing by oxygen, can be efficiently reduced. The direction of the flow of the inert gas on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between supply and exhaust of the irradiation chamber.

  Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air.

  In particular, the low refractive index layer which is the outermost layer and has a small thickness is preferably cured by this method.

  Further, by providing a front chamber in front of the reaction chamber and excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to efficiently use an inert gas, and more preferably, 0. The thickness is preferably 2 to 10 mm, and most preferably 0.2 to 5 mm.

However, in order to continuously produce webs, it is necessary to join the webs together and a method of attaching them with a joining tape or the like is widely used for joining. For this reason, when the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable, and to widen the gap by the junction thickness when the junction enters. In order to realize this, the entrance surface of the ionizing radiation reaction chamber or the front chamber is made movable in the forward and backward direction, and when the joint passes, the gap is moved back and forth to widen the gap, It is possible to move the chamber entrance surface vertically with respect to the web surface and move up and down to widen the gap as the joint passes.

  The oxygen concentration of the atmosphere when irradiating with ionizing radiation is 3% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less. In order to reduce the oxygen concentration, a large amount of an inert gas such as nitrogen is required. From the viewpoint of production cost, it is preferable not to lower the oxygen concentration more than necessary. As a means for reducing the oxygen concentration, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another inert gas, and particularly preferably with nitrogen (nitrogen purge). It is.

  In the present invention, at least one layer laminated on the transparent substrate is irradiated with ionizing radiation in an atmosphere having an oxygen concentration of 3% by volume or less, and an atmosphere having an oxygen concentration of 3% by volume or less from 0.5 second or more after the start of ionizing radiation irradiation. Is preferably maintained. The time maintained in the low oxygen concentration atmosphere is preferably 0.7 seconds or more and 60 seconds or less, and more preferably 0.7 seconds or more and 10 seconds or less. The low oxygen concentration maintaining time is preferably 0.5 seconds or longer because the curing reaction proceeds sufficiently and sufficient curing can be performed. Further, maintaining the low oxygen condition for a long time increases the size of the equipment and requires a large amount of inert gas, so the time is preferably 60 seconds or less.

  In the present invention, at least one layer laminated on the transparent substrate can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 20% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured. In particular, when increasing the production speed for high productivity, it is preferable to perform multiple ionizing radiation irradiations in order to ensure the energy of ionizing radiation necessary for the curing reaction, ensuring the reaction time necessary for the curing reaction. In addition, the above aspect is effective.

  The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. Although it can be selected, irradiation with ultraviolet rays is preferred in the present invention. Ultraviolet curing is preferred because the polymerization rate is fast, the equipment can be made compact, and there are many types of compounds that can be selected and the price is low.

  In the case of ultraviolet rays, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used. In the case of electron beam irradiation, energy of 50 to 1000 keV emitted from various electron beam accelerators such as Cockloft Walton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having the following is used.

〔Polarizer〕
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

[Polarizing film]
As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film in which the absorption axis of the polarizing film is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.

  That is, both ends of a continuously supplied polymer film are stretched by applying a tension while being held by a holding means and stretched at least 1.1 to 20.0 times in the film width direction. The difference in the longitudinal traveling speed of the holding device is within 3%, and the angle formed by the film traveling direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is tilted by 20 to 70 °. It can be produced by a stretching method in which the traveling direction is bent with both ends of the film held.

  The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

  Of the two protective films of the polarizing film, the film other than the antireflection film is preferably an optical compensation film comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen. A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

[Display device (image display device)]
The antireflection film of the present invention is used in an image 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 optical filter according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

[Liquid Crystal Display]
The antireflection film of the present invention and the polarizing plate using the same can be advantageously used in an image display device such as a liquid crystal display device, and are arranged so that the low refractive index layer is on the viewing side. It is preferably used for the outermost layer of the display.

  The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Further, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

  The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

(TN mode)
In a TN mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

(VA mode)
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

In VA mode liquid crystal cell,
(1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. ,
(2) Liquid crystal cell ("SID97, Digest of tech. Papers" (Preliminary Collection), Vol. 28 (1997), p. 845},
(3) A liquid crystal cell (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied. 58-59 (1998) description}, and
(4) Includes SURVAVAL mode liquid crystal cells (announced at "LCD International 98").

(OCB mode)
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper and lower portions of the liquid crystal cell. Nos. 825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

(IPS mode)
The IPS mode liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a lateral electric field. For details, refer to “Proc. IDRC” (Asia Display '95), p. 577-580 and p. 707-710.

(ECB mode)
In the ECB mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in, for example, JP-A-5-203946.

[Displays other than liquid crystal display devices]
(PDP)
A plasma display panel (PDP) is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. Two glass substrates are a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.

  Plasma display panels (PDP) are already commercially available. The plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.

  The front plate may be disposed on the front surface of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.

In an image display device such as a plasma display panel, the antireflection film of the present invention can be directly attached to the display surface as an optical filter. In addition, when a front plate is provided in front of the display, an antireflection film as an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.

(Touch panel)
The antireflection film of the present invention can be applied to touch panels described in JP-A Nos. 5-127822 and 2002-48913.

(Organic EL device)
The antireflection film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.

