JP2012008158A - Method for manufacturing reflection prevention member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a reflection prevention member which has reflection prevention effect and low reflectance, high transparency and low interference bands with easier manufacturing steps.SOLUTION: In a method for manufacturing a reflection prevention member in which a coating composition is once applied on at least one surface of a supporting substrate (hereinafter, the surface of the supporting member on which the coating composition is once applied is referred to as a surface A), thereby forming a reflection prevention layer composed of two layers with different refractive indices, the surface roughness (JIS-B-0601:2001) of the surface A is 8 nm or more and 40 nm or less.

Description

  The present invention relates to a method for manufacturing an antireflection member.

  In general, the antireflection member prevents a decrease in contrast and reflection of an image due to reflection of external light in an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), or a liquid crystal display (LCD). Therefore, it is placed on the outermost surface of the display so as to reduce the reflectivity using the principle of optical interference.

  As such an antireflection member, Patent Document 1 discloses that in the antireflection film formed by laminating a hard coat layer, a high refractive index layer and a low refractive index layer on a transparent substrate film, the hard coat layer, Alternatively, an “antireflection film characterized in that the hard coat layer and the high refractive index layer are mainly composed of an ionizing radiation curable resin containing a reactive organosilicon compound” is described.

  In recent years, in addition to the antireflection function, such an antireflection member is also required to have an antireflection function, and the following has been proposed.

  In Patent Document 2, “an antiglare film comprising a resin base film and an antiglare layer laminated on the surface of the resin base film and having an uneven shape on the surface, the antiglare layer comprises: It is a layer made of a transparent resin in which non-spherical light diffusing particles having an aspect ratio of more than 1 represented by the following formula (1) are dispersed, and the uneven shape of the antiglare layer surface uses a metal mold. Antiglare film formed by the embossing method.

Aspect ratio = Lmax / Lver (1)
Here, Lmax is the maximum length of the projection surface when the projection area of the light diffusing particles is minimized, and Lver is the maximum length in the direction orthogonal to the Lmax direction on the projection surface. It is. Is described.

  Further, the following has been proposed as focusing on the function of the interlayer interface of the layers constituting the antireflection member.

  Patent Document 3 states that “an optical film in which a plurality of transparent layers are formed, and a second transparent layer formed by contacting the first transparent layer with the first transparent layer constituting the optical film. The transparent layer is made of a material having a different refractive index, and the contact interface between the first transparent layer and the second transparent layer is a light scattering interface. An optical film "is described.

In Patent Document 4, “a high refractive index layer having a refractive index higher than the refractive index of the transparent substrate on the one surface of the transparent film formed with irregularities on one surface of the transparent substrate; A low refractive index layer having a refractive index lower than the refractive index of the high refractive index layer in this order, and the irregularities are formed by deforming the transparent substrate, [1] to [2 ] [1] 0.04 ≦ Ra ≦ 0.25 μm
[2] 0.001 ≦ Ra / Sm ≦ 0.005
(Ra and Sm are the arithmetic average roughness and the average interval of irregularities measured based on JIS B0601: 1994, respectively).

  Further, the following has been proposed as an antireflection member for forming two layers by one application and a method for manufacturing the same.

  Patent Document 5 states that “an antireflection laminate including a coating film formed by one coating using a coating composition in which low refractive index fine particles and medium to high refractive index fine particles are dispersed in a binder resin. By using silica fine particles treated with a fluorine-based compound as the low refractive index fine particles, low refractive index fine particles are unevenly distributed in the upper part or middle part of the coating film due to the difference in specific gravity, and in the intermediate part or lower part. Describes an antireflection laminate characterized in that medium to high refractive index fine particles are unevenly distributed.

Japanese Patent Laid-Open No. 9-254324 JP 2009-122371 A JP 2005-107005 A JP 2009-211061 A JP 2007-272132 A

  The problem to be solved by the present invention is to provide a method of manufacturing an antireflection member that achieves both prevention of reflection, low reflectance, high transparency, and low interference fringes through a simpler manufacturing process.

  The above-mentioned known technique is in the following situation for the above-mentioned problem.

  In Patent Document 1, the required level of low reflectance and high transparency has been reached. However, the present inventors have confirmed that reflection prevention is not particularly considered and is required. It is inferior to the standard, and the manufacturing process is complicated because it requires at least three coatings.

  In Patent Document 2, the prevention of the reflection is achieved by combining the embossing method using a non-spherical light diffusing particle and a metal mold for the prevention of the reflection. As an index to be expressed, the haze is as high as 2 to 40%, which is a category of a general antiglare film, and an antireflection member that achieves both high transparency and low reflectance while preventing the currently required reflection. It cannot be said.

  Patent Documents 3 and 4 focus on the function of the interlayer interface of the layers constituting the antireflection member, but the purpose is to prevent interference fringes and whiteness, and to determine the degree of roughness and the object. The roughness of the interface is rough. Although it is effective in preventing reflection and suppressing interference unevenness, it cannot achieve both low reflectance and high transparency because of the light scattering interface. Furthermore, the manufacturing process is complicated, and it is difficult to achieve the task.

  In Patent Document 5, two layers are obtained by one coat, and the interface between the low refractive index layer and the high refractive index layer forming the antireflection layer is not clear but is clearly integrated, and thus has an antireflection with a clear boundary. It is described that the problem of delamination between the respective refractive index layers as compared with the layer is solved. However, due to the unclear interface that is unifying, it is expected that the reflectivity and transparency will decrease, and it is difficult to achieve the task.

  Further, none of Patent Documents 1 to 5 has been conceived of the manufacturing method of the present invention.

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) By applying the coating composition only once on at least one surface of the supporting substrate (hereinafter, the surface of the supporting substrate on which the coating composition is applied only once is referred to as surface A), the refractive index of A method for producing an antireflection member, characterized by forming an antireflection layer comprising two different layers,
The method for producing an antireflection member, wherein the surface A has a surface roughness (JIS-B-0601: 2001) of 8 nm or more and 40 nm or less.

The coating composition comprises two or more inorganic particles, one or more binder components, and a metal chelate;
The method for producing an antireflection member according to claim 1, wherein at least one of the two or more types of inorganic particles is an inorganic particle treated with a hydrophobic compound A.
2) The coating composition contains two or more types of inorganic particles, one or more types of binder components, and a metal chelate,
The method for producing an antireflection member as described in 1) above, wherein at least one of the two or more types of inorganic particles is an inorganic particle treated with a hydrophobic compound A.
3) The method for producing an antireflection member as described in 1) or 2) above, wherein the viscosity change (Δη) of the coating composition is 0.1 mPa · s to 10 mPa · s.
(Where Δη and represents the viscosity eta ₁ at a shear rate of 0.1s ^-1, the difference in viscosity eta ₂ at a shear rate of ^{10s -1} and (η ₁ -η _2).)
4) The method for producing an antireflection member according to any one of 1) to 3) above, wherein the coating composition contains the following hydrophobic compound B.

  The hydrophobic compound B is at least one compound selected from the group consisting of a fluorine compound B, a long-chain hydrocarbon compound B, and a silicone compound B.

  The fluorine compound B is a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site.

  The long-chain hydrocarbon compound B is a compound having a hydrocarbon group having 8 or more carbon atoms and a reactive site.

Silicone compound B is a compound having a siloxane group and a reactive site.
5) The hydrophobic compound B includes a fluorine compound B,
The method for producing an antireflection member as described in 4) above, wherein the fluorine compound B has a number average molecular weight of 300 or more and 4000 or less.
6) The fluorine compound B has a viscosity η _F measured by a vibration viscometer of 1 to 100 mPa / s and a surface tension γ _{F of 6} to 26 mN / m, as described in 5) above Manufacturing method of antireflection member.
7) From the monomer derived from the following general formula (A), the monomer represented by the general formula (B), the oligomer derived from the monomer represented by the general formula (A), and the oligomer derived from the monomer represented by the general formula (B). The method for producing an antireflection member according to 5) or 6) above, wherein the method is at least one compound selected from the group consisting of:

^{_{H 2 C = C (R 1}} ) -COO-R 2 -R f1 ··· formula (A)
^{AR 3} -R ^f1 ... General formula (B)
(Wherein R ¹ is a hydrogen atom or a methyl group, R ^f1 is a linear or branched fluoroalkyl group having 4 to 7 carbon atoms, R ² and R ³ are alkyl groups having 1 to 10 carbon atoms, and A is Reactive site.)

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the reflection preventing member which made reflection prevention, low reflectance, high transparency, and also low interference fringe compatible by a simpler manufacturing process can be provided.

Configuration of antireflection member of the present invention Structure of conventional antireflection member Structure of conventional antireflection member

  First, we will discuss both the prevention of reflection, low reflectivity, and high transparency. Conventionally known basic anti-reflection technology introduces a relatively large surface irregularity shape to scatter reflected light and disturb the reflected image formed on the surface, making it difficult to understand. is there. However, in this method, light is scattered on a surface having a large difference in refractive index, so that the reflectance cannot be lowered as in the case of utilizing the light interference effect, and the transparency is significantly lowered. Further, in Patent Document 2, by containing particles having a large aspect ratio inside, anisotropy is given to light scattering inside the coating film, and the anisotropic scattering inside the layer is strengthened to prevent reflection. However, a decrease in reflectance and an improvement in transparency cannot be obtained.

