JP5309597B2 - Method for manufacturing antireflection film and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an antireflective film, the method being excellent in productivity, by which the antireflective film having excellent antireflection performance is manufactured without requiring a complicated process, and to provide an image display device excellent in surface frictional flaw resistance, alkali resistance and antireflection performance. <P>SOLUTION: The method for manufacturing the antireflective film constitutes two layers different in refractive indexes by a step of applying and drying once a one-liquid type paint composition containing two or more inorganic particles, wherein at least one inorganic particle is surface-coated with a fluorine compound, and the paint composition contains a fluorinated alkyl group containing (meth) acrylate. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an antireflection film, and an image display device including an antireflection film produced by using the production method.

  In recent years, with the spread of liquid crystal display panels (LCD), plasma display panels (PDP), etc., there are problems such as reflection of external light and reflection of external images on the display surfaces of these image display units. A structure in which an antireflection film is formed on the display surface has been proposed and used. In general, the following two methods can be mentioned. One is a method of forming an antireflection film on the surface of the substrate by vapor deposition or sputtering (see, for example, Patent Document 1), and the other method is to apply an antireflection coating solution on the surface of the substrate. This is a method of forming an antireflection film by applying and drying (for example, see Patent Document 2).

  In any method, in order to reduce the reflectance in a wider wavelength region, a multilayer antireflection film in which a layer made of a material with a high refractive index and a layer made of a material with a low refractive index are laminated, so-called Multi-coating is generally used (see, for example, Patent Document 3).

  However, in order to form such a multilayer film, it is necessary to form a high refractive index layer made of a material having a high refractive index and then to form a low refractive index layer having a low refractive index on the upper layer. The process requires two steps, and the manufacturing process is complicated and increases the cost.

  In addition, since these antireflection films are located on the outermost surface of the display surface, fingerprints and dust are likely to adhere to the display surface, and when they are wiped off using an alkaline household detergent, they are antireflective. There were problems such as scratches on the film (abrasion resistance) and damage to the film by alkali.

  Such a problem can be solved by using a low refractive index coating agent containing a monomer having an epoxy group or amino group, dimethyl silicone oil and hollow silica. However, the reflectance is higher than 1%, the characteristics of the original antireflection film are impaired, and the low refractive index layer is laminated on the high refractive index layer, so that the manufacturing process becomes complicated. (For example, see Patent Document 4).

  On the other hand, although there is a report that an ethylenic fluoropolymer is used for the low refractive index layer and the low refractive index layer and the high refractive index layer are formed in one step, the scratch resistance and antireflection properties are good, No mention is made of alkali resistance (for example, see Patent Document 5).

Thus, an antireflection film having excellent surface scratch resistance and alkali resistance without performing complicated steps and further having excellent antireflection properties has not yet been proposed, and the development of this film is an image. It can be suitably used as a display device.
Japanese Unexamined Patent Publication No. 6-0667019 JP-A-6-136062 JP-A-7-005452 JP 2007-225930 A JP 2007-39619 A

  An object of the present invention is a method for producing an antireflection film excellent in productivity, a method for producing an antireflection film having excellent antireflection properties without performing complicated steps, and a reflection obtained by the production method. An object of the present invention is to provide an image display device including a prevention film. A further object of the present invention is to provide a method for producing an antireflection film having excellent surface scratch resistance, alkali resistance and antireflection properties, and an image display device comprising the antireflection film obtained by the production method. is there.

〔式中、Ｙは酸素原子、または硫黄原子であり、ｐとｑは同一でも異なっていても良い１〜４の整数であり、ＲｆとＲｆ ^１ は同一でも異なっていても良い−Ｃ _ｎ Ｆ_２ｎ＋１ （ｎは１〜２０の整数である。）である。〕
（２） フッ素化合物により表面処理された無機粒子がシリカ粒子であり、他の無機粒子が該シリカ粒子よりも屈折率が高い無機粒子であることを特徴とする、前記（１）に記載の反射防止フイルムの製造方法。
（３） 前記表面処理が、前記シリカ粒子を下記の群（Ｉ）から選ばれる化合物で処理し、更に下記の群（ＩＩ）から選ばれる化合物で処理することを特徴とする、前記（２）に記載の反射防止フイルムの製造方法。
群（Ｉ）：
アクリロキシエチルトリメトキシシラン、アクリロキシプロピルトリメトキシシラン、アクリロキシブチルトリメトキシシラン、アクリロキシペンチルトリメトキシシラン、アクリロキシヘキシルトリメトキシシラン、アクリロキシヘプチルトリメトキシシラン、メタクリロキシエチルトリメトキシシラン、メタクリロキシプロピルトリメトキシシラン、メタクリロキシブチルトリメトキシシラン、メタクリロキシヘキシルトリメトキシシラン、メタクリロキシヘプチルトリメトキシシラン、メタクリロキシプロピルメチルジメトキシシラン、メタクリロキシプロピルメチルジメトキシシラン、およびこれら化合物中のメトキシ基が他のアルコキシル基および水酸基に置換された化合物。
群（ＩＩ）：
２，２，２−トリフルオロエチルアクリレート、２，２，３，３，３−ペンタフロオロプロピルアクリレート、２−パーフルオロブチルエチルアクリレート、３−パーフルオロブチル−２−ヒドロキシプロピルアクリレート、２−パーフルオロヘキシルエチルアクリレート、３−パーフルオロヘキシル−２−ヒドロキシプロピルアクリレート、２−パーフルオロオクチルエチルアクリレート、３−パーフルオロオクチル−２−ヒドロキシプロピルアクリレート、２−パーフルオロデシルエチルアクリレート、２−パーフルオロ−３−メチルブチルエチルアクリレート、３−パーフルオロ−３−メトキシブチル−２−ヒドロキシプロピルアクリレート、２−パーフルオロ−５−メチルヘキシルエチルアクリレート、３−パーフルオロ−５−メチルヘキシル−２−ヒドロキシプロピルアクリレート、２−パーフルオロ−７−メチルオクチル−２−ヒドロキシプロピルアクリレート、テトラフルオロプロピルアクリレート、オクタフルオロペンチルアクリレート、ドデカフルオロヘプチルアクリレート、ヘキサデカフルオロノニルアクリレート、ヘキサフルオロブチルアクリレート、２，２，２−トリフルオロエチルメタクリレート、２，２，３，３，３−ペンタフルオロプロピルメタクリレート、２−パーフルオロブチルエチルメタクリレート、３−パーフルオロブチル−２−ヒドロキシプロピルメタクリレート、２−パーフルオロオクチルエチルメタクリレート、３−パーフルオロオクチル−２−ヒドロキシプロピルメタクリレート、２−パーフルオロデシルエチルメタクリレート、２−パーフルオロ−３−メチルブチルエチルメタクリレート、３−パーフルオロ−３−メチルブチル−２−ヒドロキシプロピルメタクリレート、２−パーフルオロ−５−メチルヘキシルエチルメタクリレート、３−パーフルオロ−５−メチルヘキシル−２−ヒドロキシプロピルメタクリレート、２−パーフルオロ−７−メチルオクチルエチルメタクリレート、３−パーフルオロ−７−メチルオクチルエチルメタクリレート、テトラフルオロプロピルメタクリレート、オクタフルオロペンチルメタクリレート、オクタフルオロペンチルメタクリレート、ドデカフルオロヘプチルメタクリレート、ヘキサデカフルオロノニルメタクリレート、１−トリフルオロメチルトリフルオロエチルメタクリレート、ヘキサフルオロブチルメタクリレート。
（４） 前記シリカ粒子よりも屈折率が高い無機粒子が、金属酸化物であり、
該金属酸化物が、インジウム含有酸化スズ（ＩＴＯ）及び／またはアンチモン含有酸化スズ（ＡＴＯ）であることを特徴とする、前記（２）又は（３）に記載の反射防止フイルムの製造方法。
（５） 前記（１）〜（４）のいずれかに記載の製造方法にて得られた反射防止フィルム。
（６） 前記（５）の反射防止フイルムを設けたことを特徴とする画像表示装置。 In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
(1) An antireflection film comprising two layers having different refractive indexes by a step of coating and drying a one-component coating composition containing two or more types of inorganic particles by irradiation with heat or energy rays and then curing. A manufacturing method of
At least one kind of inorganic particles is surface-treated with a fluorine compound,
The coating composition includes an initiator and a fluorinated alkyl group-containing (meth) acrylate,
The amount of the fluorinated alkyl group-containing (meth) acrylate is 5 to 40 parts by weight with respect to 100 parts by weight of the total solid content of the coating composition,
The fluorinated alkyl group-containing (meth) acrylate is a Michael addition reaction between a compound (a) having two or more (meth) acryloyl groups and a compound (b) having a fluorinated alkyl group and active hydrogen. A fluorinated alkyl group-containing (meth) acrylate obtained in
The compound (b) having the fluorinated alkyl group and active hydrogen is a compound represented by the following general formula (1) or a compound represented by the following general formula (2). Film production method.
General formula (1)
Rf (CH ₂ ) _m ZH (1)
[In formula, m is an integer of 0-20. Rf is _-C n _{F 2n +} 1 (n is an integer from 1 to 20.). Z is a nitrogen atom, a sulfur atom , or —SO ₂ —NR— (R is an alkyl group having 1 to 6 carbon atoms) covalently bonded to an alkyl group having 1 to 6 carbon atoms. ]
General formula (2)