  When the antireflection film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653. JP, JP 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is possible to apply the contents described in each publication. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

[Various characteristic values]
Various measurement methods and preferred characteristic values relating to the antireflection film of the present invention are shown below.

[Reflectance]
The specular reflectance and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” [manufactured by JASCO Corporation], and an incident angle of 5 ° in the wavelength region of 380 to 780 nm. By measuring the specular reflectance at an exit angle of -5 °, the average reflectance of 450 to 650 nm is calculated, and the antireflection property can be evaluated. The reflectance of the film of the present invention is preferably 3.5% or less, more preferably 2.5% or less.

[Color]
The polarizing plate using the antireflection film of the present invention as its protective film is a color of regular reflection light with respect to incident light having an incident angle of 5 ° in the wavelength range of 380 nm to 780 nm of the CIE standard light source D ₆₅ , that is, By obtaining the L ^* , a ^* , and b ^* values of the CIE 1976 L ^* a ^* b ^* color space, the color can be evaluated.

The L ^* , a ^* , and b ^* values are preferably in the ranges of 3 ≦ L ^* ≦ 20, −7 ≦ a ^* ≦ 7, and −10 ≦ b ^* ≦ 10, respectively. By setting it within this range, the color of reflected light from red purple to blue purple, which has been a problem with conventional polarizing plates, is reduced, and 3 ≦ L ^* ≦ 10, 0 ≦ a ^* ≦ 5, and − 7 ≦ b ^* ≦ 0 is greatly reduced, and when applied to a liquid crystal display device, when applied to a liquid crystal display device, such as indoor fluorescent lights, the color when a little bright external light is reflected. Neutral, don't mind. Specifically, if a ^* ≦ 7, the reddishness will not be too strong, and if a ^* ≧ −7, the cyanishness will not be too strong. If b ^* ≧ −7, the bluish color does not become too strong, and if b ^* ≦ 0, the yellowish color does not become too strong.

Furthermore, the color uniformity of the reflected light is determined according to the following formula (3) from a ^* b ^* on the L ^* a ^* b ^* chromaticity diagram obtained from the reflection spectrum of the reflected light from 380 nm to 680 nm. It can be obtained as the rate of change in taste.
Formula (3):

Where a ^* _max and a ^* _min are the maximum and minimum values of a ^* values, respectively; b ^* _max and b ^* _min are the maximum and minimum values of b ^* values, respectively; a ^* _av and b ^* _av Are average values of a ^* and b ^* values, respectively. The color change rate is preferably 30% or less, more preferably 20% or less, and most preferably 8% or less.

In the antireflection film of the present invention, ΔE _w which is a change in color before and after the weather resistance test is preferably 15 or less, more preferably 10 or less, and most preferably 5 or less. In this range, low reflection and reduction in the color of reflected light can be achieved at the same time. The color tone when reflected is neutral, and the quality of the displayed image is good, which is preferable.

The color change ΔE _w can be obtained according to the following mathematical formula (4).
Formula (4): ΔE _w = [(ΔL _w ) ² + (Δa _w ) ² + (Δb _w ) ² ] ^1/2
Here, ΔL _w , Δa _w , and Δb _w are amounts of change of the L ^* value, the a ^* value, and the b ^* value before and after the weather resistance test.

[Transparent image clarity]
The transmitted image definition can be measured using an optical comb having a slit width of 0.5 mm with an image clarity measuring device “ICM-2D type” manufactured by Suga Test Instruments Co., Ltd. according to JIS K-7105.

  The transmitted image definition of the antireflection film of the present invention is preferably 60% or more. The transmitted image definition is generally an index indicating the degree of blur of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

[Surface roughness]
The centerline average roughness (Ra) in the antireflection film of the present invention can be measured according to JIS B-0601.

[Haze]
The haze of the antireflection film of the present invention is the haze value defined in JIS K-7105, and is manufactured by Nippon Denshoku Industries Co., Ltd. based on the measurement method defined in JIS K-7361-1. A value automatically measured as haze measured using a turbidimeter “NDH-1001DP” = (diffused light / total transmitted light) × 100 (%) was used.
The haze of the antireflection film of the present invention is preferably 0 to 80.0%, and more preferably 60% or less.

[Goniophotometer scattering intensity ratio]
Using an automatic goniophotometer “GP-5 type” {Murakami Color Research Laboratory Co., Ltd.}, an antireflection film is placed perpendicular to the incident light, and the scattered light profile is measured in all directions. did. It can be determined from the scattered light intensity at an exit angle of 30 ° with respect to the light intensity at an exit angle of 0 °.

[Abrasion resistance]
(Steel wool scratch resistance evaluation)
A rubbing test using a “rubbing tester” under the following conditions can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: Steel wool {made by Nippon Steel Wool Co., Ltd., Grade No. 0000} is wound around the rubbing tip (1 cm × 1 cm) of a tester that comes into contact with the sample, and the band is fixed.
Travel distance (one way): 13 cm.
Rubbing speed: 13 cm / sec.
Load: 500 g / cm ² and 200 g / cm ² .
Tip contact area: 1 cm × 1 cm.
Number of rubbing: 10 round trips.
Evaluation is performed by applying oil-based black ink to the back side of the rubbed sample, visually observing the scratches on the rubbed portion with reflected light, and observing the difference in the amount of reflected light from other than the rubbed portion.