  Next, the coexistence of interference fringes and transparency will be described. Interference fringes are caused by changes in film thickness due to fluctuations in the liquid film during the coating process, changes in film thickness due to uneven drying speed in the drying process, and changes in the thickness of the antireflection layer due to variations in substrate thickness. By appearing in a long period that can be visually observed, it is considered that a shift occurs in the interference effect and a change in reflected color is visually observed. With respect to this problem, Patent Documents 4 and 5 solve the deviation of the interference effect by making the interface light scattering, but the transparency is lowered by becoming light scattering.

  As a result, not all the problems can be achieved by the known technology. Next, the reason why the present invention can solve the above-mentioned problems will be described.

  The inventors of the present invention have focused on the interface between the support substrate and the antireflection layer as a production method that achieves both antireflection performance, low reflectance, high transparency, and low interference fringes. The above problem is solved by combining the technique of forming two layers having different refractive indexes by controlling the roughness of the interface (surface A) in a specific region and applying the coating composition once. I found it possible.

  This means that when the surface of the supporting substrate on which the coating composition is applied is the surface A, the surface A of the supporting substrate is assembled within the scope of the present invention, that is, fine irregularities are formed. As a result, the reflected light is slightly disturbed within a range that does not affect the antireflection performance and transparency, and it is possible to achieve both high transparency and antireflection.

  In addition, as described above, since the interface between the support base and the antireflection layer is finely interlaced, the thickness of the high refractive index layer has a substantial width. Misalignment can be absorbed. At this time, since the amount of finely intermingled interfaces is sufficiently shorter than the wavelength of light, light scattering does not occur and the transparency is not affected.

  Hereinafter, embodiments of the present invention will be specifically described.

  FIG. 1 shows an example of the configuration of the antireflection member of the present invention. In the antireflection member 1 of the present invention, an antireflection layer 3 composed of two layers having different refractive indexes is laminated on at least one surface of a support base 2. Note that a surface of the support base on which the coating composition is applied is referred to as a surface A.

  Here, the surface A refers to a case where a support substrate having a functional layer other than an antireflection layer such as an easy-adhesion layer, a hard coat layer, or an antistatic layer is used, chemical treatment, mechanical treatment, corona discharge treatment, flame Even when using a support substrate that has been subjected to treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., an antireflection layer is applied in the coating process. In order to indicate the surface of the supporting substrate on which the coating composition to be formed is applied, in the case of a supporting substrate having a functional layer, the surface on the side of the functional layer is treated. Refers to the side where the is made.

  In the antireflection member, two layers constituting the antireflection layer are composed of a first layer and a second layer, and the first layer, the second layer, and the support base material are laminated in this order. The first layer is preferably a low refractive index layer and the second layer is preferably a high refractive index layer.

  In the present invention, the coating composition is applied only once to at least one surface of the supporting substrate (hereinafter, the surface of the supporting substrate on which the coating composition is applied only once is referred to as “surface A”). A method for producing an antireflection member, comprising forming an antireflection layer comprising two layers having different rates, wherein the surface A has a surface roughness (JIS-B-0601: 2001) of 8 nm or more and 40 nm or less. It is a manufacturing method of an antireflection member characterized by being.

  In the present invention, it is important that the surface roughness of the surface A in the supporting substrate is from 8 nm to 40 nm, preferably from 10 nm to 35 nm, more preferably from 12 nm to 30 nm.

  When the surface roughness of the surface A is smaller than 8 nm, the interface structure between the support base material and the antireflection layer of the obtained antireflection member is in the state shown in FIG. 2, and the physical interface at the interface between the support base material and the antireflection layer is obtained. Since the effect of improving the adhesion force from a small viewpoint becomes small, the scratch resistance and wear resistance are poor. Further, since a fine uneven structure is not formed at the interface between the support base and the antireflection layer, there is a problem that low interference fringes and reflection preventing performance cannot be obtained.

  When the surface roughness of the surface A is larger than 40 nm, the interface structure between the support base material and the antireflection layer of the obtained antireflection member is in the state shown in FIG. 3, and light is transmitted at the interface between the support base material and the antireflection layer. Since scattering occurs, there is a problem that performance such as low reflectance and transparency cannot be obtained.

  Further, when a coating composition that forms two antireflection layers in one application is applied, if the surface roughness of the surface A is larger than 40 nm, the formation of a spontaneous layer structure is hindered, which is clearly An interface structure cannot be formed, and antireflection performance cannot be obtained.

Therefore, in the present invention, it is important that the surface roughness of the surface A is 8 nm or more and 40 nm or less.
[Antireflection member]
The antireflection member obtained by the present invention refers to a member in which a layer having an antireflection function (an antireflection layer comprising two layers having different refractive indexes) is formed on at least one surface of various support substrates. In the case of a plastic film, it is generally called an antireflection film. The necessity and required performance are composed of two layers having a refractive index difference of preferably 0.03 or more, more preferably 0.05 or more, as described in JP-A-59-50401. This is an aspect constituted by laminating an antireflection layer on a supporting substrate. The refractive index difference between the two layers constituting the antireflection layer is preferably 5.0 or less (that is, the refractive index difference between the first layer and the second layer is preferably 0.03 or more, more preferably 0.05 or more, and the upper limit is 5.0 or less.) This refractive index difference is a value obtained by relatively comparing the refractive indexes of 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 highly refracted. Called the rate layer. In the antireflection member, the first layer is preferably a low refractive index layer and the second layer is preferably a high refractive index layer.

  As described above, FIG. 1 shows an example of the structure of the antireflective member of the present invention. In the present invention, the second layer in contact with the support base has a high refractive index function and also has scratch resistance. Is preferred. In this case, the second layer is called a high refractive index hard coat layer. The high refractive index hard coat layer further preferably has a function of strengthening the adhesion between the support base 2 and the low refractive index layer 5. The strength of the high refractive index hard coat layer is preferably 1 or higher, more preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. As for the upper limit, there is no problem with the high strength, but in reality, the upper limit is about 9H.

  The present invention described above is characterized in that an antireflection layer comprising two layers having different refractive indexes is formed by applying the coating composition only once on at least one surface of the support substrate. It is a manufacturing method.

  Here, applying the coating composition only once refers to applying one type of coating composition to the supporting substrate only once. Therefore, coating the coating composition only once means a multi-layer simultaneous coating in which a liquid film composed of a plurality of layers is applied once at the time of a single application, and a single layer of liquid film is applied a plurality of times in a single application. It does not mean wet-on-wet coating or the like in which continuous sequential drying is performed, and one layer of liquid film is dried after being applied a plurality of times during one application.

  The coating composition preferably contains two or more kinds of inorganic particles and one or more kinds of binder components. Then, inorganic particles in which at least one of the two or more types of inorganic particles is treated with the hydrophobic compound A (hereinafter, the inorganic particles treated with the hydrophobic compound A are referred to as hydrophobic treated inorganic particles). ) Is preferable. Further, the coating composition preferably contains a metal chelate compound. The inorganic particles, binder component, hydrophobic compound A, hydrophobic treated inorganic particles, and metal chelate compound will be described later.

  The principle of forming an antireflection layer consisting of two layers having different refractive indexes on a supporting substrate by applying the coating composition only once is that two or more kinds of inorganic particles in the coating composition The inorganic particles that have moved through the Brownian motion and reached the gas-liquid / solid-liquid interface are fixed to the atmosphere side by the surface free energy difference and to the support substrate side by the low surface energy inorganic particles. Thus, it is considered that a layer structure (an antireflection layer composed of two layers having different refractive indexes) can be spontaneously formed.

  Two layers having different refractive indexes constituting the antireflection layer are measured by a reflectance spectral film thickness meter in the range of 300 to 800 nm, and by using the software [FE-Analysis] attached to the apparatus, The refractive index of the layer can be obtained.

Specifically, the reflectance is measured using a reflection spectral film thickness meter (FE-3000, manufactured by Otsuka Electronics Co., Ltd.), and manufactured by Otsuka Electronics Co., Ltd. [Film thickness measuring apparatus general catalog P6 (nonlinear least square method)]. The optical constants (C ₁ , C ₂ , C ₃ ) are calculated by the least square method (curve fitting method) using the Cauchy's dispersion formula (Formula 1) as an approximate expression of the refractive index wavelength dispersion. Thus, the refractive index can be measured. In addition, the value in 550 nm was used for the refractive index.

Here, λ represents a wavelength, and C ₁ , C ₂ , and C ₃ represent optical constants.
In addition, the arrangement of inorganic particles is between the high refractive index layer (or high refractive index hard coat layer) and the low refractive index layer (between the second layer and the first layer) which are two layers having different refractive indexes. It is preferable that there is a clear interface.

  A clear interface in the present invention refers to a state in which one layer can be distinguished from another layer. The distinguishable interface was determined by observing a cross section using a transmission electron microscope (TEM) to determine the presence or absence of a two-layer interface on the support substrate.

  In order to exhibit good performance as an antireflection member, the minimum reflectance is preferably 0% or more and 1.0% or less, more preferably 0% or more and 0.7% or less, and further preferably 0% or more and 0.0. It is 6% or less, and particularly preferably 0% or more and 0.5% or less.

  Further, in order to exhibit good properties as an antireflection member, it is desirable that the transparency is higher. If the transparency is low, it is not preferable when used as an image display device because image quality is deteriorated due to a decrease in image saturation. A haze value can be used for evaluating the transparency of the antireflection member. Haze is an index of turbidity of a transparent material defined in JIS K 7136 (2000). The smaller the haze, the higher the transparency. The haze value of the antireflection member is preferably 2.0% or less, more preferably less than 1.8%, still more preferably less than 1.5%, and the smaller the value, the better the transparency. Although it is, it is difficult to set it to 0%, and a realistic lower limit value seems to be about 0.01%. If the haze value exceeds 2.0%, the possibility of image deterioration is increased, which is not preferable.