[Wherein, Y is an oxygen atom or a sulfur atom, p and q are the same or different integers of 1 to 4, and Rf and Rf ¹ may be the same or different -C _n F _{2n + 1} (n is an integer of 1 to 20). ]
(2) The reflection according to (1), wherein the inorganic particles surface-treated with a fluorine compound are silica particles, and the other inorganic particles are inorganic particles having a higher refractive index than the silica particles. Method for manufacturing prevention film.
(3) The surface treatment is characterized in that the silica particles are treated with a compound selected from the following group (I) and further treated with a compound selected from the following group (II). A method for producing an antireflection film as described in 1. above.
Group (I):
Acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltrimethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxy Roxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, and other methoxy groups in these compounds A compound substituted with an alkoxyl group and a hydroxyl group.
Group (II):
2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-par Fluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro- 3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro-5-methyl Hexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluoro Octylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, -Perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2- Hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadeca Fluorononyl methacrylate, 1-trifluoromethyl trifluoroethyl methacrylate, hexafluorobutyl methacrylate.
(4) Inorganic particles having a refractive index higher than that of the silica particles are metal oxides,
The method for producing an antireflection film according to (2) or (3), wherein the metal oxide is indium-containing tin oxide (ITO) and / or antimony-containing tin oxide (ATO).
(5) An antireflection film obtained by the production method according to any one of (1) to (4).
(6) An image display device comprising the antireflection film of (5).

  According to the present invention, it is possible to form two layers having different refractive indexes on a supporting substrate by only applying and drying a single coating composition once, so that the antireflection exhibiting good antireflection performance. Since the film can be formed and the manufacturing process of the antireflection film can be simplified, productivity can be improved. Further, according to the production method of the present invention, an antireflection film having good scratch resistance and alkali resistance can be provided. Furthermore, by forming a functional multilayer structure such as a hard coat layer on an antireflection film and using it in an image display device, an image display device with excellent productivity can be provided.

  Hereinafter, embodiments of the present invention will be described in detail.

  As a result of intensive studies, the present inventors have obtained a one-component coating composition containing two or more types of inorganic particles, and at least one type of inorganic particles in the coating composition has been surface-treated with a fluorine compound. Furthermore, when the coating composition contains a fluorinated alkyl group-containing (meth) acrylate, the refractive index of the coating composition is different on the supporting substrate only by applying and drying the coating composition to the supporting substrate once. It has been found that a film comprising two layers and having good antireflection performance, scratch resistance and alkali resistance can be produced.

  Furthermore, as a result of intensive studies, the present inventors have found that inorganic particles that have been surface-treated with a fluorine compound that becomes a low refractive index layer when the paint is applied and dried, and a high refractive index layer when the paint is applied and dried. The coating composition is mixed with other inorganic particles and further added with a fluorinated alkyl group-containing (meth) acrylate, and the coating composition is applied to the supporting substrate once and dried. Two layers having different refractive indexes were formed on the material to produce a film having good antireflection performance, scratch resistance and alkali resistance. One of the preferred embodiments of the antireflection film of the present invention is a low refractive index layer derived from inorganic particles surface-treated with a fluorine compound, and further under the low refractive index layer and above the support substrate. And an antireflection film having a high refractive index layer formed by laminating other inorganic particles.

The present invention also includes an image display device provided with the antireflection film.
[Anti-reflective film]
The antireflection film agrees with the antireflection film, and its necessity and required performance are preferably 0.03 or more, more preferably 0.00, as described in JP-A-59-50401. This is an aspect constituted by laminating two layers having a refractive index difference of 05 or more on a support material. Moreover, it is preferable that the refractive index difference of two layers on a support base material is 5.0 or less.

  In the antireflection film, it is more preferable that the most distant layer measured from the support substrate is a low refractive index layer. That is, a mode in which a supporting substrate, a high refractive index layer, and a low refractive index layer are laminated in this order is preferable. In addition, although a support base material is mentioned later, it is also possible to provide other layers, such as a hard-coat layer, between a support base material and a high refractive index layer.

  The difference in refractive index is a value obtained by relatively comparing the refractive indexes between adjacent layers. A layer having a relatively low refractive index is called a low refractive index layer, and a layer having a relatively high refractive index is a high refractive index. Call a layer.

  According to the method for producing an antireflective film of the present invention, an antireflective film having two layers having different refractive indexes is produced by applying and drying a one-component coating composition containing two or more kinds of inorganic particles once. be able to. According to a more preferred embodiment, a single coating composition containing two or more kinds of inorganic particles is applied and dried once, thereby a high refractive index layer on the support substrate and a low refractive index on the high refractive index layer. An antireflection film having an index layer can be produced.

  In the present invention, the principle of constituting two layers from one liquid coating composition is considered to form a phase separation structure using the surface free energy difference of two or more kinds of inorganic particles as a driving force. It is considered that the lower the surface free energy, the easier the inorganic particles move to the air layer side, and the smaller the specific gravity, the easier it is to move to the upper layer side.

  In addition, in the antireflection film obtained by such a production method of the present invention, it is desirable that there is a clear interface between the high refractive index layer and the low refractive index layer.

  A clear interface in the present invention refers to a state in which one layer can be distinguished from another layer. The distinguishable interface refers to an interface that can be determined by observing a cross section using a transmission electron microscope (TEM).