(Eraser scuff resistance evaluation)
By using a “rubbing tester” and performing a rubbing test under the following conditions, it can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: A plastic eraser {Tonbo Pencil Co., Ltd. MONO} is fixed to the rubbing tip (1 cm × 1 cm) of the tester that comes into contact with the sample.
Travel distance (one way): 4 cm.
Rubbing speed: 2 cm / sec.
Load: 500 g / cm ² .
Tip contact area: 1 cm × 1 cm.
Number of rubbing: 100 reciprocations.
An oil-based black ink is applied to the back side of the rubbed sample, the scratches on the rubbing portion are visually observed with reflected light, and evaluation is made based on the difference in the amount of reflected light from other than the rubbed portion.

(Taper test)
In the Taber test according to JIS K5400, the scratch resistance can be evaluated from the wear amount of the test piece before and after the test. The smaller the amount of wear, the better.

[hardness]
(Pencil hardness)
The hardness of the antireflection film of the present invention can be evaluated by a pencil hardness test according to JIS K-5400. The pencil hardness is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

(Surface elastic modulus)
The surface elastic modulus in the antireflection film of the present invention is a value determined using a micro surface hardness meter {manufactured by Fisher Instruments: “Fischer Scope H100VP-HCU”}. Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.

(Universal hardness)
Further, the surface hardness can be obtained as a universal hardness by using the micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load. It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

The universal hardness of the crosslinkable polymer defined in the present invention is a microhardness meter “H100” manufactured by Fisher Instruments Co., Ltd. It is represented by the universal hardness (N / mm ² ) determined by the measurement procedure below.

In addition to the crosslinkable polymer, apply a coating solution with a solid content concentration of about 25% by mass containing the necessary catalyst, crosslinking agent, polymerization initiator, etc. to an appropriate bar so that the film thickness after curing is about 20-30 μm. Select the coater and select TOSHINRIKO. CO. It is coated on a glass slide plate made of LTD, (26 mm × 76 mm × 1.2 mm) polished. When the crosslinkable polymer is thermosetting, the thermosetting conditions for sufficiently curing the film are obtained in advance (as an example, 125 ° C., 10 minutes), and the same applies to the case where the crosslinkable polymer is ionizing radiation curable. The curing conditions for sufficiently curing the film are determined in advance (as an example, the oxygen concentration is 12 ppm, the UV irradiation amount is 750 mJ / cm ² ). For each film, the load is continuously increased from 0 to 4 mN, the film thickness of the base plate is not affected by 1/10 film thickness, and the cone diamond indenter is pressed against each load F. Universal hardness is calculated from N = 6 measurement average value of F / A determined from the indentation area A (mm ² ).

[Anti-fouling test]
(Magic ink wiping property)
An anti-reflection film is fixed on the glass surface with an adhesive, and a black “magic ink” (“Mckey extra fine”) {trade name: manufactured by Zebra Co., Ltd.} nib (narrow) under the conditions of 25 ° C. and 60 RH%. Write a circle of 5 mm in diameter 3 times, and “Bencot” {Brand name: Asahi Kasei Co., Ltd.}, which was folded 10 times after 5 seconds, and wiped it back and forth 20 times with a load enough to dent the “Bencot” bundle. This writing and wiping are repeated under the same conditions until the “magic ink” mark disappears by wiping, and the antifouling property can be evaluated by the number of times of wiping.
The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

  For black “Magic Ink”, use “Magic Ink No. 700 (M700-T1 Black) Extra Fine”, paint a 1 cm diameter circle on the sample, paint it for 24 hours and rub it with “Bencott”. It can also be evaluated by whether or not "" can be wiped off.

[surface tension]
In the present invention, the surface tension of the coating liquid forming the functional layer can be measured using a surface tension meter {Kyowa Interface Science Co., Ltd., “KYOWA CBVP SURFACE TENSIOMETER A3”} in an environment at a temperature of 25 ° C. it can.

[Contact angle]
Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using a pure water as a liquid in a dry state (20 ° C., 65% RH), a diameter of 1.0 mm A droplet was made on the needle tip and brought into contact with the surface of the film to form a droplet on the film. The angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other is defined as the contact angle.

[Surface free energy]
The surface energy can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” {Published by Realize Inc., 1989.12.10}. In the case of the film of the present invention, it is preferable to use a contact angle method. Specifically, two kinds of solutions having known surface energies are dropped on a cellulose acylate film, and at the intersection of the surface of the droplet and the surface of the film, the angle formed between the tangent line drawn on the droplet and the film surface, The surface angle of the film can be calculated by defining the angle containing the droplet as the contact angle.

The surface free energy (γs ^v : unit, mN / m) of the antireflection film of the present invention is defined as K. Owens, “J. Appl. Polym. Sci.”, Volume 13, p. 1741 (1969), from the contact angles θ _H2O and θ _{CH2I2 of} pure water H ₂ O and methylene iodide CH ₂ I ₂ experimentally determined on the antireflection film, the following simultaneous equations a, It is defined by a value γs ^v (= γs ^d + γs ^h ) expressed as the sum of the values γs ^d and γs ^h obtained from b {Formula (5)}, and represents the surface tension of the antireflection film. The gamma] s ^v is small, as the surface of the repellent can of high a low surface free energy, generally excellent antifouling property.
Formula (5):

_{a: 1 + cosθ H2O = 2√γs} d (√γ H2O d / γ H2O v) + 2√γs h (√γ H2O h / γ H2O v)
_{b: 1 + cosθ CH2I2 = 2√γs} d (√γ CH2I2 d / γ CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)
γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8

  The contact angle is measured using an automatic contact angle meter “CA-V150 type” manufactured by Kyowa Interface Science Co., Ltd. after conditioning the antireflection film at 25 ° C. and 60% RH for 1 hour or more. The contact angle was determined 30 seconds after 2 μL of the droplet was dropped on the film.

