JP4717491B2 - Antireflection film, antireflection light transmissive window material having the antireflection film, and display filter having the antireflection light transmissive window material - Google Patents

Description

  The present invention relates to an antireflection film useful for a front filter of a plasma display panel (PDP), a liquid crystal display (LCD), and other displays, an antireflection light transmitting window material having the antireflection film, and the antireflection light. The present invention relates to a display front filter having a transmission window material.

  In general, a front filter is always used for PDP and LCD. These front filters can cut near-infrared rays, improve color reproducibility (emission color purity improvement), electromagnetic wave shield, improve bright contrast (antireflection), protect the light-emitting panel, block heat from the light-emitting panel, etc. Plays the role of

  It is necessary to reduce the near infrared rays emitted from the light emitting panel of the PDP in order to avoid malfunctioning the remote control used for home television and video. In addition, it is necessary to reduce the electromagnetic waves emitted by the light emitting panel of the PDP in order to avoid adverse effects on the human body and precision equipment. Furthermore, in order to make the light emitted from the light emitting panel of the PDP feel a natural color for human vision, a device for improving color reproducibility (light emission color purity improvement) is also required by correction with a filter. Further, it is desirable that the display on the display is visually recognized with sufficient contrast without being hindered by reflection of light from the outside even in a bright place such as a bright room. Furthermore, even when the display product is directly touched by hand, the heat generated by the light emitting panel of the PDP is required to be cut off in order to avoid a situation where the user is surprised by the high temperature. In order to prevent the product from being easily damaged, it is desirable that the light-emitting panel be protected so that the fragments do not scatter even if it is damaged.

  The structure of a typical front filter for PDP along the above purpose is illustrated in FIG. An antireflection layer 41, an electromagnetic wave shielding layer 42, a color tone correction filter layer 44, and a near infrared cut layer 45 are laminated on a transparent substrate 43, and this is installed as a filter on the front surface of the light emitting panel 40. The order of lamination is changed according to the purpose.

  In this front filter for PDP, the antireflection layer is generally produced as an antireflection film having both light transmittance and antireflection properties, and is used as one layer of the filter. The same applies to the LCD front filter.

  Such an antireflection layer is manufactured as a multilayer laminate (antireflection film) including a plurality of thin layers having different refractive indexes designed to reduce reflected light as much as possible. Although it is possible to produce this multilayer laminate by a dry process such as a vacuum deposition method or a sputtering method, generally this dry process requires a vacuum manufacturing facility, and when mass production is required, Manufacturing costs are inevitably increased. For this reason, the formation of a multilayer laminate of antireflection films by a wet coating method such as solution coating is widely used.

  The general structure of such an antireflection film by wet coating is illustrated in FIG. This antireflection film is formed by laminating a high refractive index layer 52 having a hard coat property and a low refractive index layer 51 having a lower refractive index than the high refractive index layer 52 on a transparent base material 53. Antireflective properties are imparted by the refractive index layer 51, and it has the role of preventing external light incident from the low refractive index layer 51 side from being reflected and lowering visibility. In this case, the low refractive index layer 51 has a sufficiently low refractive index, has sufficient adhesion to the high refractive index layer 52, has sufficient hardness, and is not easily damaged. That is required. In general, it is known that the smaller the difference in refractive index between the high refractive index layer and the low refractive index layer, the smaller the minimum value of the reflectance, and the low refractive index of the low refractive index layer indicates that the antireflection performance is low. It is particularly important for securing.

  In general, examples of the material for such a low refractive index layer include fluororesin, silicon resin, and acrylic resin. Among these, since the silicon resin has problems in chemical resistance and stability in a solution (coating solution) state, more excellent fluororesin and acrylic resin are usually used in this respect.

  However, when a fluororesin is used for the low refractive index layer, a low refractive index can be sufficiently achieved, but the adhesion with the underlying high refractive index layer is insufficient or the hardness is insufficient. Therefore, there is a problem that it is easily scratched. Particularly in the case of a display filter or the like, the fact that the surface is easily scratched directly leads to a decrease in product quality and yield. Patent Document 1 (Japanese Patent Laid-Open No. 2001-350002) discloses an antireflection film having a low refractive index layer in which a fluororesin is formed as particles and dispersed in the resin as a solution to the problem caused by the use of the fluororesin. is doing.

  In addition, when an acrylic resin is used for the low refractive index layer, the hardness can be sufficiently achieved, but the refractive index is not sufficiently low, so that the antireflection performance that is most required as an antireflection film is not satisfactory. There is a problem of becoming sufficient. In Patent Document 2 (Japanese Patent Laid-Open No. 2002-031702), as a solution to such a problem due to the use of an acrylic resin, metal oxide fine particles having a high refractive index are blended in a high refractive index layer, and the refractive index of the high refractive index layer is reduced. An antireflection film has been disclosed in which the refractive index difference between the low refractive index layer and the high refractive index layer is secured by increasing the refractive index to improve the antireflection performance.

JP 2001-350002 A JP 2002-031702 A

  However, according to the study by the present inventors, it is possible to achieve low refractive index and hardness at the same time even with an antireflection film by a method as described in Patent Document 1 (Japanese Patent Laid-Open No. 2001-350002). I found that there was a limit. Further, as described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2002-031702), even when the antireflective film has improved antireflective performance by increasing the refractive index of the high refractive index layer, the refractive index of the low refractive index layer is low. The design constraints and anti-reflection performance limitations caused by the relatively high level remain, and if the anti-reflection film (anti-reflection film) has the same basic structure, a low refractive index layer with a lower refractive index is used. By doing so, it is considered that a higher degree of freedom in design and better antireflection performance can be achieved.