  In order to show good performance as an antireflection film, it is preferably 1.0% or less, more preferably 0.5% or less in spectroscopic measurement. The reflectance is preferably as small as possible, but there is no particular lower limit. However, a reflectance of about 0.01% is considered to be a sufficient value as an antireflection film. The minimum reflectance refers to the value at which the reflectance is lowest in the wavelength region from 400 nm to 800 nm when the light reflection spectrum is measured. When comparing the antireflection performance of films, the minimum reflectance is an index, and it can be said that the smaller the minimum reflectance value, the better the antireflection performance.

Further, in order to exhibit good properties as an antireflection film, it is desirable that the transparency is higher. When an antireflection film with low transparency is used for an image display device, the image display device is deteriorated due to a decrease in image saturation or the like, which is not preferable. The antireflection film of the present invention used a haze value as an evaluation of transparency. Haze is an index of turbidity of a transparent material defined in JIS K 7136. The smaller the haze, the higher the transparency. The haze value of the antireflection film is preferably 3.0% or less, more preferably 1.0% or less. Further, the lower the haze, the better in terms of transparency, but it is difficult to make it 0%, and the practical lower limit is considered to be about 0.01%. If the haze value exceeds 3.0%, the possibility of image deterioration increases, which is not preferable.
[Coating composition]
The coating composition in the present invention contains two or more kinds of inorganic particles and a fluorinated alkyl group-containing (meth) acrylate. Further, at least one kind of inorganic particles is surface-treated with a fluorine compound. The inorganic particles and the fluorinated alkyl group-containing (meth) acrylate will be described later.
[Inorganic particles]
The coating composition used in the production method of the present invention contains two or more types of inorganic particles. The number of types of inorganic particles is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, and still more preferably. Is 2 or more and 3 or less.

  The kind of the inorganic particles is not particularly limited as long as the two layers having different refractive indexes are formed when the coating composition of one liquid containing the inorganic particles is applied and dried once on the support. For example, the metal atom Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Zr, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B, Bi, Mo, Inorganic particles containing at least one metal atom selected from Ce, Cd, Be, Pb, Eu and the like can be mentioned. In addition, the inorganic particles may include a plurality of metals, and preferably, inorganic particles containing one or more and five or less metals may be used.

The inorganic particles that are preferably used as the low refractive index layer component of the antireflection film having two layers on the support substrate are inorganic particles containing an element selected from Si, Na, K, Ca, and Mg. And more preferably inorganic particles containing a compound selected from silica particles (SiO ₂ ), alkali metal fluorides (NaF, KF, etc.), and alkaline earth metal fluorides (CaF ₂ , MgF _2, etc.), Silica particles are particularly preferable from the viewpoints of durability and refractive index.

Silica particles that are preferably used as inorganic particles of the low refractive index layer component refer to particles comprising a composition comprising either a silicon compound or a polymerized (condensed) organic silicon compound. As a general example, SiO A general term for particles derived from silicon compounds such as ₂ .

  The shape of the inorganic particles constituting the low refractive index layer is not particularly limited, but is preferably spherical from the viewpoint of the refractive index of the layer formed after lamination, more preferably has a cavity inside the particle, or the surface And it is preferable to have pores inside. If the inorganic particles have a polyhedral structure, there is a possibility that the inorganic particles are laminated without any gaps in the layer, and it is considered that the transparency required for the image display device cannot be obtained. Moreover, the effect of lowering the density of the layer can be obtained by using inorganic particles having cavities inside the particles or having pores on the surface and inside. In particular, the silica particles have cavities, or have pores on the surface and inside, so that the silica particles are contained in the low refractive index layer of the antireflection film according to the production method of the present invention, and the low refractive index layer is suitable. It is preferable because it is formed. The silica particles having cavities inside or having pores on the surface and inside are hereinafter referred to as hollow silica particles.

  If the number average particle diameter of the inorganic particles contained in the low refractive index layer is smaller than 1 nm, the void density in the layer may decrease, which may cause an increase in refractive index and a decrease in transparency. If the number average particle diameter is larger than 200 nm, the thickness of the low refractive index layer is so thick that it may not be possible to obtain good antireflection performance. Therefore, at least one inorganic particle used in the production method of the present invention is not preferred. Has a number average particle size of preferably 1 nm to 200 nm, more preferably 5 nm to 180 nm, and even more preferably 10 nm to 150 nm. The number average particle diameter of the hollow silica particles is particularly preferably in the above range.

  The number average particle diameter in the present invention refers to the particle diameter determined by a transmission electron microscope. The magnification was 500,000 times, the outer diameters of 10 particles present on the screen were measured, and the average value was obtained.

  The weight ratio of the inorganic particles in the low refractive index layer is preferably 1% by weight or more and 90% by weight or less, more preferably 5% by weight or more, with respect to 100% by weight of all components of the low refractive index layer. 80% by weight or less, more preferably 10% by weight or more and 70% by weight or less. When the content of the inorganic particles is less than 1% by weight in 100% by weight of all components of the low refractive index layer, a good low refractive index may not be obtained, and the content of the inorganic particles is 90% by weight Exceeding this may cause problems such as poor film-forming properties and adhesion to the high refractive index layer, and loss of the distinguishable interface between the high refractive index layer and the low refractive index layer.

  Since inorganic particles that have been surface-treated with a fluorine compound can form a low refractive index layer suitably, at least one inorganic particle of two or more types of inorganic particles used in coating compositions contains a fluorine compound. It is important that the surface treatment is performed. It should be noted that both inorganic particles that have been subjected to a surface treatment with a fluorine compound and inorganic particles that have not been subjected to the surface treatment are compared to the case where all of the inorganic particles of two or more types of inorganic particles have been subjected to a surface treatment with a fluorine compound. It is preferable to use a one-component coating composition containing, from the viewpoint of antireflection properties because two layers having a large refractive index difference can be obtained.

  In addition, the inorganic particles subjected to the surface treatment with the fluorine compound are particularly preferably silica particles such as hollow silica particles.

  The surface treatment process using a fluorine compound may be performed in one stage or in multiple stages. Further, the fluorine compound may be used in a plurality of stages, or the fluorine compound may be used in only one stage.

  Moreover, the fluorine compound preferably used in the surface treatment step of the inorganic particles may be a single compound or a plurality of different compounds.

  Surface treatment with a fluorine compound refers to a step of chemically modifying inorganic particles and introducing a fluorine-containing compound into the inorganic particles.

  As a method of directly introducing a fluorine compound into inorganic particles, at least one fluoroalkoxysilane compound having both a fluorine segment and a silyl ether group (including a silanol group obtained by hydrolyzing a silyl ether group) in one molecule is used. There is a method in which the above and the initiator are stirred together. However, when the fluorine compound is directly introduced into the inorganic particles, it may be difficult to control the reactivity, or application spots may easily occur during application after coating.

  Further, as a further method for chemically modifying the inorganic particles and introducing the fluorine-containing compound into the inorganic particles, there is a method in which the inorganic particles are treated with a crosslinking component and are combined with a fluorine compound having a functional group.

  A crosslinking component is a compound that contains no fluorine in the molecule but has at least one site capable of reacting with a fluorine compound and one site capable of reacting with inorganic particles in one molecule. A possible site is preferably silyl ether or a hydrolyzate of silyl ether from the viewpoint of reactivity. These compounds are generally called silane coupling agents. For example, glycidoxyalkoxysilanes, aminoalkoxysilanes, acryloylsilanes, methacryloylsilanes, vinylsilanes, mercaptosilanes, etc. may be used. it can.