  The surface free energy of the film of the present invention is preferably 25 mN / m or less, and particularly preferably 20 mN / m or less.

[curl]
The curl is measured using the curl measurement template of Method A in “Measuring Method of Curling of Photographic Film” of JIS K-7619-1988.
Measurement conditions are 25 ° C., 60% RH, and a humidity control time of 10 hours.

In the antireflection film of the present invention, the value when curl is expressed by the following formula (6) is preferably in the range of −15 to +15, more preferably in the range of −12 to +12. Is -10 to +10. The measurement direction of the curl in the sample at this time is measured in the conveyance direction of the base material in the case of application in a web form.
Formula (6): Curl = 1 / R
R represents a radius of curvature (m).

  This is an important characteristic for preventing cracks and film peeling during film production, processing, and market handling. It is preferable that the curl value is in the above range and the curl is small. Here, the curl “+” means a curl in which the coating side of the film is inside the curve, and “−” means a curl in which the coating side is outside the curve.

  In the film according to the present invention, the absolute value of the difference between the curl values when the relative humidity is changed to 80% and 10% based on the curl measurement method is preferably 24 to 0, and preferably 15 to 0. Is more preferable, and 8 to 0 is most preferable. This is a property related to handling, peeling and cracking when films are attached under various humidity.

[Adhesion evaluation]
The adhesion between the layers of the antireflection film or between the support and the coating layer can be evaluated by the following method.

  On the surface having the coating layer, 11 square and 11 horizontal cuts are made at 1 mm intervals in a grid pattern with a cutter knife, and a total of 100 square squares are engraved, and polyester adhesive made by Nitto Denko Corporation. The tape “NO.31B” is pressure-bonded, and left for 24 hours and then peeled off. The test is repeated three times at the same place, and the presence or absence of peeling is visually observed. Of 100 squares, peeling is preferably within 10 mm, and more preferably within 2 mm.

[Brittleness test (crack resistance)]
Crack resistance is an important characteristic for preventing crack defects by handling such as application of antireflection film, processing, cutting, application of pressure-sensitive adhesive, and application to various objects.
Cut the antireflection film sample to 35mm x 140mm, leave it for 2 hours under the conditions of temperature 25 ° C and 60% RH, then measure the curvature diameter at which cracking starts when rolled up into a cylinder, and check the surface crack Can be evaluated.

  The crack resistance of the film of the present invention is preferably 50 mm or less, more preferably 40 mm or less, and most preferably 30 mm or less when the film is rolled with the coating layer side facing outward. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average.

[Surface resistance]
The film surface resistance of the present invention was measured under the conditions of 25 ° C. and 60% RH using a super insulation resistance / microammeter “TR8601” {manufactured by Advantest Co., Ltd.}. The log SR value is calculated by taking the common logarithm of the surface resistance (Ω / □).

[Dust removal]
The antireflection film of the present invention can be attached to a monitor, dust (futon, fiber waste from clothes) can be sprinkled on the monitor surface, dust can be wiped off with a cleaning cloth, and dust removal can be evaluated.
It is preferable to remove completely by wiping 6 times, and it is more preferable to remove dust completely by wiping within 3 times.

[Drawing performance of liquid crystal display]
Below, the evaluation method of a characteristic when using the antireflection film of this invention on a display apparatus, and a preferable condition are described.

  The polarizing plate on the viewing side provided in the liquid crystal display device “TH-15TA2” {manufactured by Matsushita Electric Industrial Co., Ltd.} using a TN type liquid crystal cell is peeled off, and the antireflection film or polarizing plate of the present invention is used instead. It sticks through an adhesive so that the application surface is on the viewing side and the transmission axis of the polarizing plate matches the polarizing plate attached to the product. In a 500 Lx bright room, the liquid crystal display device is displayed in black, and the following various characteristics can be evaluated visually from various viewing angles.

(Drawing image unevenness, tint evaluation)
Using a measuring instrument (“EZ-Contrast 160D”, manufactured by ELDIM), the drawing unevenness and the color change during black display (L1) are visually evaluated by a plurality of observers.
It is preferable that three people or less can recognize the unevenness, left-right color change, color change due to temperature and humidity, and white blur, and more preferably no one can recognize it.
In addition, reflection of external light is performed using a fluorescent lamp, and a change in reflection can be relatively evaluated visually.

(Light leakage of black display)
The light leakage rate of black display in the azimuth direction 45 ° and polar angle direction 70 ° from the front of the liquid crystal display device is measured. The light leakage rate is preferably 0.4% or less, and more preferably 0.1% or less.