  Accordingly, an object of the present invention is to obtain an antireflection film having excellent antireflection performance by providing a low refractive index layer having excellent chemical resistance, high hardness, and sufficiently low refractive index. . Another object of the present invention is to provide a production method suitable for producing the antireflection film.

  Another object of the present invention is to obtain an antireflection light transmissive window material provided with the antireflection film. Moreover, the objective of this invention is also obtaining the filter for a display provided with the said reflection preventing window material.

The inventors of the present invention are characterized in that the above object includes a fluorine-containing acrylic resin layer comprising a polymerization product of a polymerizable composition containing a fluorine-containing polyfunctional acrylic monomer represented by the following formula I: And found to be achieved by an antireflection film.

  Such an antireflection film has excellent chemical resistance, high hardness, and excellent antireflection performance by providing a fluorine-containing acrylic resin layer as a low refractive index layer having a sufficiently low refractive index. It has become. Achieving a low refractive index is considered to contribute to the fluorine atom, and a high hardness is considered to be a contribution of the polyfunctionality of the acrylic monomer.

  A preferred configuration of the antireflection film is that a fluorine-containing acrylic resin layer is provided on a high refractive index layer having a relatively high refractive index as a low refractive index layer having a lower refractive index than the high refractive index layer. It is a configuration. Such a configuration may be achieved by providing an antireflection film comprising a high refractive index layer and a low refractive index layer on a transparent substrate, but the transparent substrate itself also serves as the high refractive index layer. Thereby, the low refractive index layer may be provided as a single layer to achieve the configuration of the antireflection film.

  The polymerizable composition preferably further contains a photopolymerization initiator. This makes it possible to start photopolymerization more reliably.

The fluorine-containing polyfunctional acrylic monomer has the following formula I:

（但し、ｋは、０〜２の範囲の自然数であり、
Ｘ¹〜Ｘ³は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、又は、
−Ｈ、
であり、
Ｙは、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、
−Ｈ、又は、
次の式ＩＩ：

(Where k is a natural number ranging from 0 to 2,
X ^{1 to} X ³ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
And
Y is
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F,
-H or
The following formula II:

で表される置換基、
（但し、ｌは、０〜２の範囲の自然数であり、
Ｘ⁴〜Ｘ⁶は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、又は、
−Ｈ、
である）
であり、
且つ、置換基Ａの置換基Ｂに対する比（Ａ：Ｂ）が、平均値として２：４〜５：１の範囲にある）
で表される化合物である。上記化合物は、フッ素原子の含有により屈折率を低下させる効果と、複数のアクリロイル基により三次元網目構造を形成して硬度を上昇させる効果とが得られていると考えられる。

A substituent represented by
(Where l is a natural number ranging from 0 to 2,
X ^{4 to} X ⁶ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
Is)
And
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)
In a compound represented by. The above compound and the effect of lowering the refractive index by containing a fluorine atom, and the effect of increasing the hardness by forming a three-dimensional network structure by a plurality of acryloyl groups are considered to have been obtained.

In a preferred embodiment, X ^{1 to} X ³ and Y are preferably a substituent A or a substituent B. In another preferred embodiment, Y is preferably a substituent represented by Formula II. Furthermore, X ^{1 to} X ⁶ are preferably a substituent A or a substituent B.

  The k is preferably 1. In addition, when the substituent represented by Formula II is Y, it is preferable that 1 is 1. It is particularly preferred that k and l are 1.

  The ratio of substituent A: substituent B in formula I is preferably in the range of 3: 3 to 5: 1 as an average value. By using such a compound, it is possible to impart both hardness suitable for the low refractive index layer of the antireflection film and low refractive index.

  The fluorine-containing polyfunctional acrylic monomer is preferably contained in the polymerizable composition in the range of 1 to 70% by mass with respect to the polymerizable composition.

  The polymerization product is preferably polymerized by ultraviolet irradiation. The fluorine-containing polyfunctional acrylic monomer used in the present invention can be polymerized by various methods, but since it can be polymerized in a short time, polymerization by ionizing radiation irradiation (ionizing radiation line) Curing) is preferable, and polymerization by ultraviolet irradiation (ultraviolet curing) is particularly preferable because of easy handling.

  The polymerizable composition preferably further includes hollow silica fine particles as desired. This can further reduce the refractive index.

  The hollow silica fine particles preferably have an average particle size of 5 to 200 nm.

  The hollow silica fine particles are preferably contained in an amount of 0.1 to 50 parts by mass with respect to 10 parts by mass of the fluorine-containing polyfunctional acrylic monomer.

  Furthermore, this invention exists also in the anti-reflective light transmission window material containing said anti-reflective film.

  Moreover, this invention exists also in the anti-reflective light transmissive window material which contains said anti-reflective film as an outermost layer. The antireflection film including the low refractive index layer of the present invention having high hardness is also suitable for use as the outermost layer of the window material.

  Moreover, this invention exists also in the filter for displays containing said reflection preventing light transmission window material.

Furthermore, the object of the present invention is a method for producing an antireflection film, which comprises the following steps:
Applying a polymerizable composition containing a fluorine-containing polyfunctional acrylic monomer represented by the following formula I and a photopolymerization initiator on a high refractive index layer having a relatively high refractive index;
A step of curing the polymerizable composition applied in the step by irradiating with ultraviolet rays;
This is achieved by a manufacturing method in which a low refractive index layer having a refractive index lower than that of the high refractive index layer is provided.