  As the fluorine compound having a functional group, fluoroalkyl alcohol, fluoroalkyl epoxide, fluoroalkyl halide, fluoroalkyl acrylate, fluoroalkyl methacrylate, fluoroalkyl carboxylate (including acid anhydrides and esters), and the like can be used. it can.

  In a more preferred embodiment of the surface treatment of the inorganic particles with the fluorine compound in the present invention, the silica particles are treated with a compound represented by the following general formula (I) and further treated with a compound represented by the following general formula (II). preferable.

AR ¹ —SiR ² _n (OR ² ) _3-n General Formula (I)
AR ¹ -Rf Formula (II)
(In the above general formula, A represents a reactive double bond group, R ¹ represents an alkylene group having 1 to 3 carbon atoms and an ester structure derived therefrom, and R ² represents hydrogen or 1 to 4 carbon atoms. Rf represents a fluoroalkyl group, n represents 0, 1 or 2, and each may have a side chain in the structure.)
Specific examples of the general formula (I) include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltri Methoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxy Examples include silane and compounds in which the methoxy group in these compounds is substituted with other alkoxyl groups and hydroxyl groups. The

  Specific examples of the general formula (II) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- Perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexa Decafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl- 2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perful Rhodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5 -Methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodeca Fluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexaf Examples include bromobutyl methacrylate.

  By using the compound represented by the general formula (I) having no fluorine segment in the molecule, it becomes possible not only to modify the surface of the inorganic particles under simple reaction conditions, but also to make the surface of the inorganic particles reactive. It becomes possible to introduce a functional group that is easy to control, and as a result, it is possible to react a fluorine segment having a reactive double bond on the surface of the inorganic particles.

  The weight ratio of the fluorine compound derived from the compound represented by the general formula (II) in 100% by weight of all components in the low refractive index layer is preferably 0.1% by weight to 45% by weight, more preferably It is 1 to 40% by weight, and more preferably 5 to 35% by weight. When the content of the fluorine compound is less than 0.1% by weight in 100% by weight of all the constituent components of the low refractive index layer, good layer separation is not formed, and consequently, good antireflection performance cannot be obtained. When it is more than 45% by weight, problems such as a decrease in solubility and a deterioration in film forming property occur.

  The low refractive index layer is one of the layers laminated on the support substrate, and is a layer having a relative refractive index lower than that of one adjacent layer (excluding the air layer). is there. In addition, as described above, the antireflection film obtained by the production method of the present invention preferably has a support base, a high refractive index layer, and a low refractive index layer formed in this order. As a method for reducing the refractive index, a method using a fluorine-based polymer (Japanese Patent Laid-Open No. 2002-36457) and a method of reducing the density (Japanese Patent Laid-Open No. 8-83581) are known. It is important that the refractive index layer contains inorganic particles that have been surface-treated with a fluorine compound. The inorganic particles and the compounds represented by the general formula (I) and the general formula (II) described above remain unreacted in the coating composition used in the present invention, the inorganic particles, the general formula (I) compound and the general formula. The compound (II) may be present, or the inorganic particles may be present as a condensation and / or polymer by surface treatment with the compound of the general formula (I) and the compound of the general formula (II).

  The low refractive index layer of the present invention may further contain a binder component in addition to the above substances. The binder component is not limited as long as it is a curable resin component such as heat and active energy rays, but from the viewpoint of retaining the inorganic particles surface-treated with the fluorine compound of the present invention in the molecule. It preferably has an alkoxysilane, a hydrolyzate of alkoxysilane, or a reactive double bond.

  Next, the high refractive index layer will be described.

The high refractive index layer is one of the layers laminated on the support substrate, refers to a layer having a higher refractive index than the adjacent layers, and includes at least one kind of inorganic particles. preferable. The inorganic particles used as the high refractive index layer component are not particularly limited, but are preferably inorganic particles different from the inorganic particles used as the low refractive index layer component, Zr, Ti, Al, In, Zn, Sb. Preferably, the oxide particles are at least one metal selected from the group consisting of Sn, Sn, and Ce. The inorganic particles used as the high refractive index layer component are preferably inorganic particles having a higher refractive index than silica particles. Specifically, zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO 2), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ) One metal oxide, particularly preferably indium-containing tin oxide (ITO) or antimony-containing tin oxide (ATO) derived from Sb or Sn.

  As the number average particle diameter of inorganic particles suitable as a high refractive index layer constituent, particularly as the average particle shape of inorganic particles made of metal oxide having a higher refractive index than silica particles suitable as a low refractive index layer constituent, Is from 1 nm to 150 nm, more preferably from 5 nm to 100 nm. If the number average particle diameter of the inorganic particles is smaller than 1 nm, it is not preferable because the transparency decreases due to a decrease in the void density in the layer. If the number average particle diameter of the inorganic particles is larger than 150 nm, the high refractive index layer is not preferable. The thickness becomes large, and good antireflection performance cannot be obtained.

  The refractive index of inorganic particles suitable as a high refractive index layer constituent, particularly the refractive index of inorganic particles made of a metal oxide having a higher refractive index than silica particles suitable as a low refractive index layer constituent, is preferably 1. It is 60-2.80, More preferably, it is 1.60-2.50. When the refractive index of the inorganic particles is smaller than 1.60, the refractive index of the high refractive index layer may be lowered. When the refractive index of the inorganic particles is larger than 2.80, the refractive index of the high refractive index layer is increased. In some cases, good antireflection performance cannot be obtained.

  As described above for the inorganic particles used as the high refractive index layer component, if the inorganic particles that have been surface-treated with a fluorine compound are silica particles, the inorganic particles may have higher refractive index than the silica particles. Particularly preferred as such inorganic particles having a higher refractive index than the silica particles are metal oxides having a number average particle diameter of 1 to 150 nm and a refractive index of 1.60 to 2.80. . Specific examples of such metal oxides include indium-containing tin oxide (ITO) and / or antimony-containing tin oxide (ATO).

  In the coating composition used in the production method of the present invention, when the inorganic particles surface-treated with the fluorine compound are silica particles and the other inorganic particles are inorganic particles having a higher refractive index than the silica particles, A preferred embodiment because a layer containing the silica particles and a high refractive index layer containing inorganic particles having a higher refractive index than the silica particles can be suitably formed by applying and drying the coating composition once on the material. It is.

The coating composition used in the present invention may further contain a binder component. Although it does not specifically limit as a binder component, It is preferable that it is a binder (resin) hardened | cured with a heat | fever and / or active energy ray from a viewpoint of manufacturability, and the resin component as a binder is one type. Alternatively, two or more types may be mixed and used. In the case of curing with heat, the temperature is preferably from room temperature to 200 ° C. from the production cost, and in the case of active energy rays, EB and / or UV rays are preferred from the viewpoint of versatility.
[Fluorinated alkyl group-containing (meth) acrylate]
The coating composition used in the production method of the present invention includes two or more types of inorganic particles in which at least one type of inorganic particles are surface-treated with a fluorine compound, and further contains a fluorinated alkyl group-containing (meth) acrylate. It is important to include. As a more preferred embodiment, particles suitable as a low refractive index layer constituent component such as silica particles subjected to surface treatment with the aforementioned fluorine compound, and particles suitable as a high refractive index layer constituent component such as the above metal oxide particles And a fluorinated alkyl group-containing (meth) acrylate.