(Contrast and viewing angle)
Contrast and viewing angle are measured using the measuring instrument “EZ-Contrast 160D” (manufactured by ELDIM) and contrast angle and viewing angle in the left and right direction (direction perpendicular to the rubbing direction of the cell) (angle range in which the contrast ratio is 10 or more) Can be checked.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

<Preparation of antireflection film>
[Preparation of coating solution for hard coat layer]
{Preparation of sol solution (a-1)}
After adding 100 parts by mass of 3-acryloyloxypropyltrimethoxysilane, 6 parts by mass of diisopropoxyaluminum ethylacetoacetate, and 12 parts by mass of i-propanol to a reactor equipped with a stirrer and a reflux condenser, ion exchange is performed. After adding 30 parts by mass of water and reacting at 60 ° C. for 4 hours, the mixture was cooled to room temperature and 6 parts by mass of acetylacetone was added to obtain a sol solution (a-1).

{Preparation of coating solution for hard coat layer (HL-1)}
“DPHA” 150.0g
Methyl ethyl ketone / cyclohexanone (50/50) 206.0 g
“MEK-ST” (30% by mass) 333.0 g
"Irgacure 184" 7.5g
Methyl ethyl ketone 49.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HL-1).

{Preparation of coating solution for hard coat layer (HL-2)}
“Desolite Z7526” (72% by mass) 347.0 g
Methyl ethyl ketone / cyclohexanone (50/50) 403.0 g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HL-2).

{Preparation of hard coat layer coating solution (HL-3)}
"DPHA" 135.0g
Methyl ethyl ketone / cyclohexanone (50/50) 196.0 g
“MEK-ST” (30% by mass) 300.0 g
Sol solution (a-1) 25.0 g
Methyl ethyl ketone 82.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HL-3).

{Preparation of hard coat layer coating solution (HL-4)}
“DPHA” 50.0g
"Irgacure 184" 2.0g
“SX-350” (30% by mass) 1.7 g
Cross-linked acrylic-styrene particles (30% by mass) 13.3 g
"FP-132" 0.75g
"KBM-5103" 10.0g
Toluene 38.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HL-4).

{Preparation of hard coat layer coating solution (HL-5)}
"Desolite Z7401" 195.0g
“DPHA” 82.0g
Sol solution (a-1) 25.8 g
“SX-350” (30% by mass) 1.7 g
Methyl ethyl ketone / cyclohexanone (50/50) 368.0 g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HL-5).

{Preparation of hard coat layer coating solution (HL-6)}
"PETA" 285.0g
"Irgacure 184" 15.0g
Sol solution (a-1) 25.8 g
Agglomerated silica (secondary particle system 1.0 μm-30 wt%) 1.7 g
Fluorine leveling agent “R-30” 0.5g
Methyl isobutyl ketone 175.0g

  The liquid mixture was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a hard coat layer forming coating liquid (HL-6).

{Preparation of hard coat layer coating solution (HL-7)}
"PETA" 285.0g
"Irgacure 184" 15.0g
Agglomerated silica (secondary particle system 1.0 μm-30 wt%) 1.7 g
Fluorine leveling agent “R-30” 0.5g
Methyl isobutyl ketone 175.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HL-7).

{Preparation of hard coat layer coating solution (HL-8)}
"PETA" 285.0g
"Irgacure 184" 15.0g
Agglomerated silica (secondary particle system 1.0 μm-30 wt%) 1.7 g
Amino compound (1-1 of the present invention) 0.4 g
p-Toluenesulfonic acid / triethylamine salt 0.004 g
Fluorine leveling agent “R-30” 0.5g
Methyl isobutyl ketone 175.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HL-8).

The compounds used are shown below.
“PETA”: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.
“DPHA”: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
"Desolite Z7526": Commercially available silica-containing UV curable hard coat solution, solid content concentration 72 mass%, silica content 38 mass%, average particle size 20 nm, manufactured by JSR Corporation.
"Desolite Z7401": Commercially available inorganic component-containing UV curable hard coat solution, solid content concentration 48.4% by mass, manufactured by JSR Corporation.
“MEK-ST”: Silica sol, average particle size 15 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Co., Ltd.
“Irgacure 184”: photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.
“SX-350”: Cross-linked polystyrene particles having an average particle size of 3.5 μm (refractive index of 1.60), 30% by mass toluene dispersion, manufactured by Soken Chemical Co., Ltd. Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
Cross-linked acrylic-styrene particles: average particle size 3.5 μm (refractive index 1.55), 30% by weight toluene dispersion, manufactured by Soken Chemical Co., Ltd.
“KBM-5103”: Silane coupling agent, acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
“FP-132”: a fluorine-based surface modifier having the following structural formula.

Agglomerated silica (secondary particle system 1.0 μm): manufactured by Nippon Silica Industry Co., Ltd.
Fluorine leveling agent “R-30”: manufactured by Dainippon Ink & Chemicals, Inc.

[Preparation of coating solution for low refractive index layer]
{Preparation of coating solution for low refractive index layer (LL-1)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Methyl ethyl ketone 116.0 g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-1) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-2)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-2) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-3)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Amino compound (1-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution (LL-3) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-4)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Amino compound (2-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-4) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-5)}
"JTA-113" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Amino compound (3-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution (LL-5) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-6)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Amino compound (5-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-6) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-7)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Amino compound (7-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for low refractive index layer (LL-7).