  The antireflection film is preferably manufactured by such a manufacturing method. Since the polymerizable composition used in this production method is a stable composition without starting unintended polymerization before polymerization, it can be polymerized in a short time by ultraviolet irradiation. According to the production method of the present invention, handling during production is easy, and product variations due to unintended polymerization do not occur.

The fluorine-containing polyfunctional acrylic monomer has the following formula I:

（但し、ｋは、０〜２の範囲の自然数であり、
Ｘ¹〜Ｘ³は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、又は、
−Ｈ、
であり、
Ｙは、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、
−Ｈ、又は、
次の式ＩＩ：

(Where k is a natural number ranging from 0 to 2,
X ^{1 to} X ³ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
And
Y is
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F,
-H or
The following formula II:

で表される置換基、
（但し、ｌは、０〜２の範囲の自然数であり、
Ｘ⁴〜Ｘ⁶は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、又は、
−Ｈ、
である）
であり、
且つ、置換基Ａの置換基Ｂに対する比（Ａ：Ｂ）が、平均値として２：４〜５：１の範囲にある）
で表される化合物である。好適な実施の態様においては、前記Ｘ¹〜Ｘ³、及びＹが、置換基Ａ又は置換基Ｂであるが好ましい。また好適な別の実施の態様においては、前記Ｙが、式ＩＩで表される置換基であることが好ましい。さらに前記Ｘ¹〜Ｘ⁶が、置換基Ａ又は置換基Ｂであることが好ましい。前記ｋが１であることが好ましい。また、式ＩＩで表される置換基がＹである場合には、前記ｌが１であることが好ましい。ｋ及びｌが１であることが特に好ましい。前記式Ｉの置換基Ａ：置換基Ｂの比が、平均値として３：３〜５：１の範囲にあることが好ましい。また、前記フッ素含有多官能性アクリル系モノマーは、重合性組成物に対して１〜７０質量％の範囲で重合性組成物に含まれていることが好ましい。

A substituent represented by
(Where l is a natural number ranging from 0 to 2,
X ^{4 to} X ⁶ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
Is)
And
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)
In a compound represented by. In a preferred embodiment, X ^{1 to} X ³ and Y are preferably a substituent A or a substituent B. In another preferred embodiment, Y is preferably a substituent represented by Formula II. Furthermore, X ^{1 to} X ⁶ are preferably a substituent A or a substituent B. The k is preferably 1. In addition, when the substituent represented by Formula II is Y, it is preferable that 1 is 1. It is particularly preferred that k and l are 1. The ratio of substituent A: substituent B in formula I is preferably in the range of 3: 3-5: 1 as an average value. Moreover, it is preferable that the said fluorine-containing polyfunctional acrylic monomer is contained in polymeric composition in 1-70 mass% with respect to polymeric composition.

  The polymerizable composition preferably further includes hollow silica fine particles as desired. The hollow silica fine particles preferably have an average particle size of 5 to 200 nm. The hollow silica fine particles are preferably contained in an amount of 0.1 to 50 parts by mass with respect to 10 parts by mass of the fluorine-containing polyfunctional acrylic monomer.

  Furthermore, this invention exists also in the anti-reflective light transmissive window material containing the anti-reflective film manufactured by the said manufacturing method.

  Moreover, this invention exists also in the filter for a display containing the said antireflection light transmissive window material.

  The antireflection film of the present invention is an antireflection film having excellent antireflection performance by providing a low refractive index layer having excellent chemical resistance, high hardness, and a sufficiently low low refractive index. For this reason, the antireflection light-transmitting window material using the antireflection film of the present invention has excellent antireflection performance and is hardly damaged. Therefore, the antireflective light-transmitting window material using the antireflective film of the present invention is easy to handle and high in productivity, and has a low defective product rate due to scratches. When used as a product, it is easy to handle, withstands long-term handling, and does not lose excellent visibility due to an increase in scratches. These excellent properties are particularly noticeable when used in display filters. However, the present invention is not limited to this, and any application in which high hardness and excellent antireflection performance are advantageous in antireflection films and antireflection light-transmitting window materials. Can be advantageously used.

  The manufacturing method of the present invention is particularly suitable for manufacturing the antireflection film. The polymerizable composition used in the production method of the present invention is a stable composition that does not start unintended polymerization before polymerization, but can be polymerized in a short time by ultraviolet irradiation. it can. Therefore, according to the production method of the present invention, handling during production is easy, and there is no variation in products due to unintended polymerization. The antireflective light transmissive window material including the antireflective film manufactured by the manufacturing method of the present invention and the display filter including the antireflective light transmissive window material are advantageous in that variations in products do not occur. It has characteristics.

  Embodiments of the present invention will be described below in detail with reference to the drawings.

  FIG. 1 is an explanatory view illustrating an example of the flow of manufacturing the antireflection film of the present invention having the structure shown in FIG. First, the high refractive index layer 12 is provided on the transparent substrate 13 (step 1a). Next, the polymerizable composition used in the present invention is applied on the high refractive index layer 12, and this is polymerized to provide the low refractive index layer 11 (step 1b). The combination of the low refractive index layer and the high refractive index layer forms the antireflection film of the present invention that exhibits the antireflection effect.