  The fluorinated alkyl group-containing (meth) acrylate in the coating composition used in the production method of the present invention is not particularly limited. For example, the compound (a) having two or more (meth) acryloyl groups, a fluorinated alkyl group, A fluorinated alkyl group-containing (meth) acrylate compound obtained from the compound (b) having active hydrogen is preferable. Two or more (meth) acryloyl groups are a generic term for acryloyl groups and methacryloyl groups. The fluorinated alkyl group-containing (meth) acrylate preferably has 10 or less (meth) acryloyl groups. More preferably, the fluorinated alkyl group-containing (meth) acrylate has 2 or more and 6 or less (meth) acryloyl groups.

Here, the fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group), and one in which some hydrogen atoms in the alkyl group are substituted with fluorine atoms. (For example, HCF ₂ CF ₂ CF ₂ CF ₂ — etc.) is a general term. Incidentally, those containing an oxygen atom in the fluorinated alkyl group _{(e.g., CF 3 - (OCF 2 CF} 2) 2 - , etc.) is also included in this definition.

  The use of fluorinated alkyl group-containing (meth) acrylates alone, or the use of curable compositions containing them, as an optical material such as an antireflection film, has a three-dimensional structure due to optical properties such as reducing the refractive index and crosslinking reaction. It is useful for forming scratches and exhibiting scratch resistance and alkali resistance. The fluorinated alkyl group-containing (meth) acrylate is considered to exist in the low refractive index layer and / or at the interface between the low refractive index layer and the high refractive index layer.

  Specific examples of the compound (a) having two or more (meth) acryloyl groups include the following compounds.

  First, as the bifunctional (meth) acrylate, for example, 1,3-butylene glycol diacrylate (for example, SR-212 manufactured by Kayaku Sartomer Co., Ltd.), 1,4-diol diacrylate (for example, Osaka Organic Chemistry) Biscoat # 195, etc.), 1,6-hexanediol diacrylate (for example, 1,6HX-A manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide (hereinafter abbreviated as EO) modified 1,6-hexanediol diacrylate (for example, RCC13-361 manufactured by San Nopco Co., Ltd.), epichlorohydrin (hereinafter abbreviated as ECH) modified 1,6-hexanediol diacrylate (eg, Kayrad R-167 manufactured by Nippon Kayaku Co., Ltd.), 1,9-nonanediol Diacrylate (for example, Biscoe manufactured by Osaka Organic Chemical Co., Ltd.) # 215 etc.), diethylene glycol diacrylate (for example, Bremer ADE-100 manufactured by NOF Corporation), ECH-modified hexahydrophthalic acid diacrylate (for example, Denacol acrylate DA-722 manufactured by Nagase Kasei Co., Ltd.), hydroxypivalic acid, etc. Neopentyl glycol diacrylate (such as Kyoeisha Chemical Co., Ltd. light acrylate HPP-A), neopentyl glycol diacrylate (such as Kayrad NPGDA manufactured by Nippon Kayaku Co., Ltd.), EO-modified neopentyl glycol diacrylate (such as San Nopco shares) Company photomer 4160), propylene oxide (hereinafter abbreviated as PO) modified neopentyl glycol diacrylate (eg, SR-9003 manufactured by Kayaku Sartomer Co., Ltd.), Phosphoric acid-modified pentaerythritol diacrylate (for example, Aronix M-233 manufactured by Toagosei Co., Ltd.), polyethylene glycol diacrylate (for example, Bremer ADE-200 manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol diacrylate (for example, Nippon Oil & Fats, Inc.) Bremermer ADP-200, etc.), polyethylene glycol-propylene glycol-polyethylene glycol diacrylate (for example, Bremermer ADC series, manufactured by NOF Corporation), polytetramethylene diglycol diacrylate (for example, light manufactured by Kyoeisha Chemical Co., Ltd.) Acrylate PTMGA-250), polyethylene glycol diacrylate (for example, Light Acrylate 3EG-A manufactured by Kyoeisha Chemical Co., Ltd.), dimethylo Dicyclopentane diacrylate (for example, IRR214 manufactured by Daicel UCB Corporation), tricyclodecane dimethanol diacrylate (for example, LUMICURE DCA-200 manufactured by Dainippon Ink & Chemicals, Inc.), neopentyl glycol modified trimethylolpropane di Examples thereof include acrylates (for example, Kayrad R-604 manufactured by Nippon Kayaku Co., Ltd.) and triglycerol diacrylates (for example, epoxy ester 80MFA manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the trifunctional (meth) acrylate include, for example, EO-modified glycerol acrylate (for example, New Frontier GE3A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), PO-modified glycerol triacrylate (for example, Beam Set 720 manufactured by Arakawa Chemical Co., Ltd.), Pentaerythritol triacrylate (PETA) (for example, New Frontier PET-3 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), EO-modified phosphate triacrylate (for example, Biscoat 3A manufactured by Osaka Organic Chemical Co., Ltd.), trimethylolpropane triacrylate ( TMTPA) (for example, New Frontier TMTP manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), caprolactone-modified trimethylolpropane triacrylate (for example, Ebecryl 2047 manufactured by Daicel UCB Corporation), H A-modified trimethylolpropane triacrylate (for example, Kayrad THE-330 manufactured by Nippon Kayaku Co., Ltd.), (EO) or (PO) -modified trimethylolpropane triacrylate (for example, LUMICURE ETA- manufactured by Dainippon Ink & Chemicals, Inc.) 300, New Frontier TMP-3P manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), alkyl-modified dipentaerythritol triacrylate (e.g. Kayrad D-330 manufactured by Nippon Kayaku Co., Ltd.), tris (acryloxyethyl) isocyanurate (e.g. , Hitachi Chemical Co., Ltd. FANCLIL FA-731A, etc.).

  Examples of the tetrafunctional (meth) acrylate include ditrimethylolpropane tetraacrylate (DTMPTA) (for example, LUMICURETA-400 manufactured by Dainippon Ink & Chemicals, Inc.), pentaerythritol ethoxytetraacrylate (for example, Mitsubishi Rayon Co., Ltd.). Diamond Beam UK-4154, etc.), pentaerythritol tetraacrylate (PETTA) (for example, NK Ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  As pentafunctional or hexafunctional (meth) acrylate, dipentaerythritol hydroxypentaacrylate (for example, SR-399E manufactured by Kayaku Sartomer Co., Ltd.), alkyl-modified dipentaerythritol pentaacrylate (for example, Nippon Kayaku Co., Ltd.) Kayalad D-310), dipentaerythritol hexaacrylate (for example, DAP-600 manufactured by Dainippon Ink & Chemicals, Inc.), dipentaerythritol penta and hexaacrylate based polyfunctional monomer mixture (for example, Dainippon Ink and Chemicals Inc.) And LMICURE DPA-620 manufactured by the company).

  Of course, the compound (a) having two or more (meth) acryloyl groups used in the production method of the present invention is not limited by these specific examples. The compound (a) having two or more (meth) acryloyl groups may be used alone or in combination with a plurality of compounds having different numbers of (meth) acryloyl groups, or a plurality of compounds having different structures. May be used in combination. Further, the compound (a) that is generally commercially available is often a mixture of compounds having different numbers of (meth) acryloyl groups with respect to the target compound as the main component. In use, the compound having the desired number of (meth) acryloyl groups may be extracted and used by various purification methods such as chromatography and extraction, but may be used as a mixture.

  Moreover, as said compound (a) used by this invention, it is also possible to use urethane (meth) acrylate. The method for producing the urethane (meth) acrylate is not limited at all, and can be obtained, for example, by a polyaddition reaction between a hydroxyl group-containing (meth) acrylate having two or more (meth) acryloyl groups and an isocyanate compound. Is possible.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol hydroxypentaacrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate (for example, Japan Such as Bremer GAM manufactured by Yushi Co., Ltd.).