  In order to exhibit good properties as an antireflection member, the thickness of the second layer and the first layer is preferably a specific thickness, and the thickness of the first layer (low refractive index layer) is preferably 50 nm or more and 200 nm or less. More preferably, it is 70 nm or more and 150 nm or less, and particularly preferably 90 nm or more and 130 nm or less. If the thickness of the first layer (low refractive index layer) is less than 50 nm, the light interference effect cannot be obtained, the antireflection effect cannot be obtained, and the reflection of the image increases, which is not preferable. Further, when the thickness exceeds 200 nm, the light interference effect cannot be obtained, and the reflection of the image becomes large, which is not preferable.

The antireflection member may further be provided with an easy adhesion layer, a moisture proof layer, an antistatic layer, a shield layer, an undercoat layer, a protective layer, and the like. The shield layer is provided to shield electromagnetic waves and infrared rays. In order to form these layers in the antireflective member, a method of applying a film having these layers as a supporting substrate can be used.
[Metal chelate compounds]
The coating composition preferably contains a metal chelate compound. The metal chelate compound in the present invention is a general term for compounds in which a compound having a multidentate ligand in a molecule forms a complex so that a metal ion is sandwiched between them.

  The metal chelate compound has an effect of assisting the curing of the resin containing silanol and the like, and the curing of the resin containing silanol and the like proceeds stably in the drying step. Therefore, the film hardness is increased, and the scratch resistance and wear resistance are improved, so that a metal chelate compound is preferably included.

  Moreover, the effect is accelerated | stimulated by heating, The temperature suitable for a drying process becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 130 degreeC or more. Setting the heating temperature to 100 ° C. or higher is preferable because curing of a resin containing silanol or the like proceeds stably in a very short time.

  Although the metal ion in a metal chelate compound will not be specifically limited if it is an alkali metal element, an alkaline-earth metal element, a metal element, etc., Preferably titanium or aluminum, More preferably, aluminum can be mentioned.

  Specific examples of the metal chelate compound include, for example, aluminum trisethyl acetoacetate, aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate, aluminum trisacetylacetonate, aluminum ethylacetoacetate / diisopropylate. Titanium chelate compounds such as aluminum chelate compounds such as rate, triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium, Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tris ( It can be mentioned acetylacetonate) compounds of zirconium chelate compounds such as mono (ethylacetoacetate) zirconium.

These metal chelate compounds may be used alone or in combination of two or more. Of these metal chelate compounds, aluminum chelate compounds are particularly preferred from the viewpoints of coating stability and film curability contribution.
[Inorganic particles contained in the coating composition]
The coating composition preferably contains two or more kinds 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, still more preferably 2 or more and 3 or less, and most preferably 2 types.

Here, the kind of inorganic particles is determined by the kind of elements constituting the inorganic particles (in the hydrophobic treated inorganic particles described later, the kind is determined by the kind of elements constituting the inorganic particles before being treated with the hydrophobic compound A). .) For example, since titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO _2−x N _x ) in which part of oxygen in titanium oxide is replaced with nitrogen as an anion, the elements constituting the inorganic particles are different, Different types of particles. Further, if inorganic particles (ZnO) consisting only of the same element, for example, Zn, O, even if there are a plurality of inorganic particles having different particle diameters, and the composition ratio of Zn and O is different, These are the same kind of inorganic particles. Even if there are a plurality of Zn particles having different oxidation numbers, as long as the elements constituting the inorganic particles are the same (in this example, all elements other than Zn are the same), these are the same kind of inorganic particles. It is.

  First, the inorganic particles that are suitably used as the first layer (low refractive index layer) component will be described.

The at least one inorganic particle in the two or more types of inorganic particles of the coating composition is preferably an inorganic particle treated with a hydrophobic compound A (referred to as a hydrophobically treated inorganic particle). Is suitable as a constituent component of the first layer (low refractive index layer). (The hydrophobic compound A will be described later.) Inorganic particles suitable as a constituent material of the hydrophobic treated inorganic particles preferably include inorganic particles containing an element selected from Si, Na, K, Ca, and Mg. More preferably, it is an inorganic particle 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.), and is durable. From the viewpoint of refractive index, silica particles are particularly preferable. The silica particles treated with the hydrophobic compound A are hereinafter referred to as hydrophobic treated silica particles.

The silica particles preferably used as the inorganic particles of the constituent material of the hydrophobically treated inorganic particles are a general term for particles derived from a silicon compound such as SiO ₂ as a general example. In a more preferred embodiment of the present invention, the silica particles are embodiments of hollow silica particles. Here, the hollow silica particles are silica particles having cavities inside the particles. ).

  Then, the number average particle diameter of the inorganic particle which is a constituent material of the hydrophobic treatment inorganic particle suitable for the first layer (low refractive index layer) will be described. When the number average particle diameter (number average particle diameter before being processed) of such inorganic particles is smaller than 1 nm, the first layer on the support substrate in the antireflection member obtained from the coating composition containing the particles The number average particle diameter of the inorganic particles (number average particle diameter before being processed) is undesirable because the refractive index may increase and the transparency may decrease due to a decrease in void density in the (low refractive index layer). If the thickness exceeds 200 nm, the thickness of the low refractive index layer of the antireflection member obtained from the coating composition containing the particles becomes thick, and it is not preferable because good antireflection performance cannot be obtained. Therefore, the inorganic particles treated with the hydrophobic compound A in the coating composition have a number average particle size (number average particle size before treatment) of preferably 1 nm to 200 nm, more preferably 20 nm to 200 nm, More preferably, it is 40 nm or more and 150 nm or less.

  Here, the number average particle size of the particles in the coating composition refers to the particle size obtained by observing the antireflection layer in the antireflection member obtained by the production method of the present invention with a transmission electron microscope. The magnification was 500,000 times, the outer diameter of 100 particles present on the screen was measured, and the average value was obtained.

  Here, the outer diameter means the maximum diameter of the particle (that is, the longest diameter of the particle and indicates the longest diameter in the particle). Similarly, in the case of a particle having a cavity inside, the maximum diameter of the particle is also defined. To express.

  Hydrophobic treated inorganic particles are preferably moved to the air side (outermost surface layer) and can preferably form the first layer (low refractive index layer), so that two or more types of inorganic particles used in the coating composition At least one kind of inorganic particles is preferably treated with the hydrophobic compound A. In addition, rather than all the inorganic particles of two or more types of inorganic particles being hydrophobically treated inorganic particles, the hydrophobically treated inorganic particles and other inorganic particles that have not been treated (hereinafter referred to as hydrophobically treated inorganic particles). The use of a coating composition containing both of the removed inorganic particles (referred to as other inorganic particles) is preferable in terms of antireflection properties because two layers having a large refractive index difference can be obtained. That is, it is preferable that the coating composition used in the present invention includes at least one kind of both hydrophobic treated inorganic particles and other inorganic particles. In addition, since other inorganic particles are used suitably as a 2nd layer (high refractive index layer) structural component, it demonstrates later.

  The inorganic particles to be treated with the hydrophobic compound A are preferably silica particles, that is, the hydrophobic treated inorganic particles are particularly preferably hydrophobic treated silica particles.

  The treatment process with the hydrophobic compound A for the inorganic particles may be performed in one stage or may be performed in multiple stages. Further, the hydrophobic compound A may be used in a plurality of stages, or the hydrophobic compound A may be used only in one stage.

  The hydrophobic compound A in the present invention is a compound having a hydrophobic group and a reactive site.

  The hydrophobic group of the hydrophobic compound A in the present invention is not particularly limited as long as it generally has a hydrophobic function, but specific examples of the hydrophobic group include a fluoroalkyl group having 4 or more carbon atoms and a hydrocarbon having 8 or more carbon atoms. And at least one functional group selected from the group consisting of a group and a siloxane group is exemplified (in the following description, a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site is represented by fluorine compound A). A compound having a hydrocarbon group having 8 or more carbon atoms and a reactive site is referred to as a long-chain hydrocarbon compound A, and a compound having a siloxane group and a reactive site is referred to as a silicone compound A). Moreover, the hydrophobic compound A used for the treatment of the inorganic particles may be a single compound or a plurality of different compounds. When the hydrophobic compound A is any compound selected from the group consisting of a fluorine compound A, a long-chain hydrocarbon compound A, and a silicone compound A, the same compound as the hydrophobic compound B described later is used. be able to.

  The long-chain hydrocarbon compound A in the present invention represents a compound having a hydrocarbon group having 8 or more carbon atoms which is a hydrophobic group in the molecule and a reactive site. The hydrocarbon group having 8 or more carbon atoms preferably has 8 to 30 carbon atoms. The hydrocarbon group having 8 or more carbon atoms can be selected regardless of a linear structure, a branched structure, or an alicyclic structure. More preferably, the long-chain hydrocarbon compound A is a compound in which the hydrophobic group has a linear alkyl group having 10 to 22 carbon atoms, and includes alkyl alcohol, alkyl epoxide, alkyl acrylate, alkyl methacrylate, alkyl carboxylate (acid Including anhydrides and esters), and the like.

  Specific examples of the long-chain hydrocarbon compound A include polyhydric alcohols such as octanol, hexanediol, heptanediol, octanediol, stearyl alcohol, octyl acrylate, octyl methacrylate, 2-hydroxyoctyl acrylate, 2-hydroxyoctyl methacrylate, Acrylate silane such as acrylate (methacrylate), octyltrimethoxysilane, and the like.