  FIG. 2 is an explanatory diagram illustrating an example of the flow of manufacturing the antireflection film of the present invention having a structure in which a transparent base material also serves as a high refractive index layer, unlike FIG. First, the polymerizable composition used in the present invention is applied on the transparent substrate 23, and this is polymerized to provide the low refractive index layer 21 (step 2a). The transparent base material 23 has a refractive index sufficiently higher than that of the low refractive index layer 21. For this reason, the present invention exhibits an antireflection effect by a combination using the transparent base material as a high refractive index layer. The antireflection film is formed. That is, the antireflection property is imparted by providing the single low refractive index layer 21 on the transparent substrate 23.

  In the antireflection film of the present invention, such a low refractive index layer is a fluorine-containing polyfunctional acrylic system having one or more fluorine atoms and two or more acryloyl groups and / or methacryloyl groups in the molecule. A fluorine-containing acrylic resin layer made of a polymerization product of a polymerizable composition containing a monomer. Such an antireflection film has excellent chemical resistance, high hardness, and excellent antireflection performance by providing a fluorine-containing acrylic resin layer as a low refractive index layer having a sufficiently low refractive index. It has become.

  The polymerizable composition preferably contains a monomer having three or more acryloyl groups and / or methacryloyl groups in the molecule from the viewpoint of improving the hardness.

  The polymerizable composition may be applied in any way as long as it can be applied with a desired thickness and uniformity. However, it is generally preferable to apply the polymerizable composition by forming a coating liquid of the polymerizable composition. is there. The coating method can be applied by a general wet coating method, and a liquid phase method (dip coating method, spin coating method, spray coating method, roll coating method, gravure roll coating method, reverse coating method). (Coating method), transfer roll coating method, micro gravure coating method, cast coating method, calendar coating method, die coating method, etc.).

  In addition, the polymerization of the applied polymerizable composition can be started by a method such as heating, humidification, ionizing radiation irradiation, etc. In order to take advantage of the characteristics of the polymerizable composition of the present invention, ultraviolet irradiation is performed. Alternatively, electron beam irradiation is preferable from the viewpoint of curing speed, and ultraviolet irradiation is particularly preferable from the viewpoint of simplicity of equipment. In addition, it is preferable to add a polymerization initiator advantageous for the polymerization initiation method to the polymerizable composition as described later.

  As a fluorine-containing polyfunctional acrylic monomer in the polymerizable composition, the following formula I:

（但し、ｋは、０〜２の範囲の自然数であり、
Ｘ¹〜Ｘ³は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、又は、
−Ｈ、
であり、
Ｙは、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、
−Ｈ、又は、
次の式ＩＩ：

(Where k is a natural number ranging from 0 to 2,
X ^{1 to} X ³ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
And
Y is
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F,
-H or
The following formula II:

で表される置換基、
（但し、ｌは、０〜２の範囲の自然数であり、
Ｘ⁴〜Ｘ⁶は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂ、又は、
−Ｈ、
である）
であり、
且つ、置換基Ａの置換基Ｂに対する比（Ａ：Ｂ）が、平均値として２：４〜５：１の範囲にある）

で表される化合物を含むことが好ましい。

A substituent represented by
(Where l is a natural number ranging from 0 to 2,
X ^{4 to} X ⁶ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
Is)
And
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)

It is preferable that the compound represented by these is included.

In a preferred embodiment, X ^{1 to} X ³ and Y are preferably the substituent A or the substituent B. In another preferred embodiment, Y is preferably a substituent represented by Formula II. When the compound represented by this way Formula II is Y is, X ¹ to X ⁶ is preferably a substituent A or the substituent B. It is thought that all of the substituents contribute to either the low refractive index due to the inclusion of fluorine atoms or the achievement of hardness due to the polymerizable double bond.

  Further, k is preferably 1. When the substituent represented by Formula II is Y, 1 is preferably 1. The sum of k and l is preferably 2, and it is particularly preferred that both k and l are 1.

  Thus, compounds of formula I having a preferred structure include the following formula Ia:

（但し、Ｘ¹〜Ｘ⁶は、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、又は、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂであり、
且つ、置換基Ａの置換基Ｂに対する比（Ａ：Ｂ）が、平均値として２：４〜５：１の範囲にある）
及び、次の式Ｉｂ：

(However, X ^{1 to} X ⁶ are each independently
-CO-CH = substituent represented by CH ₂ A, or,
-CO (CF ₂₎ a substituent B represented by ₃ F,
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)
And the following formula Ib:

（但し、Ｘ¹〜Ｘ³、及びＹは、それぞれ独立して、
−ＣＯ−ＣＨ＝ＣＨ₂ で表される置換基Ａ、又は、
−ＣＯ（ＣＦ₂）₃Ｆ で表される置換基Ｂであり、
且つ、置換基Ａの置換基Ｂに対する比（Ａ：Ｂ）が、平均値として２：４〜５：１の範囲にある）

を挙げることができる。

(However, X ^{1 to} X ³ and Y are each independently
-CO-CH = substituent represented by CH ₂ A, or,
-CO (CF ₂₎ a substituent B represented by ₃ F,
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)

Can be mentioned.

  Suitable compounds included in Formula Ib include pentaerythritol diacrylate difluorobutyrate.

  It is preferred that the ratio of substituent A of formula I: substituent B is in the range of 3: 3 to 5: 1 as an average value, with an average value of 3.5: 2.5 to 4.5: 1.5. It is especially preferable that it is in the range. In particular, in the formulas Ia and Ib, the ratio of substituent A: substituent B is preferably in the above range. By using such a compound, it is possible to impart both hardness suitable for the low refractive index layer of the antireflection film and low refractive index.