  As the isocyanate compound, any of an aromatic isocyanate compound, an aliphatic isocyanate compound, and an alicyclic isocyanate compound can be used. For example, toluene diisocyanate, tolylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene. Diisocyanate, trimethylhexamethylene diisocyanate, adamantyl diisocyanate and the like can be mentioned. From the viewpoint of the glass transition temperature of the cured product to be obtained and the scratch resistance of the cured product, it is preferable to have an alicyclic structure. It is preferable to use norbornane diisocyanate, isophorone diisocyanate, or adamantyl diisocyanate. That is, the urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate having two or more (meth) acryloyl groups with an isocyanate compound having an alicyclic structure. Is preferred. In addition, the compound obtained by introducing a fluorinated alkyl group into the urethane (meth) acrylate by Michael addition uses a compound having a hydroxyl group as the compound, and after introducing the fluorinated alkyl group into the urethane by a Michael addition reaction, It can also be synthesized by reacting with an isocyanate compound, and the reaction sequence is not particularly limited.

  Next, the compound (b) having a fluorinated alkyl group and active hydrogen will be described.

  The fluorinated alkyl group is preferably a perfluoroalkyl group because it can effectively exhibit the performance derived from fluorine atoms, but is not particularly limited, and some hydrogen atoms in the alkyl group are fluorine atoms. It may be replaced with.

As the compound (b), the following general formula (1) can be used from the viewpoint that industrial availability is easy and mild reaction conditions can be selected.
Rf (CH ₂ ) _m ZH (1)
[In the formula, m is an integer of 0 to 20, Rf is —C _n F _{2n + 1} (n is an integer of 1 to 20), and Z is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. A nitrogen atom, an oxygen atom, a sulfur atom, or —SO ₂ —NR— (wherein R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms). Or a compound represented by the following general formula (2)

[Wherein, Y is an oxygen atom or a sulfur atom, p and q are the same or different integers of 1 to 4, and Rf and Rf ¹ may be the same or different -C _n F _{2n + 1} (n is an integer of 1 to 20). Z is preferably a nitrogen atom having a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a sulfur atom, or —NRSO ₂ — ( R is an alkyl group having 1 to 6 carbon atoms), or Y in the general formula (2) is a sulfur atom, and the carbon number n of Rf ¹ is 4, 6, or 8; It is particularly preferable that the carbon number n of Rf in the general formula (1) is 4, 6, or 8.

Examples of the compound represented by the general formula (1) include the following compounds (b-1) to (b-12), which may be used alone or as a mixture of two or more.
_{C 4 F 9 SO 2 N (} CH 3) H (b-1)
_{C 4 F 9 SO 2 N (} C 3 H 7) H (b-2)
_{C 4 F 9 CH 2 CH 2} N (C 8 H 17) H (b-3)
_{C 4 F 9 CH 2 CH 2} SH (b-4)
_{C 6 F 13 CH 2 CH 2} SO 2 N (C 8 H 17) H (b-5)
_{C 6 F 13 CH 2 CH 2} SH (b-6)
_{C 6 F 13 CH 2 CH 2} N (C 4 H 9) H (b-7)
_{C 8 F 17 CH 2 CH 2} SH (b-8)
_{C 8 F 17 CH 2 N (} C 3 H 7) H (b-9)
_{C 9 F 19 CH 2 CH 2} SH (b-10)
_{C 10 F 21 CH 2 CH 2} CH 2 N (C 3 H 7) H (b-11)
_{C 12 F 25 CH 2 CH 2} SH (b-12)
The fluorinated alkyl group-containing (meth) acrylate used in the present invention is preferably obtained from the compound (a) and the compound (b), but the reaction between the compound (a) and the compound (b). Can be prepared by the usual Michael addition reaction method, and no special consideration is required by having a fluorine atom, and can be produced in the absence of a solvent or in the presence of a solvent. When a solvent is used, it is appropriately selected in consideration of the solubility, boiling point, equipment used, etc. of the compound (a) and the compound (b). Specifically, ethyl acetate, Esters such as butyl acetate, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), methyl isobutyl ketone (Hereinafter abbreviated as MIBK), alcohols such as methanol, ethanol and isopropanol, aprotic polar compounds such as dimethylformamide, dimethylformacetamide and dimethylsulfoxide, ethers such as diethyl ether and tetrahydrofuran, Aliphatic systems such as hexane and heptane Reduction such as hydrogen acids and the like, may be used in combination of two or more solvents may alone. Among these, it is preferable to use esters, aromatic hydrocarbons, ketones, alcohols, ethers, dimethylformacetamide, dimethyl sulfoxide, etc., and esters, ketones, alcohols, ethers are preferably used. Particularly preferred.

  As described above, it is possible to pass fluorine through a Michael addition reaction between the compound (a) and the compound (b) under a simpler and milder condition without undergoing a condensation reaction that requires a strong acid catalyst. An alkyl group-containing (meth) acrylate can be produced.

  Specific examples of the fluorinated alkyl group-containing (meth) acrylate obtained by the compound (a) and the compound (b) include the following compounds (i) to (xxv). The following specific examples show the case of acrylate, and any acryloyl group in the formula can be changed to a methacryloyl group. Further, the following specific examples are compounds purified when acrylate is used as the (meth) acrylate used as a raw material, and any one of the hydrogen atoms in the methylene group bonded to the carbonyl carbon can be changed to a methyl group.

  The content of these fluorinated alkyl group-containing (meth) acrylates in the coating composition is a one-component coating composition comprising a composition for inducing a high refractive index layer, a composition for inducing a low refractive index layer, and a solvent. The amount is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight based on 100 parts by weight of the total solid content of the product. If the content of the fluorinated alkyl group-containing (meth) acrylate exceeds 40 parts by weight with respect to 100 parts by weight of the total solid content of the coating composition, the transparency may decrease and the minimum reflectance may increase. If the amount is less than parts by weight, the scratch resistance and alkali resistance may decrease.

  The coating composition used in the present invention includes inorganic particles suitable as the low refractive index layer constituents described above, inorganic particles suitable as the high refractive index layer constituents described above, and the fluorinated alkyl group-containing (meth) described above. It is desirable to include an acrylate and a solvent. As long as the coating composition is in a state where the coating composition can be applied, there is no restriction on the required amount and properties, and thus a solvent that is generally used as a coating solvent can be used although it is not particularly described.

  The coating composition used in the present invention preferably further contains an initiator, a curing agent and a catalyst. The initiator and the catalyst are used for promoting the reaction between the inorganic particles and the resin or for promoting the reaction between the resins. The initiator is preferably one that initiates or promotes the polymerization and / or condensation and / or crosslinking reaction of the coating composition by anion, cation, radical reaction or the like.

  Known or well-known initiators and curing agents and catalysts can be used. A plurality of initiators may be used at the same time or may be used alone. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of photopolymerization initiators include, but are not limited to, aryl ketone compounds, sulfur-containing compounds, acyl phosphine oxide compounds, and amine compounds. The addition ratio of the initiator and the curing agent is preferably 0.001% to 30% by weight, more preferably 0.05% to 20% by weight, based on the solid content in one liquid coating composition. More preferably, it is 0.1 to 10% by weight.