{Preparation of coating solution for low refractive index layer (LL-8)}
"JN-7228" 177.0g
"MEK-ST" 15.2g
Sol solution (a-1) 7.3 g
Amino compound (9-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for low refractive index layer (LL-8).

{Preparation of coating solution for low refractive index layer (LL-9)}
"P-3" 9.0g
"RMS-033" 3.3g
"MEK-ST" 7.34g
"MP-triazine" 0.11g
Sol solution (a-1) 1.14 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-9) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-10)}
"P-3" 9.0g
"RMS-033" 3.3g
"MEK-ST" 7.34g
"MP-triazine" 0.11g
Sol solution (a-1) 1.14 g
Amino compound (5-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution (LL-10) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-11)}
"P-3" 9.0g
"RMS-033" 3.3g
"MEK-ST" 7.34g
"MP-triazine" 0.11g
Sol solution (a-1) 1.14 g
Amino compound (7-1 of the present invention) 0.4 g
Methyl ethyl ketone 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-11) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-12)}
"P-3" 9.0g
"RMS-033" 3.3g
"CS-60 IPA" 12.2g
"MP-triazine" 0.11g
Sol solution (a-1) 1.14 g
Methyl ethyl ketone 85.0g
Cyclohexanone 5.5g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution (LL-12) for a low refractive index layer.

{Preparation of coating solution for low refractive index layer (LL-13)}
"P-3" 9.0g
"RMS-033" 3.3g
"CS-60 IPA" 12.2g
"MP-triazine" 0.11g
Sol solution (a-1) 1.14 g
Amino compound (7-1 of the present invention) 0.4 g
Methyl ethyl ketone 85.0g
Cyclohexanone 5.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution (LL-13) for a low refractive index layer.

The compounds used above are shown below.
“JN-7228”: thermally crosslinkable fluorine-containing polymer (refractive index: 1.42), solid content concentration: 6% by mass, manufactured by JSR Corporation.
“JTA-113”: thermally crosslinkable fluorine-containing polymer (refractive index: 1.44), solid content concentration: 6% by mass, manufactured by JSR Corporation.
“P-3”: a fluorine-containing copolymer (P-3) described in JP-A No. 2004-45462, a weight average molecular weight of about 50,000, and a solid content concentration of 23.8% by mass / MEK.
“MEK-ST”: Silica sol, average particle size 15 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Co., Ltd.
“CS-60 IPA”: “KBM-5103” surface-modified hollow silica sol (surface modification rate vs. 30% by mass of silica), refractive index 1.31, average particle size 60 nm, shell thickness 10 nm, solid content concentration 18.2%, Made by Catalytic Chemical Industry Co., Ltd.
“RMS-033”: Reactive silicone resin, manufactured by Gelest.
“MP-triazine”: photopolymerization initiator, manufactured by Sanwa Chemical Co., Ltd.

[Preparation of antireflection film]
Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-6
The hard coat layers (HL-1) to (HL-8) and the low refractive index layers (LL-1) to (LL-8) were applied as follows, and the antireflection film sample (101-1) to (108-1), (201-1) to (207-1), (301-1) to (305-1) and (40
1-1) to (405-1) were obtained. The stacking combination was performed as described in Table 1.

(1) Application of hard coat layer Triacetyl cellulose film “TAC-TD80U” (trade name) {manufactured by Fuji Photo Film Co., Ltd.} having a thickness of 80 μm is unrolled in a roll form and used for the hard coat layer. Using any of the coating liquids (HL-1) to (HL-5), a gravure roll rotation speed of 30 rpm using a microgravure roll having a diameter of 180 lines / inch and a gravure pattern of 40 μm in depth and a doctor blade. , Applied at a transfer speed of 10 m / min, dried at 120 ° C. for 2 minutes, and then “air-cooled metal halide lamp” of 160 W / cm under a nitrogen purge with an oxygen concentration of 0.1% by volume or less {eye graphics ( using Ltd.)}, illuminance 400 mW / cm ^2, and an irradiation dose of 110 mJ / cm ² to cure the coating layer, the thickness of 6.0μm Dokoto layer was formed respectively, and wound.

(2) Coating of low refractive index layer-1 (thermal curing + ionizing radiation curing system)
The triacetyl cellulose film coated with each hard coat layer as described above is unwound again, and the above-mentioned coating solution for low refractive index layer has a gravure pattern with a line number of 180 lines / inch and a depth of 40 μm, and a micro gravure roll with a diameter of 50 mm. And a doctor blade using a gravure roll at a rotation speed of 30 rpm and a conveying speed of 10 m / min, dried at 80 ° C. for 2 minutes, heated and cured at 110 ° C. for 10 minutes, and further under a nitrogen purge (oxygen concentration) Using an “air-cooled metal halide lamp” {made by Eye Graphics Co., Ltd.} of 240 W / cm at 200 ppm or less), an ultraviolet ray with an irradiation amount of 300 mJ / cm ² is irradiated to form a low refractive index layer having a thickness of 95 nm. I took it.