  The fluorine-containing polyfunctional acrylic monomer is contained in the polymerizable composition in an amount of 1 to 70% by weight, preferably 5 to 50% by weight, particularly 10 to 30% by weight, based on the polymerizable composition. Is preferred. By using the content in this range, the handleability before polymerization and the certainty of polymerization can be achieved.

  The polymerizable composition can be used by further containing a solvent and, if desired, a polymerization initiator.

  As the polymerization initiator, a general polymerization initiator can be used as long as it can initiate the polymerization of the fluorine-containing polyfunctional acrylic monomer, but the characteristics of the acrylic monomer of the present invention are utilized. For this purpose, it is particularly preferable to use a photopolymerization initiator. Examples of photopolymerization initiators include benzoin, benzophenone, benzoyl methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 5-nitroacenaphthene, hexachlorocyclopentadiene, p-nitrodiphenyl, p-nitroaniline. 2,4,6-trinitroaniline, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone; acetophenone, acetophenone benzyl ketal, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone compounds, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimene Xylbenzophenone, 4,4′-diaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Carbazole, xanthone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compound, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, triphenylamine, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, bis- (2,6-dimethyl) Toxibenzoyl) -2,4,4-trimethylpentylphosphine oxide, bisacylphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Fluorenone, fluorene, benzaldehyde, Michler's ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 3-methylacetophenone, 3,3 ′, 4,4′-tetra ( t-butylperoxycarbonyl) benzophenone (BTTB) and the like, and combinations of BTTB and dye sensitizers such as xanthene, thioxanthene, coumarin, ketocoumarin and the like. Of these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one is preferred. These can be used alone or in combination. The content of the photopolymerization initiator is preferably 7 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin.

  As the solvent, a general solvent can be used as long as it can disperse the fluorine-containing polyfunctional acrylic monomer and the like contained in the polymerizable composition and can be volatilized and removed without adversely affecting the subsequent polymerization. . As such a solvent, for example, ethers, ketones, toluenes, esters and the like can be used. For example, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), methyl ethyl ketoxime, toluene, xylene, hexane, heptane. Ethyl acetate, butyl acetate and the like can be suitably used. These can be used alone or in combination.

  The polymerizable composition can be used by further containing other polymerizable monomers, polymerizable oligomers, and other additives as desired.

  In order to achieve a lower refractive index and further improve the antireflection performance, the polymerizable composition can be used by further containing a filler such as hollow silica fine particles (porous silica). In particular, since the hollow silica fine particle is an inorganic compound filler, it is preferable in that a relatively hard low refractive index layer can be formed.

  Since the hollow silica fine particles are hollow and contain air inside, the refractive index (about 1.34 to 1.44) is much lower than that of ordinary silica (refractive index: about 1.46). This can be produced by covering the surface of porous silica fine particles with an organic silicon compound or the like and closing the pore entrance. The average particle diameter of the hollow silica fine particles can generally be in the range of 1 nm to 1 μm, preferably 5 to 200 nm, and particularly preferably 10 to 100 nm. From the viewpoint of the size of the contribution to lowering the refractive index, the larger the particle size, the better. However, if the particle diameter exceeds about 1 μm, the transparency is extremely lowered and the contribution of diffuse reflection becomes large, and it looks whitish. . From the viewpoint of transparency, the smaller the particle diameter, the better. However, in addition to the above-mentioned contribution to lowering the refractive index, the hollow silica fine particles tend to agglomerate when the particle diameter is smaller than about 0.5 nm. Dispersion is not easy.

  The hollow silica fine particles are generally used in an amount of 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, particularly 5 to 30 parts by weight per 10 parts by weight of the fluorine-containing polyfunctional acrylic monomer. Is preferable from the viewpoint of the balance between the dispersibility of the hollow silica fine particles and the reduction in the refractive index.

  Examples of other polymerizable monomers or polymerizable oligomers added to the polymerizable composition include, for example, urethane oligomers having a plurality of ethylenic double bonds (preferably acryloyl group units or methacryloyl groups), polyester oligomers, epoxy oligomers, and the like, Polymerizable oligomers such as pentaerythritol tetraacrylate (PETA), pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate (DPEHA) and / or polyfunctional monomers can be used. These can be used alone or in combination.

  In addition to the above, various additives that can be optionally added to the polymerizable composition include, for example, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, anti-aging agents, thermal polymerization inhibitors, colorants, Examples include leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, inorganic fillers, organic fillers, fillers, wettability improvers, and coating surface improvers. These can be used alone or in combination.

  The low refractive index layer is formed by the polymerization of the polymerizable composition as described above, and can achieve a very low refractive index by increasing the content of the fluorine-containing polyfunctional acrylic monomer. It can be used for membrane design. However, the refractive index of the low refractive index layer is preferably 1.20 to 1.50, particularly 1.25 to 1.45, from the viewpoint of antireflection performance. .

  The thickness (d) of the low refractive index layer preferably satisfies the formula nd = λ / 4 (where λ is the wavelength of light and n is the refractive index). d is generally 50 to 400 nm, and preferably 50 to 200 nm.

  As described above, the high refractive index layer may have a mode in which the transparent substrate also serves as described above, but the material of the high refractive index layer when formed separately from the transparent substrate will be first described below. As the high refractive index layer, any light-transmitting material having a relatively high refractive index can be used. However, from the viewpoint of ensuring hardness as an antireflection film, the high refractive index layer has a hard coat property. It is preferable to form the layer.