  The silicone compound A in the present invention represents a compound having a siloxane group which is a hydrophobic group in the molecule and a reactive site. As the reactive site of the silicone compound A, a (meth) acrylate group is preferably used.

The siloxane group referred to in the present invention is a polymer having a continuous siloxane bond (—Si—O—) as a skeleton, and a polysiloxane group represented by the general formula (C) is preferably used as the siloxane group.
^{- (Si (R 8) (} R 9) -O) m - ··· formula (C)
(M is an integer of 10 to 200.)
(R ⁸ and R ⁹ are not particularly limited, but any alkyl group having 1 to 6 carbon atoms, phenyl group, 3-acryloyl-2-hydroxypropylsiloxane group, 2-acryloyl-3-hydroxypropylsiloxane group, terminal (Selected from a polyethylene glycol propyl ether group having an acrylate group, a polyethylene glycol propyl ether group having a terminal hydroxy group, etc.)
Specific examples of the silicone compound A having a polysiloxane group of the general formula (C) as a hydrophobic group include compounds having a dimethylsiloxane group represented by the following general formula (III) and a reactive site. Here, R represents a reactive site, and a preferred embodiment of R is a methacryl group, an epoxy group, or a carboxyl group. Specific examples of the silicone compound A having a dimethylsiloxane group of the general formula (III) and a reactive site include X-22-164B, X-22-164C, X-22-5002, X-22-174D, And X-22-167B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The fluorine compound A in the present invention represents a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site in the molecule. The fluorine compound A is the same as the fluorine compound B described later, and the detailed description and specific examples of the fluorine compound A are the same as the description of the fluorine compound B described later.

  A method of directly introducing a hydrophobic compound A such as a fluorine compound A into inorganic particles such as hollow silica particles includes a hydrophobic segment and a silyl ether group (including a silanol group obtained by hydrolyzing a silyl ether group) in one molecule. There is a method which comprises at least one kind of hydrophobic compound A having both and an initiator together. However, when the hydrophobic compound A is directly introduced into inorganic particles such as hollow silica particles, it may be difficult to control the reactivity, or coating spots may be easily generated during coating after coating.

  Further, as a further method for introducing a hydrophobic group such as a fluoroalkyl group into inorganic particles such as hollow silica particles by subjecting inorganic particles such as hollow silica particles to surface treatment with a hydrophobic compound A such as fluorine compound A, There is a method in which inorganic particles such as silica particles are treated with a cross-linking component and are combined with the hydrophobic compound A.

  In addition, the hydrophobic compound A can be obtained by directly surface-treating inorganic particles such as hollow silica particles to obtain hydrophobic-treated inorganic particles, but before the surface treatment with the hydrophobic compound A, the inorganic particles Is preferably treated with a crosslinking component. As a crosslinking component when treating inorganic particles such as hollow silica particles with a crosslinking component, there is no hydrophobic group such as fluorine element in the molecule, but a site capable of reacting with hydrophobic compound A such as fluorine compound A, The compound which has at least one site | part which can react with inorganic particles, such as a hollow silica particle, can be mentioned. And as a site | part which can react with inorganic particles, such as a hollow silica particle, it is preferable that it is a hydrolyzate of a silyl ether and a silyl ether from a reactive viewpoint. These compounds are generally called silane coupling agents. For example, glycidoxyalkoxysilanes, aminoalkoxysilanes, acryloylsilanes, methacryloylsilanes, vinylsilanes, mercaptosilanes, etc. may be used. it can.

  Moreover, as such a crosslinking component, the compound of the following general formula (I) is preferable. In other words, the hydrophobic treated inorganic particles suitable for the coating composition of the present invention are preferably treated by treating the inorganic particles once with the crosslinking component of the following general formula (I) and then treating with the hydrophobic compound A. The treatment in two steps in this manner is preferable because the hydrophobic compound A can be easily treated with respect to the inorganic particles.

B—R ⁴ —SiR ⁵ _n (OR ⁶ ) _3-n General Formula (I)
Further, with respect to the hydrophobically treated inorganic particles obtained by treating in such two steps, a more preferred form of the hydrophobically treated inorganic particles A suitable for the coating composition of the present invention is silica particles represented by the following general formula (I): And particles treated with a fluorine compound A represented by the following general formula (II).
B—R ⁴ —SiR ⁵ _n (OR ⁶ ) _3-n General Formula (I)
D—R ⁷ —R ^f2 general formula (II)
(B and D in the above general formula represent reactive sites, R ⁴ and R ⁷ represent an alkylene group having 1 to 3 carbon atoms and an ester structure derived therefrom, and R ⁵ and R ⁶ represent hydrogen or carbon. The number represents an alkyl group having 1 to 4, R ^f2 represents a fluoroalkyl group, n represents an integer of 0 to 2, and each side chain 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.

  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) that does not have a fluoroalkyl group R ^f2 in the molecule, it is possible not only to modify the surface of the silica particles under simple reaction conditions, It is possible to introduce a functional group whose reactivity is easy to control on the surface, and as a result, a fluorine compound A (general formula (II)) having a reactive site and a fluoroalkyl group R ^f2 is represented by the general formula (I). It is possible to react on the surface of the silica particles via the compound shown.

  Subsequently, other inorganic particles excluding the hydrophobic treated inorganic particles A will be described. The coating composition used in the present invention preferably contains two or more types of inorganic particles, but at least one of the inorganic particles is preferably another inorganic particle. Other inorganic particles excluding the hydrophobic treated inorganic particles A are suitably used as the constituent component of the second layer (high refractive index layer).

Other inorganic particles are not particularly limited, but are preferably metal or metalloid oxides, and are at least one metal selected from the group consisting of Zr, Ti, Al, In, Zn, Sb, Sn, and Ce. It is more preferable that the oxide particles are semi-metal oxide particles. The other inorganic particles suitably used as the constituent component of the second layer (high refractive index layer) are preferably inorganic particles having a refractive index higher than that of 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 ( At least one metal oxide selected from In ₂ O ₃ ) or a semimetal oxide, particularly preferably antimony-containing tin oxide (ATO), titanium oxide (TiO ₂ ), or zirconium oxide (ZrO ₂ ).

  It is preferable that the coating composition contains at least one kind of other inorganic particles (particles made of a metal oxide or a semimetal oxide) excluding these hydrophobic treated inorganic particles A. More preferably, it is an embodiment including one or more types and 5 or less types of other inorganic particles excluding the hydrophobic treated inorganic particles A, and an embodiment including one type is particularly preferable.

  Number average particle diameter of other inorganic particles suitable as a second layer (high refractive index layer) component in the coating composition, particularly a metal oxide having a higher refractive index than silica particles suitable as a low refractive index layer component The average particle size of the inorganic particles made of or semimetal oxide is preferably 1 nm to 150 nm, more preferably 2 nm to 100 nm, still more preferably 25 nm or less, and particularly preferably 20 nm or less. When the number average particle diameter of other inorganic particles is smaller than 1 nm, it is not preferable because transparency decreases due to a decrease in void density in a layer that mainly contains other inorganic particles. When the number average particle diameter is larger than 150 nm, the thickness of the high refractive index layer becomes too large, and it is difficult to obtain good antireflection performance, which is not preferable.

  Refractive index of other inorganic particles suitable as a component of the second layer (high refractive index layer) in the coating composition, in particular, refraction of inorganic particles made of metal oxide or semimetal oxide having a higher refractive index than silica particles The rate is preferably 1.58 or more and 2.80 or less, more preferably 1.60 or more and 2.50 or less. If the refractive index of the inorganic particles is smaller than 1.58, the refractive index of the second layer (high refractive index layer) may be lowered, and if the refractive index of the inorganic particles is larger than 2.80, the second layer. The difference in refractive index between the (high refractive index layer) and the supporting substrate is increased, so that good antireflection performance cannot be obtained, and an interference pattern may be generated to deteriorate the appearance.

Other inorganic particles used as the second layer (high refractive index layer) component in the coating composition are as described above, but when the inorganic particles treated with the hydrophobic compound A are silica particles, the silica particles Inorganic particles having a refractive index higher than that of the particles are particularly preferable. As such inorganic particles having a refractive index higher than that of the silica particles, the number average particle diameter is 1 nm to 150 nm and the refractive index is 1. A metal oxide or metalloid oxide of 60 to 2.80 is preferably used. Specific examples of such metal oxides and metalloid oxides include antimony-containing tin oxide (ATO) and / or titanium oxide (TiO ₂ ). Particularly, titanium oxide having a high refractive index in terms of antireflection properties. Is more preferable.

In the coating composition used in the present invention, when the hydrophobic treated inorganic particles A are fluorinated silica particles and the other inorganic particles are inorganic particles having a higher refractive index than the silica particles, the surface A of the supporting substrate The coating composition is applied only once, followed by drying, so that a first layer containing fluorinated silica particles (low refractive index layer) and a second layer containing other inorganic particles (high This is a preferred embodiment because an antireflection layer composed of a (refractive index layer) can be suitably formed in the order of the support substrate, the second layer (high refractive index layer), and the first layer (low refractive index layer).
[Viscosity of coating composition]
The coating composition used in the present invention preferably has a viscosity change (Δη) of 0.1 mPa · s to 10 mPa · s. In the process of applying and drying the coating composition, the solid content concentration increases and the fluidity decreases with the volatilization of the organic solvent, but the viscosity change (Δη) of the coating composition is 0.1 mPa · s to 10 mPa · s. In some cases, the fluidity can be prevented from being lowered, the interaction between the hydrophobic treated inorganic particles can be suppressed, and the formation of aggregates between the particles can be suppressed. Thus, it is possible to exhibit good antireflection properties.