(3) Coating of low refractive index layer-2 (ionizing radiation curing system)
The triacetyl cellulose film coated with each hard coat layer as described above was unwound again, and the low refractive index layer coating solution was applied at a coating speed of 25 m / min using a die coater. After drying at 120 ° C. for 70 seconds, under a nitrogen purge (oxygen concentration of 200 ppm or less), using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), irradiating with an ultraviolet ray of 400 mJ / cm ² Then, a low refractive index layer having a thickness of 95 nm was formed and wound up.

[Evaluation of antireflection film sample]
The following items were evaluated for the obtained antireflection film sample. The results are shown in Table 1.

(1) Specular reflectance Reflector hardness meter "V-550" {manufactured by JASCO Corporation} is equipped with an adapter "ARV-474" and an emission angle with respect to an incident angle of 5 ° in the wavelength region of 380 to 780 nm- The specular reflectance at 5 ° was measured, the average reflectance between 450 nm and 650 nm was calculated, and the antireflection property was evaluated.

(2) Pencil hardness Pencil hardness evaluation described in JIS K-5400 was performed.
After conditioning the antireflection film at a temperature of 25 ° C. and 60% RH for 2 hours, it was evaluated using the H-5H test pencil specified in JIS S-6006 at a load of 500 g as follows. The highest hardness that results in OK was taken as the evaluation value.
In evaluation of n = 5, there is no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG

(3) Steel wool rubbing resistance A load of 500 g / cm ² was applied to steel wool of # 0000, and the state of scratches after 10 reciprocations was observed and evaluated in the following five stages.
(Double-circle): The thing which did not scratch at all.
○: Slightly invisible scratches.
Δ: Scratches clearly visible.
X: Scratches clearly visible.
XX: The film peeled off.

  By using any of the amino compounds of the general formulas (1) and (2) having a polymerization initiation site, which is an essential requirement of the present invention, the antireflection film has sufficient antireflection performance while being resistant to antireflection. It can be seen that the film has excellent scratch resistance.

Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6
In the production methods of the samples (101-1) to (405-1) of Example 1, as shown in Table 2 below, the sample (101-2) which differs only in the amount of ultraviolet irradiation when the low refractive index layer was formed. ) To (108-2), (103-3), (201-2) to (207-2), (301-2) to (305-2), and (401-2) to (405-2). A similar evaluation was made.
The amount of ultraviolet irradiation was adjusted by changing the amount of light emitted from the ultraviolet light source or changing the coating speed.

  By using any of the amino compounds of the general formulas (1) and (2) having a polymerization initiation site, which is an essential requirement of the present invention, sufficient scratch resistance is exhibited even when the amount of UV irradiation light is reduced. It can be seen that the curing reaction proceeds efficiently.

<Preparation of polarizing plate>
Example 3
[Production of protective film for polarizing plate]
A 1.5 mol / L sodium hydroxide aqueous solution was kept at 50 ° C. to prepare a saponification solution. Furthermore, a 0.005 mol / L dilute sulfuric acid aqueous solution was prepared.

  In the antireflection films prepared in Examples 1 and 2, the surface of the transparent support opposite to the side having the low refractive index layer of the present invention was saponified using the saponification solution. Next, the aqueous sodium hydroxide solution on the surface of the saponified transparent support is thoroughly washed with water, then with the above dilute sulfuric acid aqueous solution, and the dilute sulfuric acid aqueous solution is thoroughly washed with water. Dried.

  The contact angle with water on the surface of the transparent support that had been subjected to saponification treatment on the side opposite to the side having the low refractive index layer of the antireflection film was evaluated to be 40 ° or less. Thus, the protective film for polarizing plates was produced.

[Preparation of polarizing plate]
[Preparation of polarizing film]
A polyvinyl alcohol film {made by Kuraray Co., Ltd.} having a film thickness of 75 μm was immersed in an aqueous solution consisting of 1000 parts by mass of water, 7 parts by mass of iodine, and 105 parts by mass of potassium iodide to adsorb iodine. Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.

A saponified triacetyl cellulose surface of the antireflection film of the present invention (protective film for polarizing plate) was bonded to one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive. Further, a triacetyl cellulose film saponified in the same manner as described above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.

[Evaluation with image display device]
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or semi-finished polarizing plate of the present invention, which is prepared as described above, is mounted so that the antireflection film is the outermost surface of the display. The transmissive liquid crystal display device was excellent in antireflection performance and extremely excellent in visibility. In particular, the effect is remarkable in the VA mode.

Example 4
[Preparation of polarizing plate]
For the optical compensation film “Wide View Film SA 12B” {manufactured by Fuji Photo Film Co., Ltd.} having an optical compensation layer, the surface opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 3. .

  An antireflection film (protective film for polarizing plate) prepared in Examples 1 and 2 on one surface of a polarizing film using a polyvinyl alcohol adhesive as an adhesive for the polarizing film prepared in the same manner as in Example 3. The saponified surfaces of each were bonded together. Further, on the other surface of the polarizing film, the surface opposite to the side having the optical compensation layer of the saponified optical compensation film was bonded using the same polyvinyl alcohol-based adhesive.

[Evaluation with image display device]
Each of the TN, STN, IPS, VA, and OCB mode transmission type and reflection type in which the polarizing plate with an optical compensation film of the present invention prepared as described above is mounted so that the antireflection film becomes the outermost surface of the display. Or, transflective liquid crystal display devices have better contrast in a bright room than liquid crystal display devices equipped with polarizing plates that do not use an optical compensation film, have a very wide viewing angle in the vertical and horizontal directions, and reflectivity. Excellent prevention performance and extremely excellent visibility and display quality. In particular, the effect is remarkable in the VA mode.