  Such a hard coat layer is, for example, a layer formed of a cured film of a thermosetting resin or an ultraviolet curable resin. In particular, the hard coat layer can be easily made transparent by using an ultraviolet curable resin. It can be provided on a substrate.

  As the thermosetting resin, a thermosetting silicone composition (for example, methyltrimethoxysilane that forms an organic polysiloxane) is preferable, and three-dimensional crosslinking is performed in the dehydration condensation of silanol groups to obtain a high hardness coating. Generally, it can be cured by heating at 80 to 220 ° C. for 10 minutes to 1 hour.

  Further, as the curable resin, a resin or oligomer having an ethylenic double bond (preferably an acryloyl group or a methacryloyl group) can be used, and this can be generally made into a hard coat layer by photocuring. .

  As the ultraviolet curable resin, a known ultraviolet curable resin (including a polymerizable oligomer, a polyfunctional monomer, a monofunctional monomer, a photopolymerization initiator, an additive, and the like) can be used.

  Examples of such ultraviolet curable resins include urethane oligomers having a plurality of ethylenic double bonds (preferably acryloyl groups or methacryloyl groups), oligomers such as polyester oligomers and epoxy oligomers, pentaerythritol tetraacrylate (PETA), and pentaerythritol. It is preferably composed mainly of a polymerizable oligomer such as tetramethacrylate and dipentaerythritol hexaacrylate (DPEHA) and / or a polyfunctional monomer.

  The ultraviolet curable resin is generally composed of an oligomer, if necessary, a reactive diluent (polyfunctional monomer, monofunctional monomer), and a photopolymerization initiator as described above. As a photoinitiator, the photoinitiator mentioned above about the polymeric composition of a low refractive index layer can be used similarly. Each of the oligomer, reactive diluent and initiator may be used alone or in combination of two or more. As for content of a reactive diluent, 0.1-10 mass parts is common with respect to 100 mass parts of ultraviolet curable resin, and 0.5-5 mass parts is preferable. The content of the photopolymerization initiator is preferably 7 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin.

  Various additives can be further added to the resin of the high refractive index layer as necessary. Examples of these additives include antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, anti-aging agents, thermal polymerization inhibitors, colorants, leveling agents, surfactants, storage stabilizers, and plasticizers. , Lubricants, solvents, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like.

  The refractive index of the high refractive index layer can be various refractive indexes depending on the relationship with the refractive index of the low refractive index layer from the viewpoint of antireflection performance, but is generally in the range of 1.49 to 1.60, preferably Is preferably in the range of 1.51 to 1.58, particularly in the range of 1.53 to 1.56. The thickness of the high refractive index layer is generally 1 to 10 μm, preferably 2 to 8 μm.

  The transparent substrate is generally provided with a high refractive index layer on the transparent substrate. However, the transparent substrate can also be provided as a high refractive index layer with a material having a high refractive index. Or you may provide the intermediate | middle layer for the purpose of provision of adhesiveness, reduction of an interference fringe, etc. between a transparent base material and a high refractive index layer.

  As the material of the transparent substrate, various materials can be used as long as the light transmittance is good. For example, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), acrylic resin, polycarbonate Polytetrafluoroethylene (PTFE), 4-fluorinated ethylene-perchloroalkoxy copolymer (PFA), 4-fluorinated ethylene-6-fluorinated propylene copolymer (FEP), 2-ethylene-4-fluoride Examples thereof include films made of fluororesin such as fluorinated ethylene copolymer (ETFE), poly-3-fluoroethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). A PET film and a TAC film are particularly preferable from the viewpoint of transparency and flexibility. From the viewpoint of self-supporting properties, it is preferable to use a glass substrate.

  The thickness of the transparent substrate layer is preferably about 6 to 250 μm.

  In the embodiment in which the intermediate layer is provided between the transparent base material and the high refractive index layer as described above, the refractive index of the intermediate layer varies depending on the refractive index of the transparent base material and the high refractive index layer. However, it is excellent to set to about the middle of the refractive index of the transparent base material and the high refractive index layer, generally in the range of 1.53 to 1.63, preferably 1.54 to 1. A range of .62, in particular a range of 1.55 to 1.61, is preferred. The thickness of the intermediate layer can be set to various thicknesses by setting the refractive index, but is generally in the range of 60 to 115 nm, preferably in the range of 63 to 109 nm, particularly in the range of 65 to 103 nm. By setting the values within these ranges, it is possible to realize an interference fringe prevention function in addition to the antireflection function. In particular, when PET (refractive index: 1.65) or a material having a refractive index close thereto is used as the transparent substrate, an excellent interference fringe prevention function can be realized by setting the above range.

  Another aspect of the flow of manufacturing the antireflection film of the present invention will be described below. Unlike FIG.1 and FIG.2, FIG. 3 is explanatory drawing explaining an example of the flow of manufacture using a release film. On the release film 34, the polymerizable composition used in the present invention is applied, and this is polymerized to provide the low refractive index layer 31 (step 3a). The low refractive index layer thus formed can be handled as a single layer of the low refractive index layer by peeling off the release film 34 (step 3b). Can be affixed. Alternatively, the low refractive index layer 31 provided in the step 3a may be limited to partial polymerization and may be completely polymerized on a separately prepared high refractive index layer. As the release film, a generally used release film (or release paper) may be used. By using such a manufacturing flow, the antireflective film of the present invention can be completed in a separate process using a low refractive index layer manufactured in advance. Also in the manufacturing flow illustrated in FIG. 3, the components and processing methods relating to the polymerizable composition, the low refractive index layer, the high refractive index layer, and the like can be similarly performed.