  From these points, the viscosity change (Δη) of the coating composition is more preferably 0.1 mPa · s or more and 9 mPa · s or less, further preferably 0.1 mPa · s or more and 8 mPa · s or less, and 0.1 mPa · s or more. 7 mPa · s or less is particularly preferable.

Here, the viscosity change of the coating composition (.DELTA..eta), is the difference in viscosity viscosity eta ₂ at viscosity eta ₁ and shear rate ^{10s -1} at a shear rate of 0.1s ^-1 (η ₁ -η ₂₎ . The viscosity eta ₂ at viscosity eta ₁ and shear rate ^{10s -1} at a shear rate of 0.1s ^-1 can be measured by using a general rotary rheometer.

In order to set the viscosity change (Δη) of the coating composition to 0.1 mPa · s or more and 10 mPa · s or less, at least one kind of inorganic particles in the two or more kinds of inorganic particles in the coating composition is hydrophobically treated inorganic particles. It is important that the coating composition contains a hydrophobic compound B, which will be described later, and a polyfunctional acrylate having 3 or more acryloyloxy groups in one molecule is used as a binder component. The method of doing is also preferable.
[Hydrophobic Compound B]
The coating composition preferably contains the following hydrophobic compound B. When the coating composition contains the hydrophobic compound B, the antireflection layer of the antireflection member obtained by using the coating composition can contain a component derived from the hydrophobic compound B.

  The hydrophobic compound B is at least one compound selected from the group consisting of the following fluorine compound B, long-chain hydrocarbon compound B, and silicone compound B.

  The hydrophobic compound B in the present invention has a function of suppressing the formation of aggregates between inorganic particles, and the antireflection member obtained using the coating composition can exhibit good antireflection properties. Therefore, it is preferably contained in the coating composition, and the more preferable hydrophobic compound B is a fluorine compound B.

  Further, the hydrophobic compound B may be the same compound as the hydrophobic compound A used for the treatment for obtaining the hydrophobic treated inorganic particles. That is, the hydrophobic compound A is a compound having a hydrophobic group and a reactive site, but when the hydrophobic compound A is selected from a fluorine compound A, a long-chain hydrocarbon compound A, and a silicone compound A, the hydrophobic compound B and the hydrophobic compound A can be the same compound, but there is no problem even if the hydrophobic compound A and the hydrophobic compound B are the same compound. However, in addition to the hydrophobic compound A used for the treatment for obtaining the hydrophobic treated inorganic particles, the hydrophobic treated inorganic particles are preferably contained on the air side by containing the hydrophobic compound B that is not bonded to the particle surface. It is preferable that the coating composition of the present invention contains the hydrophobic compound B, since the low refractive index layer can be suitably formed by moving to the outermost surface layer.

  The fluorine compound B is a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site. The fluoroalkyl group referred to in the present invention is a substituent in which all hydrogens in the alkyl group are replaced with fluorine, and is a substituent composed of only a fluorine atom and a carbon atom. Details will be described later.

  The long-chain hydrocarbon compound B is a compound having a hydrocarbon group having 8 or more carbon atoms and a reactive site. That is, the preferred embodiment of the long-chain hydrocarbon compound B is the same as the description of the preferred embodiment of the long-chain hydrocarbon compound A described above. Specific examples of the long-chain hydrocarbon B are also the same as those of the long-chain hydrocarbon A described above. The same as the specific example.

Silicone compound B is a compound having a siloxane group and a reactive site. The siloxane group referred to in the present invention is a polymer having a continuous siloxane bond (—Si—O—) as a skeleton, and as a preferred mode of the silicone compound B, the general formula (C) (— (Si (R _{^{8) (R 9) -O)}} m -) is a form of having a polysiloxane group represented by the.

  Preferred embodiments of the silicone compound B are the same as those described above for the preferred embodiments of the silicone compound A, and specific examples of the silicone compound B are also the same as the specific examples of the silicone compound A described above.

Moreover, the reactive site as used in the field of this invention refers to the site | part which reacts with the binder component in a coating composition by external energy, such as a heat | fever or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. Can be mentioned.
[Fluorine compound B]
The coating composition preferably contains the aforementioned fluorine compound B. When the coating composition contains the fluorine compound B, the antireflection layer of the antireflection member obtained using the coating composition can contain a component derived from the fluorine compound B.

  The number of fluoroalkyl groups in the fluorine compound B is not necessarily one, and the fluorine compound B may have a plurality of fluoroalkyl groups.

The fluoroalkyl group of the fluorine compound B, it is important that at least 4 carbon atoms, is preferably a fluoroalkyl group R ^f1 linear or branched 4-7 carbon atoms. The fluoroalkyl group R ^f1 preferably has 5 or more and 7 or less carbon atoms, more preferably 6 or more and 7 or less carbon atoms, from the viewpoint of suppressing the interparticle interaction between the hydrophobic treated inorganic particles when the coating composition is dried. . The direction of linear compared to branched small steric hindrance, from the viewpoint easily adsorbed on the hydrophobic-treated inorganic particles, fluoroalkyl group R ^f1 is preferably a straight chain structure. By making the fluoroalkyl group a linear or branched fluoroalkyl group R ^f1 having 4 to 7 carbon atoms, the separability of the particles is improved and the spontaneous formation of two layers having different refractive indexes is facilitated. And antireflection properties are improved, which is preferable.

The reactive site in the fluorine compound B is A in the general formula (B) described later and an acrylic group (H ₂ C═C (R ¹ ) —) in the general formula (A). The number of reactive sites in the fluorine compound B is not necessarily one, and may have a plurality of reactive sites. The reactive site is preferably an alkoxysilyl group, a silanol group, or an acryloyl (methacryloyl) group from the viewpoints of reactivity and handling properties.

  The number average molecular weight of the fluorine compound B is preferably 300 or more and 4000 or less. When the coating composition contains a fluorine compound B having a number average molecular weight of 300 or more and 4000 or less, the fluorine compound B is adsorbed on the surface of the hydrophobic treated inorganic particles due to the affinity of the fluorine compound B, and particles between the hydrophobic treated inorganic particles Suppresses the interaction between particles or the formation of agglomerates, and as a result, prevents the fluidity of the coating composition from being lowered when it is dried. It is preferable that the fluorine compound B having a number average molecular weight of 300 to 4000 is included.

The fluorine compound B preferably has a viscosity η _F measured by a vibration viscometer of 1 to 100 mPa · s and a surface tension γ _{F of 6} to 26 mN / m. The viscosity η _F of the fluorine compound B is more preferably 1 to 90 mPa · s, and further preferably 1 to 80 mPa · s.

Here, the viscosity η _F by the vibration type viscometer represents the viscosity when the fluorine compound B is measured at 25 ° C., and is measured by a tuning fork type vibration type viscometer SV-10A manufactured by A & D Corporation. can do. The principle of the vibratory viscometer is to obtain the viscosity by resonating the vibrator with a certain width in the liquid and measuring the current value that makes the viscous resistance of the vibrator an exciting force. More specifically, an electromagnetic drive unit is installed at the center of two leaf springs having a tuning fork shape to resonate the leaf springs with a constant set amplitude, and different drive currents are detected by viscous resistance and stored in advance. The viscosity is measured by calculating corresponding to the calibration curve.

Further, the surface tension γ _F of the fluorine compound B in the present invention is more preferably 6 mN / m or more and 24 mN / m or less, and further preferably 6 mN / m or more and 22 mN / m or less.

The viscosity η _F and surface tension γ _F of the fluorine compound B measured by a vibration viscometer are parameters that affect the affinity of the fluorine compound B to the surface of the hydrophobic treated inorganic particles, and the viscosity η _F of the fluorine compound B is 1 to 100 mPa When s and the surface tension is 6 mN / m or more and 26 mN / m or less, the affinity of the fluorine compound B facilitates the adsorption of the fluorine compound B to the surface of the hydrophobic treated inorganic particles, and the hydrophobic treated inorganic particles As a result, it is possible to prevent the fluidity of the coating composition from being lowered when it is dried, to facilitate the spontaneous formation of two layers having different refractive indexes, and to exhibit good antireflection properties. It becomes possible. Therefore, the fluorine compound B preferably has a viscosity η _F measured by a vibration viscometer of 1 to 100 mPa · s and a surface tension of 6 mN / m to 26 mN / m.

  The fluorine compound B in the coating composition may be one type or a mixture of two or more types. Further, the fluorine compound B may be the same compound as the fluorine compound A. Further, when the coating composition contains the fluorine compound B that is cured by ultraviolet rays or the like, oxygen inhibition can be prevented. Therefore, it is preferable that the oxygen concentration in the curing process by ultraviolet rays is as low as possible. It is more preferable to cure by purging.

Further, the fluorine compound B in the present invention is derived from the monomer of the following general formula (A), the monomer of the general formula (B), the oligomer derived from the monomer of the general formula (A), and the monomer of the general formula (B). More preferably, it is at least one compound selected from the group consisting of oligomers.
^{_{H 2 C = C (R 1}} ) -COO-R 2 -R f1 ··· formula (A)
^{AR 3} -R ^f1 ... General formula (B)
Wherein R ¹ is a hydrogen atom or a methyl group, R ^f1 is a linear or branched fluoroalkyl group having 4 to 7 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, and R ³ is a carbon number. 1-10 alkyl groups, A is a reactive site.)
In addition, although the fluorine compound B has a fluoroalkyl group and a reactive site, for an oligomer derived from the monomer of the general formula (A) or the monomer of the general formula (A), R ^f1 is a fluoroalkyl group, and H ₂ C = C (R ¹ )-is a reactive site. Moreover, about the oligomer derived from the monomer of General formula (B) and the monomer of General formula (B), ^Rf1 is a fluoroalkyl group and A is a reactive site.