FIG. 1 is a schematic cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention. FIG. 2 is a schematic cross-sectional view schematically showing another preferred embodiment of the antireflection film of the present invention. FIG. 3 is a schematic sectional view schematically showing still another preferred embodiment of the antireflection film of the present invention. FIG. 4 is a schematic cross-sectional view schematically showing still another preferred embodiment of the antireflection film of the present invention. FIG. 5 is a schematic sectional view schematically showing still another preferred embodiment of the antireflection film of the present invention.

FIG. 6 is a cross-sectional view of the coater 10 using the slot die 13 used in the practice of the present invention. 7A shows the sectional shape of the slot die 13 used in the practice of the present invention, and FIG. 7B shows the sectional shape of the conventional slot die 30. FIG. 8 is a perspective view showing the slot die 13 and its periphery in the coating process employed in the practice of the present invention. FIG. 9 is a cross-sectional view showing the vacuum chamber 40 and the web W that are close to each other. (The back plate 40a is integrated with the main body of the chamber 40)

Explanation of symbols

1: Support 2: Hard coat layer, antiglare layer, antistatic layer 3: Medium refractive index layer 4: High refractive index layer 5: Low refractive index layer

10: Coater 11: Backup roll W: Web 13: Slot die 14: Coating liquid 14a: Bead 14b: Coating film 15: Pocket 16: Slot 16a: Slot opening 17: Tip lip 18: Land 18a: Upstream lip land 18b : Ripland on the downstream side

I _UP : Land length of the upstream lip land 18a I _LO : Land length of the downstream lip land 18b LO: Over bite length (difference in distance between the downstream lip land 18b and the web W of the upstream lip land 18a )
G _L : gap between the tip lip 17 and the web W (gap between the downstream lip land 18b and the web W)

30: conventional slot-die 31a: upstream lip land 31b: downstream lip land 32: Pocket 33: Slot 40: vacuum chamber 40a: back plate 40b: side plate 40c: threaded G _B: between the back plate 40a and the web W G _S : Gap between the side plate 40b and the web W

Claims (12)

The layer coated on the transparent support has at least an amino compound represented by the following general formula (1) or (2) having a polymerization initiation site having a photo-radical polymerization initiator or a thermal radical polymerization initiator as a basic skeleton. The optical film characterized by including the hardened | cured material of the composition containing any 1 type .
General formula (1):

General formula (2):

(In the formula, X represents an alkyl group or a substituted or unsubstituted alkyl group or aryl group having the polymerization initiation site, provided that at least one of X is a substituted or unsubstituted group having the polymerization initiation site. An alkyl group or an aryl group.) An antireflection film having at least an antireflection layer on a transparent support, wherein at least one of the layers laminated on the support is a polymerization initiator having a radical radical polymerization initiator or a thermal radical polymerization initiator as a basic skeleton. It is a layer formed by curing a composition containing at least one of amino compounds represented by the following general formula (1) or (2) having a moiety with light and / or heat energy Antireflection film.
General formula (1):

General formula (2):

(In the formula, X represents an alkyl group or a substituted or unsubstituted alkyl group or aryl group having the polymerization initiation site, provided that at least one of X is a substituted or unsubstituted group having the polymerization initiation site. An alkyl group or an aryl group.) An antireflective film having a low refractive index layer formed of a composition containing at least a hard coat layer and a binder polymer on a transparent support, wherein any one of the layer forming compositions has the general formula (1) The antireflection film according to claim 2, comprising at least one of amino compounds represented by (2) or (2) .   The antireflection film according to claim 3, wherein the low refractive index layer contains an inorganic filler selected from silica, hollow silica and magnesium fluoride.   The antireflection film according to claim 3 or 4, wherein the binder polymer of the low refractive index layer is a fluorine-containing polymer.   The hard coat layer contains an inorganic filler made of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and silicon. Antireflection film. The method for producing an optical film according to claim 1, wherein the coated layer is formed by coating on a transparent support by a die coating method.   The method for producing an antireflection film according to any one of claims 2 to 6, wherein at least one layer of the antireflection film is formed on a transparent support by a die coating method. Method. The method for producing an antireflection film according to any one of claims 3 to 6, wherein the low refractive index layer is applied and dried and then cured by irradiation with ionizing radiation in an atmosphere having an oxygen concentration of 3% or less. . The antireflective film according to any one of claims 3 to 6, wherein the low refractive index layer is applied, dried, heat-cured, and cured by irradiation with ionizing radiation in an atmosphere of 3% or less . A manufacturing method or a manufacturing method of an antireflection film according to claim 9.   The antireflection film according to any one of claims 2 to 6 or the antireflection film produced by the production method according to any one of claims 8 to 10, wherein the two protective films of the polarizing layer in the polarizing plate A polarizing plate characterized by being used for at least one of them. The antireflection film according to any one of claims 2 to 6, the antireflection film produced by the production method according to any one of claims 8 to 10, or a display device comprising the polarizing plate according to claim 11. A display device, wherein the antireflection layer or the low refractive index layer is disposed on the viewing side.

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