  The following examples further illustrate the present invention. The present invention is not limited by the following examples.

[Example 1]
Production of Antireflection Film and Display Filter Containing Antireflection Film of the Present Invention Immediately after the formation of a PET film (refractive index: 1.65, 100 μm thickness) as a transparent substrate, a sulfur-modified acrylic resin was applied on this PET film. This was cast and rolled and bonded to form an intermediate layer (intermediate refractive index layer) having a refractive index of 1.57 and a thickness of 80 nm. Next, 75 parts by mass of dipentaerythritol hexaacrylate (DPHA) (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional acrylate monomer, 25 parts by mass of zirconia, 100 parts by mass of MEK, 100 parts by mass of toluene, polymerization start A coating solution containing 4 parts by mass of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name Irgacure 184) as an agent was prepared and applied on the above-described intermediate layer. Next, after drying at 80 ° C. for about 1 minute, the film was cured by ultraviolet irradiation (light amount 500 mJ / cm ² ) to form a hard coat high refractive index layer (refractive index 1.54, thickness 3 μm).

Next, 10 parts by mass of dipentaerythritol polyacrylate polyperfluorobutyrate, 0.5 parts by mass of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name Irgacure 184) as a polymerization initiator, and 90 parts by mass of MIBK as a solvent A coating solution containing was prepared and applied on the hard coat layer described above. Next, after drying at 80 ° C. for about 1 minute, the film was cured by ultraviolet irradiation (light quantity 1000 mJ / cm ² ) to form a low refractive index layer (refractive index 1.42, thickness 100 nm). The dipentaerythritol polyacrylate polyperfluorobutyrate used above contains, as an average ratio, acrylate / fluorobutyrate = 4/2, which is the compound of formula I already described, wherein Y is of formula II It corresponds to a compound in which k and l are 1, and substituent A: substituent B = 4: 2.

  Furthermore, this was bonded together to the glass plate of thickness 2.5mm, and the filter for displays was created.

[Example 2]
Production of antireflection film including antireflection film of the present invention using hollow silica fine particles and filter for display First, an intermediate layer and a hard coat high refractive index layer were formed on a PET film in the same manner as in Example 1. Formed.

Next, 5 parts by mass of the compound dipentaerythritol polyacrylate polyperfluorobutyrate (average ratio acrylate / fluorobutyrate = 4/2) used in Example 1, porous silica (hollow silica fine particles) (average particle diameter 60 nm) ) 5 parts by mass, a photopolymerization initiator as a polymerization initiator (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.5 parts by mass, a coating solution containing 90 parts by mass of MIBK as a solvent was prepared, and the hard coat described above Applied on top of the layer. Next, after drying at 80 ° C. for about 1 minute, the film was cured by ultraviolet irradiation (light quantity 1000 mJ / cm ² ) to form a low refractive index layer (refractive index 1.39, thickness 100 nm).

  Furthermore, this was bonded together to the glass plate of thickness 2.5mm, and the filter for displays was created.

[Comparative Example 1]
Production of antireflection film including low refractive index layer and display filter using fluororesin First, an intermediate layer and a hard coat high refractive index layer were formed in the same manner as in Example 1 on a PET film.

  Next, a fluororesin layer made of perfluorovinyl polymer was provided to form a low refractive index layer (refractive index 1.39, thickness 100 nm).

  Furthermore, this was bonded together to the glass plate of thickness 2.5mm, and the filter for displays was created.

[Comparative Example 2]
Production of antireflection film including antireflection film using acrylic resin as low refractive index layer and filter for display First, an intermediate layer and a high refractive index layer having a hard coat property are formed on the PET film as in Example 1. It formed similarly.

Next, a coating solution containing 10 parts by mass of dipentaerythritol hexaacrylate, a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a polymerization initiator, and 0.5 parts by mass of MIBK as a solvent is prepared. It was coated on the above-described hard coat high refractive index layer. Next, after drying at 80 ° C. for about 1 minute, the film was cured by ultraviolet irradiation (light quantity 200 mJ / cm ² ) to form a low refractive index layer (refractive index 1.49, thickness 100 nm).

  Furthermore, this was bonded together to the glass plate of thickness 2.5mm, and the filter for displays was created.

[Method and results of evaluation]
The antireflection films and display filters obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated by the following methods.

  The luminous reflectance (reflection stimulus value Y defined in JIS Z 8701) was measured using a Hitachi spectrophotometer U-4000.

  The pencil hardness was evaluated by a pencil hardness test based on JIS K5400-1990.

Steel wool resistance is # 0000 steel wool, and the surface of the low refractive index layer is subjected to 10 reciprocations while applying a load of 100 g / cm ² , and then the presence or absence of scratches and the degree of scratches are visually observed. And evaluated according to the following criteria.

A: Generation of scratches was not observed. B: Several scratches were observed. C: Countless scratches were observed. The results of the above evaluation are shown in the following table.

  As listed in the table, in the antireflection film of Comparative Example 1 using a fluororesin, the luminous reflectance is sufficiently low, but the pencil hardness and steel wool resistance are low, UV curing It was found that the antireflection film of Comparative Example 2 using a transparent acrylic resin had sufficiently high pencil hardness and steel wool resistance, but had high luminous reflectance. On the other hand, the antireflection film of the invention shown as Example 1 and Example 2 has low luminous reflectance, high pencil hardness, and high steel wool resistance at the same time as compared with the comparative example, that is, It was found that excellent antireflection performance, hardness and scratch resistance were achieved at the same time.