  Specific examples of the monomer of the general formula (A) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl ethyl acrylate, 3- Perfluorobutyl-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 Chlorate, 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- -Fluorodecylethyl 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, Dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, Examples include hexafluorobutyl methacrylate.

  Specific examples of the oligomer derived from the monomer of the general formula (A) include compounds having an average degree of polymerization of about 2 to 10 obtained by a reaction such as radical polymerization using the monomer of the general formula (A). Is done.

  Specific examples of the monomer of the general formula (B) include heptadecafluorodecyltrimethoxysilane (TSL8233, manufactured by Momentive Performance Materials Japan GK), tridecafluorooctyltrimethoxysilane (TSL8257, Momentive Performance. Examples include fluoroalkylsilanes having a fluoroalkyl group, such as Materials Japan GK.

  A specific example of the oligomer derived from the monomer of the general formula (B) is obtained by adding a predetermined amount of water to the above-mentioned fluoroalkylsilane and reacting the alcohol by-produced in the presence of an acid catalyst while distilling off. And the like. By this reaction, a part of the fluoroalkylsilane is hydrolyzed and further undergoes a condensation reaction to obtain an oligomer. The hydrolysis rate can be adjusted by the amount of water used. The amount of water used for hydrolysis is usually 1.5 mol times or more with respect to the silane coupling agent. Furthermore, it is preferable that the average degree of polymerization of the oligomer obtained is a compound of 2-10.

In order to obtain a fluorine compound B having a viscosity η _F by a vibration viscometer of 1 mPa · s to 100 mPa · s and a surface tension γ _F of 6 mN / m to 26 mN / m, the number of carbon atoms is 4 to 7 It is preferable to have a linear or branched fluoroalkyl chain, and the monomer of general formula (A), the monomer of (B), the oligomer derived from the monomer of general formula (A), and the general formula (B ) Is preferably at least one compound selected from oligomers derived from monomers. Examples of such a fluorine compound B include 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyltrimethoxysilane, and the like.
[solvent]
The coating composition preferably further contains an organic solvent in addition to the two or more kinds of inorganic particles and fluorine compound B described above. When the coating composition contains an organic solvent, the interparticle interaction of the fluorinated inorganic particles is suppressed, and the aggregates of the fluorinated inorganic particles are easily suppressed. Moreover, since it becomes possible to prevent the fluidity | liquidity fall at the time of drying of a coating composition, spontaneous layer formation of the antireflection layer which consists of two layers from which a refractive index differs becomes easy, and favorable antireflection property is obtained. It is particularly preferable because it can be expressed.

  The organic solvent is not particularly limited, but usually a solvent having a boiling point of 200 ° C. or less at normal pressure is preferable. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides, fluorines and the like are used. These can be used alone or in combination of two or more. Specific examples include propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, isopropyl alcohol and the like, and isopropyl alcohol, propylene glycol and the like are particularly preferable from the viewpoint of the stability of the inorganic particles. .

  Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, phenethyl alcohol, and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether and propylene glycol monoethyl ether acetate. Examples of the esters include ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, and ethyl acetoacetate. Examples of aromatics include toluene and xylene. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  The coating composition preferably contains 1% by mass to 30% by mass of the hydrophobic compound B, more preferably 2% by mass to 25% by mass when the total of all components is 100% by mass. More preferably, it is 3 mass% or more and 20 mass% or less. Here, all the components of this invention represent all the components contained in a coating composition, and represent all the components including an organic solvent, the binder component mentioned later, and other various additives.

When the coating composition contains 1% by mass to 30% by mass of the hydrophobic compound B in a total of 100% by mass of all components, the hydrophobic compound B is adsorbed on the surface of the hydrophobic treated inorganic particles, and the hydrophobic process is performed. Suppresses the formation of agglomerates between inorganic particles, and as a result, prevents a decrease in fluidity during drying of the coating composition, facilitates thickness control of two layers having a large refractive index difference, and exhibits good antireflection properties. Therefore, the content of the hydrophobic compound B in the coating composition is preferably as described above. Further, since the hydrophobic compound B contributes to the dispersion stabilization of the inorganic particles in the process of applying and drying the coating composition, the ratio to the total components including the solvent is important, not the ratio to the inorganic particles, It is preferable to contain the hydrophobic compound B in the above range in a ratio to the component.
[Binder component]
The coating composition preferably further contains a binder component. That is, in the low refractive index layer and the high refractive index layer in the antireflection layer of the antireflection member obtained by the coating composition of the present invention, components derived from the binder component in the coating composition separately from the above-described substances ( A binder). Here, in the present invention, the binder contained in the coating composition is referred to as “binder component”, and the component derived from the binder component contained in the antireflection member is simply referred to as “binder”. Although it does not specifically limit as a binder component, From a viewpoint of manufacturability, it is preferable that it is a binder component which can be hardened | cured with a heat | fever and / or active energy ray, etc., and a binder component may be one type. Two or more types may be mixed and used. In addition, from the viewpoint of retaining the hydrophobic treated inorganic particles in the present invention and inorganic particles other than the hydrophobic treated inorganic particles in the film, alkoxysilane, alkoxysilane hydrolyzate or reactive double bond in the molecule It is preferable that it is a binder component which has.

As such a binder component, it is preferable to use a polyfunctional acrylate in the component, and typical ones are exemplified below. Polyfunctional acrylate having 3 (more preferably 4 or 5) or more (meth) acryloyloxy groups in one molecule and a modified polymer thereof, for example, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate Pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer and the like can be used. These monomers can be used alone or in combination of two or more. Commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” series, etc.), Shin-Nakamura Co., Ltd .; (Product name “NK Ester” series, etc.), Dainippon Ink and Chemicals Co., Ltd .; (Product name “UNIDIC”, etc.), Toagosei Chemical Industry Co., Ltd. (“Aronix” series, etc.), Nippon Oils and Fats Corporation; Such as “Blenmer” series), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” series, etc.), Kyoeisha Chemical Co., Ltd .; (trade name “light ester” series, etc.), etc. be able to.
[Other components in the coating composition]
The coating composition of 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 hydrophobic treated inorganic particles and the binder component, or for promoting the reaction between the binder components. As the initiator, those capable of initiating or accelerating polymerization and / or condensation and / or crosslinking reaction by anion, cation, radical reaction or the like of the coating composition are preferable.

  Various initiators, 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 the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds, but are not limited thereto, but from the viewpoint of curability. Alkylphenone compounds are preferred, and specific examples include 2.2-dimethoxy-1.2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylpheny ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2-ethoxy) ) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like.

  The content ratio of the initiator and the curing agent is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the binder component in the coating composition. It is a mass part, More preferably, it is 0.1 mass part-10 mass parts.

In addition, the coating composition of the present invention may further contain additives such as a surfactant, a thickener, and a leveling agent as necessary.
[Supporting substrate]
The supporting substrate can be a glass plate or a plastic film, but is preferably a plastic film. 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, among which triacetylcellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are particularly preferable.

  As described above, it is important that the surface roughness of the surface A in the supporting substrate is 8 nm or more and 40 nm or less. In addition, as a support base material, it is possible to use as a support base material the plastic film which has various functional layers or in which various processes were performed. In the present invention, it is preferable to use a support substrate having a functional layer from the viewpoint of improving physical properties. When a plastic film having a functional layer is used as a supporting substrate, the surface A is not particularly limited even if it is a surface on the plastic film side or a surface on the functional layer side. However, when the obtained antireflection member has a hard coat property, it is important that the hard coat layer side of the plastic film having the hard coat layer is the surface A, and the antireflection layer, the supporting substrate, In order to improve the adhesiveness, it is important that the easy adhesion layer side of the plastic film having the easy adhesion layer is the surface A. When a plastic film having a functional layer is used as a support substrate, when an antireflection member is formed on the functional layer side (when the functional layer side is the surface A), the functional layer (surface A It is important that the surface roughness of () is 8 nm or more and 40 nm or less. In this case, the surface roughness of the surface A is preferably 10 nm to 35 nm, more preferably 12 nm to 30 nm. By forming a fine concavo-convex structure on the surface (surface A) on the side of forming the antireflection layer of the supporting substrate, when the coating composition is applied once to the surface A side, the interlayer adhesion is improved, Scratch resistance and abrasion resistance can be obtained. Moreover, since it is a fine concavo-convex structure, it is possible to achieve both high transparency, low interference fringes, and anti-reflection performance.

  In a preferred embodiment of the present invention, a plastic film having no hard coat layer as described above and lacking scratch resistance is used as a support substrate, and the coating composition is applied once on the support substrate. In addition to antireflection properties, scratch resistance can also be imparted by providing the step of performing. Therefore, in a preferred embodiment of the present invention, there is an advantage that it is not necessary to provide a hard coat layer on a support substrate as in the prior art (it is not necessary to use a film having a hard coat layer as a support substrate).

  In the case of using a plastic film that does not have the hard coat layer and lacks scratch resistance as a supporting substrate, the high refractive index layer is made to have a high refractive index hard by increasing the thickness of the resulting high refractive index layer. Since it can be used as a coat layer, it is possible to impart scratch resistance. In this case, the thickness of the high refractive index layer is preferably 500 nm to 4000 nm, and more preferably 550 nm to 3000 nm.