In addition, additives such as various silane coupling agents, surfactants, thickeners, and leveling agents may be appropriately added to the coating composition used in the present invention as necessary.
[Other layers]
The antireflection film may further be provided with a hard coat layer, a moisture proof layer, an antistatic layer, an undercoat layer or a protective layer.

  The hard coat layer is provided for imparting scratch resistance to the support substrate. The hard coat layer also has a function of strengthening the adhesion between the transparent support and the layer thereon. The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer, or a silica compound. A pigment may be added to the hard coat layer. The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Further, two or more kinds of polymers may be used in combination. As the silica compound, colloidal silica is preferably used. The strength of the hard coat layer is preferably a pencil hardness of 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

In addition to the hard coat layer, the support substrate may be provided with an adhesive layer, a shield layer, and a sliding layer. The shield layer is provided to shield electromagnetic waves and infrared rays.
[Support substrate]
Except for the case where the antireflection film is directly provided on the CRT image display surface or the lens surface, the antireflection film preferably has a supporting substrate. As the support substrate, a plastic film is more preferable than a glass plate. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethene Tacrylate and polyetherketone are included, but among these, triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are particularly preferable.

  The light transmittance of the supporting substrate is preferably 80% or more and 100% or less, and more preferably 86% or more and 100% or less. Here, the light transmittance is a ratio of light transmitted through the sample when irradiated with light, and is an index of transparency of the transparent material that can be measured according to JIS K 7361-1. The larger the value of the light transmittance of the antireflection film, the better. The smaller the value, the higher the haze value and the higher the possibility of image deterioration. The haze of the supporting substrate is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the supporting substrate is preferably 1.4 to 1.7. The refractive index referred to in the present invention is a ratio of changing the angle of the traveling direction at the interface when light travels from the air into a certain substance, and is measured by the method defined in JIS K 7142. Can do.

An infrared absorber or an ultraviolet absorber may be added to the support substrate. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass and more preferably 0.05 to 10% by mass with respect to 100% by mass of all the components of the support substrate. You may add the particle | grains of an inert inorganic compound as a sliding agent to a support base material. Examples of the inorganic compound used as a _{lubricant, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. Further, the support substrate may be subjected to a surface treatment.

Various surface treatments can be applied to the surface of the support substrate. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.
[Coating drying]
The coating composition used in the production method of the present invention performs a coating process such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, and a gravure coating method once on a supporting substrate. By doing so, an antireflection film can be produced by subsequent drying of the coating composition.

  According to the production method of the present invention, two layers having different refractive indexes can be simultaneously formed by applying and drying one liquid coating composition once. The formation of the two layers having different refractive indices is performed in the drying process after the application of the coating composition in which the composition for inducing the low refractive index layer of the present invention, the composition for inducing the high refractive index layer, and the solvent are mixed. Made.

  In addition to completely removing the solvent from the obtained antireflection film, it is preferable to heat in the drying step from the viewpoint of separation into two layers without defects. The heating temperature can be determined from the boiling point of the solvent used and the glass transition temperature of the polymer, but is not particularly limited.

  Furthermore, you may perform hardening operation by irradiating a heat | fever or an energy ray with respect to the formation layer after drying. When curing is performed by heat, the drying step and the curing step may be performed simultaneously.

  Moreover, the antireflection film obtained by the production method of the present invention can be provided on the viewing side surface of various image display devices such as PDP, thereby providing an image display device having excellent antireflection properties.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

Examples 1-4, Comparative Examples 1-5
[Production example]
[Adjustment of high refractive index component]
Opstar TU4005 (manufactured by JSR), which is an antimony-containing tin oxide as a high refractive index component, was diluted by adding isopropyl alcohol to a solid content concentration of 3.2% by weight.
[Adjustment of low refractive index component]
[Adjustment of low refractive index component (a)]
2.75 g of methacryloxypropyltrimethoxysilane and 0.34 g of 10% by weight aqueous formic acid solution were mixed with 20 g of Sulria TR-113 (manufactured by Catalyst Kasei Kogyo Co., Ltd .: solid content 20% by weight) which is a hollow silica at 70 ° C. Stir for 1 hour. Subsequently, 2.76 g of 2-perfluorooctylethyl acrylate and 0.115 g of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C. for 1 hour. The obtained liquid was diluted with isopropyl alcohol to obtain a low refractive index component (a) having a solid content concentration of 3.6% by weight.
[Adjustment of low refractive index component (b)]
2.75 g of methacryloxypropyltrimethoxysilane and 0.34 g of 10 wt% formic acid aqueous solution were mixed with 20 g of through silica TR-113 (manufactured by Catalyst Kasei Kogyo Co., Ltd .: solid content 20 wt%) which is a hollow silica, and 1 at 70 ° C. Stir for hours. The obtained liquid was diluted with isopropyl alcohol to obtain a low refractive index component (b) having a solid concentration of 3.1% by weight.
[Adjustment of low refractive index component (c)]
20 g of Thruria TR-113 (manufactured by Catalytic Chemical Industry Co., Ltd .: solid content 20% by weight), which is hollow silica, was diluted with isopropyl alcohol to obtain a low refractive index component (c) having a solid content concentration of 3.4% by weight.
[Fluorinated alkyl group-containing (meth) acrylate]
As the fluorinated alkyl group-containing methacrylate, Defensor: TF-3042ME (manufactured by Dainippon Ink & Chemicals, Inc .: solid content 90% by weight) was diluted with isopropyl alcohol to 3.5% by weight and used.
[Multifunctional acrylate]
As a polyfunctional acrylate, UN-904 (manufactured by Negami Kogyo Co., Ltd .: solid content 63 wt%) was diluted with isopropyl alcohol to 3.5 wt% and used.
Using.
[Fluorosurfactant]
As a fluorosurfactant, MegaFac: RS-101 (Dainippon Ink Chemical Co., Ltd .: solid content 40% by weight) was diluted with isopropyl alcohol to 3.5% by weight and used.
[Coating 1]
5 parts by weight of a fluorinated alkyl group-containing methacrylate is added to 100 parts by weight of a solution (solid content concentration: 3.4% by weight) in which a low refractive index component (a) and a high refractive index component are mixed at a weight ratio of 4: 6. Part was added.
[Coating agent 2]
10 parts by weight of fluorinated alkyl group-containing methacrylate is added to 100 parts by weight of a solution (solid content concentration: 3.4% by weight) in which the low refractive index component (a) and the high refractive index component are mixed to have a weight ratio of 4: 6. Added.
[Coating agent 3]
30 parts by weight of a fluorinated alkyl group-containing methacrylate is added to 100 parts by weight of a solution (solid content concentration: 3.4% by weight) in which a low refractive index component (a) and a high refractive index component are mixed at a weight ratio of 4: 6. Part was added.
[Coating agent 4]
40 parts by weight of a fluorinated alkyl group-containing methacrylate is added to 100 parts by weight of a solution (solid content concentration: 3.4% by weight) in which a low refractive index component (a) and a high refractive index component are mixed at a weight ratio of 4: 6. Part was added.
[Coating 5]
The low refractive index component (a) and the high refractive index component were mixed at a weight ratio of 4: 6 (solid content concentration: 3.4 wt%).
[Coating agent 6]
20 parts by weight of polyfunctional acrylate is added to 100 parts by weight of a solution (solid content concentration: 3.4% by weight) in which the low refractive index component (a) and the high refractive index component are mixed at a weight ratio of 4: 6. did.
[Coating agent 7]
20 parts by weight of a fluorosurfactant is added to 100 parts by weight of a solution (solid content concentration: 3.4% by weight) in which a low refractive index component (a) and a high refractive index component are mixed at a weight ratio of 4: 6. did.
[Coating 8]
Fluorinated alkyl group-containing methacrylate is added to 100 parts by weight of a solution (solid content concentration: 3.2% by weight) in which the low refractive index component (b) and the high refractive index component are mixed at a weight ratio of 4: 6. 20 parts by weight were added.
[Coating agent 9]
20 parts by weight of fluorinated alkyl group-containing methacrylate was added to 100 parts by weight of only the low refractive index component (c).
[Preparation of antireflection film]
As a supporting substrate, Lumiclear SR-HC (Toray Film Processing Co., Ltd.) in which a hard coat paint was applied and cured on a PET resin film was used. Using a bar coater (# 10) on this support substrate, coating agents 1 to 9 shown in Table 1 were applied for each Example and Comparative Example, and then dried at 100 ° C. for 1 minute, and 400 mJ / cm ^2. Were irradiated with ultraviolet rays to produce an antireflection film.
[Evaluation of antireflection film]
The produced antireflection film was subjected to the following performance evaluation, and the results obtained are shown in Table 1. Unless otherwise specified, in each of the examples and comparative examples, the measurement was performed three times at different locations for one sample, and the average value was used.
[Antireflection performance]
The antireflection performance was evaluated using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation in the wavelength range of 400 nm to 800 nm, and the minimum value (minimum reflectance) of the light reflectance was measured.