  Furthermore, in the antireflection films of Example 1 and Example 2, the low refractive index layer was sufficiently in close contact with the hard coat high refractive index layer below it, and no anxiety was generated during handling. It was. In addition, the coating liquid (coating liquid) for the low refractive index layer of the antireflection film of the present invention has no change in viscosity throughout the coating process at the time of manufacture, the liquid properties are stable, and the handling property is excellent. there were.

  Further, the antireflection films of Example 1 and Example 2 have no interference fringes visible, that is, an excellent interference fringe prevention effect is brought about by the presence of the intermediate layer (intermediate refractive index layer). It had been.

FIG. 1 is an explanatory diagram illustrating an example of the flow of manufacturing the antireflection film of the present invention. FIG. 2 is an explanatory view illustrating an example of the flow of manufacturing the antireflection film of the present invention having another structure. FIG. 3 is an explanatory diagram illustrating an example of a manufacturing flow using a release film. FIG. 4 is an explanatory diagram illustrating an example of the structure of a typical front filter for PDP. FIG. 5 is an explanatory view illustrating an example of a general structure of an antireflection film by wet coating.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Low refractive index layer 12 High refractive index layer 13 Transparent base material 21 Low refractive index layer 23 Transparent base material 31 Low refractive index layer 34 Release film 40 Light emitting panel 41 Antireflection layer 42 Electromagnetic wave shield layer 43 Transparent substrate 44 Color correction filter Layer 45 Near-infrared cut layer 51 Low refractive index layer 52 High refractive index layer having hard coat properties 53 Transparent substrate

Claims (21)

The following formula I:

(Where k is a natural number ranging from 0 to 2,
X ^{1 to} X ³ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
And
Y is
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F,
-H or
The following formula II:

A substituent represented by
(Where l is a natural number ranging from 0 to 2,
X ^{4 to} X ⁶ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
Is)
And
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)
An antireflection film comprising a fluorine-containing acrylic resin layer made of a polymerization product of a polymerizable composition containing a fluorine-containing polyfunctional acrylic monomer represented by the formula:   The antireflection according to claim 1, wherein the fluorine-containing acrylic resin layer is provided on a high refractive index layer having a relatively high refractive index as a low refractive index layer having a refractive index lower than that of the high refractive index layer. film. The antireflection film according to claim 1 , wherein the polymerizable composition further contains a photopolymerization initiator. The antireflection film according to claim 1 , wherein X ^{1 to} X ³ and Y are a substituent A or a substituent B. The antireflection film according to claim 1 , wherein Y is a substituent represented by Formula II. The antireflection film according to claim 5 , wherein X ^{1 to} X ⁶ are a substituent A or a substituent B. The antireflection film according to any one of claims 1 to 6 , wherein k is 1. The l is 1, and the antireflection film according to any one of claims 1 to 3 and claims 5 to 7 . The antireflection film according to any one of claims 1 to 8 , wherein the ratio (A: B) of the substituent A to the substituent B is in the range of 3: 3 to 5: 1 as an average value. The antireflection film according to any one of claims 1 to 9 , wherein the fluorine-containing polyfunctional acrylic monomer is contained in the polymerizable composition in a range of 1 to 70 mass% with respect to the polymerizable composition. The antireflection film according to claim 1 , wherein the polymerization product is polymerized by ultraviolet irradiation. The antireflection film according to claim 1 , wherein the polymerizable composition further contains hollow silica fine particles. The antireflection film according to claim 12 , wherein the hollow silica fine particles have an average particle diameter of 5 to 200 nm. The antireflection film according to claim 12 or 13 , wherein the hollow silica fine particles are contained in a range of 0.1 to 50 parts by mass with respect to 10 parts by mass of the fluorine-containing polyfunctional acrylic monomer. The anti-reflective light transmissive window material containing the anti-reflective film in any one of Claims 1-14 . The anti-reflective light transmissive window material which contains the anti-reflective film in any one of Claims 1-14 as an outermost layer. A display filter comprising the antireflective light-transmitting window material according to claim 15 or 16 . A method for producing an antireflection film, comprising the following steps:
The following formula I:

(Where k is a natural number ranging from 0 to 2,
X ^{1 to} X ³ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
And
Y is
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F,
-H or
The following formula II:

A substituent represented by
(Where l is a natural number ranging from 0 to 2,
X ^{4 to} X ⁶ are each independently
A substituent A represented by -CO-CH = CH ₂ ;
-CO (CF ₂₎ substituent B represented by ₃ F, or,
-H,
Is)
And
And the ratio of the substituent A to the substituent B (A: B) is in the range of 2: 4 to 5: 1 as an average value)
A step of applying a polymerizable composition containing a fluorine-containing polyfunctional acrylic monomer represented by : and a photopolymerization initiator on a high refractive index layer having a relatively high refractive index,
A step of curing the polymerizable composition applied in the step by irradiating with ultraviolet rays;
The manufacturing method which provides the low-refractive-index layer whose refractive index is lower than the said high-refractive-index layer by the method containing these. The production method according to claim 18 , wherein the polymerizable composition further contains hollow silica fine particles. An antireflective light-transmitting window material comprising an antireflective film manufactured by the manufacturing method according to claim 18 or 19 . A display filter comprising the antireflective light-transmitting window material according to claim 20 .

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