  When the thickness of the high refractive index layer is increased to 500 nm to 4000 nm, it is important that the viscosity change (Δη) of the coating composition used in the present invention is 0.1 mPa · s to 10 mPa · s. is there. Simply increasing the content ratio of the high refractive index layer component in the coating composition increases the solids concentration as the organic solvent evaporates during the drying process, and the hydrophobic treated inorganic particles form agglomerates and form hydrophobic. It becomes difficult to move the property-treated inorganic particles to the air side (outermost surface layer), and as a result, the antireflection property is lost. Therefore, the thickness of the high refractive index layer can be increased by adjusting the viscosity change of the coating composition within the above range.

  Even more preferably, the coating composition contains a hydrophobic compound B such as a fluorine compound B, and by containing the hydrophobic compound B, aggregation of the hydrophobic treated inorganic particles can be suppressed, and the refractive index. It is easy to control the thickness of two large layers. Therefore, the antireflection member obtained by using the coating composition exhibits good antireflection properties, and the thickness of the high refractive index layer can be increased.

  Further, as described above, the supporting base material can be a film having various functional layers such as an adhesive layer, a shield layer, and a sliding layer.

  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 a transparent material that can be measured according to JIS K 7361-1 (1997). The larger the value of the light transmittance of the antireflection member, the better. The smaller value is not preferable because the haze value increases and the possibility of image deterioration increases. Haze is an index of turbidity of a transparent material defined in JIS K 7136 (2000). The smaller the haze, the higher the transparency.

  The haze of the support substrate is preferably 0.01% or more and 2.0% or less, and more preferably 0.05% or more and 1.0% or less.

  The refractive index of the supporting substrate is preferably 1.4 to 1.7. Here, the refractive index is a ratio of changing the angle of the traveling direction at the interface when light travels from the air to a certain substance, according to the method defined in JIS K 7142 (1996). Can be measured.

The support substrate may contain an infrared absorber or an ultraviolet absorber. The content of the infrared absorber is preferably 0.01% by mass or more and 20% by mass or more, more preferably 0.05% by mass or more and 10% by mass or more, based on 100% by mass of all the components of the support substrate. . As a slipping agent, particles of an inert inorganic compound may be contained in the transparent support. Examples of the inert inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. Furthermore, you may implement a process to a support base material.
[Production Method of Antireflection Member]
In the method for producing an antireflection member, the above-mentioned coating composition is applied to at least one surface of a supporting substrate by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, etc. It is important to have a process (application process) of applying only once by the application method. Then, an antireflection member can be obtained by a step of drying the applied coating composition by heating or the like (drying step).

  According to the production method of the present invention, two layers having different refractive indexes can be simultaneously formed on a supporting substrate by applying the coating composition only once on at least one surface of the supporting substrate.

  The following model is considered as a mechanism for simultaneously forming an antireflection layer composed of two layers having different refractive indexes. In the following, the mechanism of an embodiment containing a fluorine compound B which is a preferred embodiment of the present invention will be described as an example.

  First, in the coating composition, the hydrophobic compound B having high affinity with the hydrophobic treated inorganic particles is selectively adsorbed on the surface of the hydrophobic treated inorganic particles, and the hydrophobic treated inorganic particles and other inorganic particles are uniformly dispersed. Keeps the state. Even after the coating composition is applied on the support substrate, the applied coating composition similarly maintains a state in which the hydrophobic treated inorganic particles and other inorganic particles are uniformly dispersed. In the drying step, the hydrophobic treated inorganic particles, which are low refractive index constituents, move to the energetically stable air side (outermost surface), and the outermost layer has a low refractive index layer made of hydrophobic treated inorganic particles. Form. However, in this state, since it is in the middle of drying, there are many solvents that have not been volatilized, and volatilization proceeds in parallel. Although the low refractive index layer once formed in the volatilization process is destroyed once, the hydrophobic treated inorganic particles are aggregated even in a state of a small amount of solvent due to the presence of the coexisting low volatility hydrophobic compound B. Therefore, the low refractive index layer once destroyed can be rearranged to form a uniform low refractive index layer again, and a high refractive index layer is formed as a lower layer. Even when the hydrophobic compound B is not included, the viscosity change (Δη) of the coating composition is set to 0.1 mPa · s or more and 10 mPa · s or less in this way, thereby suppressing aggregation between the hydrophobic treated inorganic particles. It is considered that the same phenomenon as in the case of containing the hydrophobic compound B occurs, and two layers having different refractive indexes can be simultaneously formed on the supporting base material by the step of applying only once.

  In order to obtain the antireflection member as described above, in addition to completely removing the solvent from the obtained antireflection member, it is preferable to heat in the drying step from the viewpoint of separation into two layers without defects. . The drying process is divided into (A) material preheating period, (B) constant rate drying period, and (C) reduced rate drying period. From the material preheating period (period in which the temperature is raised to the temperature at which the entire material is dried), the drying process is continued. Over the drying period (the period until the coating liquid stops moving), two layers with different refractive indexes are formed as the solvent evaporates. However, in order to ensure sufficient time for the movement of the inorganic particles forming the two layers, the wind speed Therefore, it is preferable to dry at as low a temperature as possible.

  The wind speed in the initial drying period (A) material preheating period and (B) constant rate drying period is preferably 1 m / s or more and 10 m / s or less, more preferably 1 m / s or more and 5 m / s or less. is there. In the decreasing rate drying period in the latter stage of drying, the wind speed is preferably 10 m / s or more and 70 m / s or less, and the temperature is preferably 100 ° C. or more and 200 ° C. or less from the viewpoint of reducing the residual solvent. 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. Examples of the heating method in the drying process include hot air injection, infrared rays, microwaves, induction heating and the like. Among these, in the (A) material preheating period and (B) constant rate drying period which are the initial stages of drying, hot air drying which blows in parallel to the coated surface is preferable from the viewpoint of wind speed and temperature, but is particularly limited. It is not a thing. Moreover, in the (C) decreasing rate drying period which is the latter stage of drying, it is preferable that it is hot-air drying which blows | pants perpendicularly | vertically with respect to an application surface from the point of versatility and a drying speed.

  Furthermore, you may perform the further hardening operation (curing process) by irradiating a heat | fever or an energy ray with respect to two layers on the support base material formed after the drying process. In the curing step, when cured with heat, the temperature is preferably from room temperature to 200 ° C., more preferably from 100 ° C. to 200 ° C. from the viewpoint of solvent evaporation and a curing aid for the resin containing silanol and the like. More preferably, it is 130 degreeC or more and 200 degrees C or less. Setting the temperature to 100 ° C. or higher is preferable because the amount of the remaining solvent is reduced and the curing of the resin containing silanol proceeds in a very short time.

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. In the case of curing with ultraviolet rays, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, the curing of the outermost surface is inhibited, the curing becomes insufficient, and the scratch resistance and alkali resistance may be insufficient. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays 100 mW / cm ² or more 3000 mW / cm ² or less, preferably 200 mW / cm ² or more 2000 mW / cm ² or less, more preferably 300 mW / cm ² above is preferably carried out with ultraviolet radiation at 1500 mW / cm ² or less become conditions, the integrated quantity of ultraviolet light is 100 mJ / cm ² or more 3000 mJ / cm ² or less, preferably 200 mJ / cm ² or more 2000 mJ / cm ² or less, more preferably 300mJ It is more preferable to perform ultraviolet irradiation under the condition of / cm ² or more and 1500 mJ / cm ² or less. Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

  When curing is performed by heat, the drying step and the curing step may be performed simultaneously.

  Moreover, the antireflection member 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. In this case, it is important to provide an antireflection member or the like with the support base material side of the antireflection member as the image display device side.

Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these. In addition, the following high refractive index layer components are the second layer components as described above, and the low refractive index layer components are the first layer components as described above.
[Adjustment of high refractive index layer component (A-8)]
The following materials were mixed to obtain a high refractive index layer constituent (A-8).
72 parts by mass of titanium dioxide particle dispersion
(ELCOM JGC Catalysts & Chemicals Co., Ltd .: solid content 30% by mass, number average particle size 8 nm)
Binder component A 18 parts by mass (Kayarad DPHA Nippon Kayaku Co., Ltd .: solid content 100% by mass)
2-Propanol 1 part by mass Ethylene glycol monobutyl ether 9 parts by mass [Adjustment of high refractive index layer component (A-25)]
The high refractive index layer constituent component (A-25) is obtained in the same manner except that the titanium dioxide particle dispersion is changed to the following ATO particle dispersion with respect to the high refractive index layer constituent component (A-8). It was.
ATO particle dispersion (Ryoduras Toyo Ink Co., Ltd .: solid content 30% by mass, number average particle size 25 nm)
[Adjustment of High Refractive Index Layer Component (B-8)]
A high refractive index layer constituent component (B-8) was obtained in the same manner as in the high refractive index layer constituent component (A-8) except that the binder component A was changed to the following material.
Binder component B
(Kayarad PET-30 Nippon Kayaku Co., Ltd .: 100% by mass solid content)
[Adjustment of high refractive index layer component (B-15)]
For the high refractive index layer constituent component (B-8), the high refractive index layer constituent component (B-15) was changed in the same manner except that the titanium dioxide particle dispersion was changed to the following zirconium dioxide particle dispersion. Obtained.
Zirconium dioxide particle dispersion (OZ-S30K manufactured by Nissan Chemical Industries, Ltd .: solid content 30% by mass, number average particle size 15 nm)
[Adjustment of low refractive index layer components]
[Adjustment of low refractive index layer component (a)]
15 g of hollow silica, which is hollow silica manufactured by JGC Catalysts & Chemicals Co., Ltd .: solid content concentration 20 mass%, number average particle diameter 60 nm, 1.37 g of methacryloxypropyltrimethoxysilane and 0.17 g of 10 mass% formic acid aqueous solution Mix and stir at 70 ° C. for 1 hour. Next, 1.38 g of H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F (hydrophobic compound A) and 0.057 g of 2,2-azobisisobutyronitrile were added, followed by 90 minutes for 60 minutes. The mixture was heated and stirred at ° C. Thereafter, isopropyl alcohol was added for dilution to obtain a low refractive index layer constituting component (a) having a solid content of 14% by mass.