A minimum reflectance of 1.0% or less was accepted.
[Abrasion resistance]
Steel wool (# 0000) with a load of 250 g / cm ² was placed vertically on the antireflection film, and the number of scratches observed when the length of 1 cm was reciprocated 10 times was visually measured.

The number of visible scratches was 15 or less.
[Alkali resistance]
A 1 wt% NaOH solution was added dropwise, and after 30 minutes, wiping was performed using gauze. By observing the surface state after wiping, it was visually determined whether or not the surface was damaged.

If there was no trace of the droplet, the evaluation was ○, and if the trace was confirmed, the evaluation was ×. Of the three samples with different locations for one sample, the most evaluated result is adopted.
[transparency]
Transparency was determined by measuring the haze value. The measurement was based on JIS K 7136 using a Nippon Denshoku Industries Co., Ltd. haze meter. Less than 2.0% was evaluated as ◯, 2.0% or more and less than 3.0% as Δ, and 3.0% or more as x.
[Refractive index of inorganic particles including silica particles]
The method for measuring the refractive index of the inorganic particles of the present invention was performed by the following method.

The dispersion liquid of inorganic particles is taken in an evaporator and the dispersion medium is evaporated. This is dried at 120 ° C. to obtain a powder. A standard refracting liquid having a known refractive index is dropped onto a glass drop of a few drops, and the above powder is mixed therewith. The above operation (3) was carried out with various standard refractive liquids, and the mixed liquid (in many cases, the standard refractive liquid when the paste became transparent was measured as the refractive index of the inorganic particles.
[Presence or absence of two-layer interface]
By observing a cross section using a transmission electron microscope (TEM), the presence or absence of the interface of two layers was judged.
[Individual refractive index of two layers]
The refractive index of each of the two layers in the present invention is measured with a reflection spectral film thickness meter (trade name “FE-3000”, manufactured by Otsuka Electronics Co., Ltd.), and the wavelength dispersion of a typical refractive index is measured. The nk Cauchy dispersion formula was cited as an approximate expression, and it was obtained by fitting with the measured value of the spectrum.

  As is clear from Table 1, in the case of containing a fluorinated alkyl group-containing (meth) acrylate (Examples 1 to 4), the balance was excellent in antireflection, scratch resistance, alkali resistance, and transparency. It was a film.

  Further, when no fluorinated alkyl group-containing (meth) acrylate was contained (Comparative Example 1), although the transparency was good, the scratch resistance and alkali resistance were insufficient.

  Further, when polyfunctional acrylate was included instead of the fluorinated alkyl group-containing (meth) acrylate (Comparative Example 2), the scratch resistance and transparency were good, but the alkali resistance was poor.

  When a fluorinated surfactant was included instead of the fluorinated alkyl group-containing (meth) acrylate (Comparative Example 3), the transparency was good, but the scratch resistance and alkali resistance were poor.

  In the case where the surface treatment with the fluorine compound was not performed in the low refractive index component (Comparative Example 4), although the scratch resistance, alkali resistance and transparency were good, the antireflection property was lacking.

  Even when the high refractive index component was not included (Comparative Example 5), although the scratch resistance, alkali resistance and transparency were good, the antireflection property was lacking.

Claims (6)

A method for producing an antireflection film comprising two layers having different refractive indices by a step of coating and drying a one-component coating composition containing two or more kinds of inorganic particles, and then irradiating and curing with heat or energy rays Because
At least one kind of inorganic particles is surface-treated with a fluorine compound,
The coating composition includes an initiator and a fluorinated alkyl group-containing (meth) acrylate,
The amount of the fluorinated alkyl group-containing (meth) acrylate is 5 to 40 parts by weight with respect to 100 parts by weight of the total solid content of the coating composition,
The fluorinated alkyl group-containing (meth) acrylate is a Michael addition reaction between a compound (a) having two or more (meth) acryloyl groups and a compound (b) having a fluorinated alkyl group and active hydrogen. A fluorinated alkyl group-containing (meth) acrylate obtained in
The compound (b) having the fluorinated alkyl group and active hydrogen is a compound represented by the following general formula (1) or a compound represented by the following general formula (2). Film production method.
General formula (1)
Rf (CH ₂ ) _m ZH (1)
[In formula, m is an integer of 0-20. Rf is _-C n _{F 2n +} 1 (n is an integer from 1 to 20.). Z is a nitrogen atom, a sulfur atom , or —SO ₂ —NR— (R is an alkyl group having 1 to 6 carbon atoms) covalently bonded to an alkyl group having 1 to 6 carbon atoms. ]
General formula (2)

[Wherein, Y is an oxygen atom or a sulfur atom, p and q are the same or different integers of 1 to 4, and Rf and Rf ¹ may be the same or different -C _n F _{2n + 1} (n is an integer of 1 to 20). ]   2. The antireflection film according to claim 1, wherein the inorganic particles surface-treated with a fluorine compound are silica particles, and the other inorganic particles are inorganic particles having a higher refractive index than the silica particles. Method. The said surface treatment treats the said silica particle with the compound chosen from the following group (I), and also processes with the compound chosen from the following group (II), The reflection of Claim 2 characterized by the above-mentioned. Method for manufacturing prevention film.
Group (I):
Acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltrimethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxy Roxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, and other methoxy groups in these compounds A compound substituted with an alkoxyl group and a hydroxyl group.
Group (II):
2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-par Fluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro- 3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro-5-methyl Hexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluoro Octylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, -Perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2- Hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadeca Fluorononyl methacrylate, 1-trifluoromethyl trifluoroethyl methacrylate, hexafluorobutyl methacrylate. Inorganic particles having a refractive index higher than that of the silica particles are metal oxides,
4. The method for producing an antireflection film according to claim 2, wherein the metal oxide is indium-containing tin oxide (ITO) and / or antimony-containing tin oxide (ATO).   An antireflection film obtained by the production method according to claim 1.   An image display apparatus comprising the antireflection film according to claim 5.