[Adjustment of low refractive index layer component (b)]
H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F was replaced with H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₆ F for the low refractive index layer component (a). The low refractive index layer constituent component (b) was obtained in the same manner as above.

[Antireflection coating composition 1]
The following materials were mixed to obtain an antireflection coating composition 1.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-8) 29 parts by mass Hydrophobic Compound B (Fluorine Compound B-1) 7.6 parts by mass 2-Hydroxy-2- Methyl-1-phenyl-propan-1-one 0.36 parts by mass 2-propanol 57 parts by mass (The hydrophobic compound B is similarly shown in Table 1 below.)
[Antireflection coating composition 2] to [Antireflection coating composition 14]
Antireflective coating composition 1 is similarly antireflective from antireflective coating composition 2 except that high refractive index layer constituents, low refractive index layer constituents and hydrophobic compound B are replaced as shown in Table 1. A coating composition 14 was obtained.

[Antireflection coating composition 15]
The following materials were mixed to obtain an antireflection coating composition 15.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-8) 7.1 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.10 25.8 parts by mass of 2-propanol [antireflection coating composition 16]
An antireflection coating composition 16 was obtained in the same manner as in the antireflection coating composition 15 except that the high refractive index layer constituent component (A-8) was replaced with the high refractive index layer constituent component (A-25). .

[Antireflection coating composition 17]
The following materials were mixed to obtain an antireflection coating composition 17 (low refractive index layer coating composition).
Low refractive index layer component (a) 13 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.03 parts by mass 2-propanol 86 parts by mass [Antireflection coating composition 18]
The following materials were mixed to obtain an antireflection coating composition 18 (high refractive index layer coating composition).
High refractive index layer component (A-8) 29 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.36 parts by mass 2-propanol 30 parts by mass [Antireflection coating composition 19]
The following materials were mixed to obtain an antireflection coating composition 19.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-8) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass Hydrophobic Compound B (Fluorine Compound B-1) 4.8 parts by mass 2-propanol 70.3 parts by mass [Antireflection coating composition 20]
The following materials were mixed to obtain an antireflection coating composition 20.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-8) 49.8 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.63 Part by mass Hydrophobic compound B (fluorine compound B-1) 13.1 part by mass 2-propanol 3.0 part by mass [Hard coat coating composition 1]
The following materials were mixed to obtain a hard coat coating composition 1.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hardcoat paint composition 2]
The following materials were mixed to obtain a hard coat coating composition 2.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 5 parts by mass (ELCOM TO-1023SIV JGC Catalysts & Chemicals, Inc.
30% by weight Number average particle size: 25 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard coat coating composition 3]
The following materials were mixed to obtain a hard coat coating composition 3.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 10 parts by mass (ELCOM TO-1023SIV JGC Catalysts & Chemicals Co., Ltd.
30% by weight Number average particle size: 25 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard coat paint composition 4]
The following materials were mixed to obtain a hard coat coating composition 4.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 5 parts by mass (ELCOM TO-1024SIV JGC Catalysts & Chemicals Co., Ltd.
30% by weight number average particle size: 45 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard coat coating composition 5]
The following materials were mixed to obtain a hard coat coating composition 5.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 10 parts by mass (ELCOM TO-1024SIV JGC Catalysts & Chemicals, Inc.
30% by weight number average particle size: 45 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard coat coating composition 6]
The following materials were mixed to obtain a hard coat coating composition 6.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 5 parts by mass (ELCOM TO-1025SIV JGC Catalysts & Chemicals, Inc.
30% by weight number average particle size: 120 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard coat coating composition 7]
The following materials were mixed to obtain a hard coat coating composition 7.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 10 parts by mass (ELCOM TO-1025SIV JGC Catalysts & Chemicals Co., Ltd.
30% by weight number average particle size: 120 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard coat coating composition 8]
The following materials were mixed to obtain a hard coat coating composition 8.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 12 parts by mass (ELCOM TO-1025SIV JGC Catalysts & Chemicals, Inc.
30% by weight number average particle size: 120 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Hard Coat Coating Composition 9]
The following materials were mixed to obtain a hard coat coating composition 9.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Colloidal silica particle dispersion 20 parts by mass (ELCOM TO-1025SIV JGC Catalysts & Chemicals Co., Ltd.
30% by weight number average particle size: 120 nm)
Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass [Easily Adhesive Coating Composition 1]
The following materials were mixed to obtain an easy-adhesion coating composition 1.
30.0 parts by mass of aqueous acrylic resin (Nicazole A08, 20% by weight manufactured by Nippon Carbide Industries, Ltd.)
Colloidal silica particle dispersion 6.0 parts by mass (Snowtex OL Nissan Chemical Industries, Ltd. 20% by weight number average particle size: 40 nm)
0.1 parts by mass of surfactant (Olfin EXP4051F manufactured by Nissin Chemical Industry Co., Ltd.)
100 parts by weight of water
[Easily adhesive coating composition 2]
The following materials were mixed to obtain an easy-adhesion coating composition 2.
30.0 parts by mass of aqueous acrylic resin (Nicazole A08, 20% by weight manufactured by Nippon Carbide Industries, Ltd.)
Colloidal silica particle dispersion 1.5 parts by mass (Spherica 140 JGC Catalysts & Chemicals Co., Ltd. 40% by weight number average particle size: 140 nm)
0.1 parts by mass of surfactant (Olfin EXP4051F manufactured by Nissin Chemical Industry Co., Ltd.)
100 parts by weight of water [Easily-adhesive coating composition 3]
The following materials were mixed to obtain an easy-adhesion coating composition 3.
30.0 parts by mass of aqueous acrylic resin (Nicazole A08, 20% by weight manufactured by Nippon Carbide Industries, Ltd.)
Colloidal silica particle dispersion 3.0 parts by mass (Spherica 140 JGC Catalysts & Chemicals Co., Ltd. 40% by weight number average particle size: 140 nm)
0.1 parts by mass of surfactant (Olfin EXP4051F manufactured by Nissin Chemical Industry Co., Ltd.)
100 parts by weight of water [Adhesive coating composition 4]
The following materials were mixed to obtain an easy-adhesion coating composition 4.
30.0 parts by mass of aqueous acrylic resin (Nicazole A08, 20% by weight manufactured by Nippon Carbide Industries, Ltd.)
Colloidal silica particle dispersion 3.0 parts by mass (Seahoster KEP30W made by Nippon Shokubai Co., Ltd.
20% by weight number average particle size: 300 nm)
0.1 parts by mass of surfactant (Olfin EXP4051F manufactured by Nissin Chemical Industry Co., Ltd.)
100 parts by weight of water [Production method 1 of supporting substrate]
A PET resin film (Lumirror T60 manufactured by Toray Industries, Inc.) is subjected to corona treatment, and the hard coat coating composition 1-9 is applied to the corona-treated surface with a bar coater (# 16), followed by the first stage drying shown below. Followed by a second stage of drying.

First stage hot air temperature 70 ℃
Hot air speed 2m / s
Air direction Parallel drying time to coated surface 1.5 minutes Second stage hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical drying time with respect to coated surface 1.5 minutes
After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 500 mJ / cm ² under an oxygen concentration of 0.1 vol%. Then, the base materials 1 to 4, 9 to 11, 13 and 14 having a hard coat layer were cured.

[Production method 2 of supporting substrate]
The PET resin film (Lumirror T60 manufactured by Toray Industries, Inc.) is subjected to corona treatment, and the easy-adhesion coating compositions 1 to 4 are applied to the corona-treated surface using a bar coater (# 2). Drying was performed, followed by a second stage of drying.

First stage hot air temperature 100 ℃
Hot air speed 2m / s
Wind direction Parallel drying time to coated surface 1.5 minutes Second stage hot air temperature 150 ° C
Hot air wind speed 5m / s
Wind direction Vertical drying time with respect to the coated surface 1.5 minutes After drying and curing, the support substrates 5 to 8 having an easy-adhesion layer were obtained.

[Method 3 for creating support substrate]
A PET resin film (Lumirror T60 manufactured by Toray Industries, Inc.) was subjected to corona treatment, and this was used as a support substrate 12.

[Preparation of antireflection member 1]
Antireflective coating composition on the surface of the supporting substrate prepared by the above method (when the supporting substrate has a hard coat layer or an easy-adhesion layer, on the surface having a hard coat layer or an easy-adhesion layer) After the product was applied using a bar coater (# 10), the first stage drying described below was performed, followed by the second stage drying.

First stage hot air temperature 35 ℃
Hot air wind speed 1.5m / s
Air direction Parallel drying time to coated surface 1.5 minutes Second stage hot air temperature 130 ° C
Hot air speed 7m / s
Wind direction Drying time perpendicular to coated surface 2 minutes
In addition, the measured value by a dynamic / static pressure tube was used for the wind velocity of hot air.

After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured.

  As shown in Table 3, Examples 1 to 20, 23 and 24 and Comparative Examples 1 to 3 were produced using the antireflection coating compositions 1 to 16.

[Preparation of antireflection member 2]
For the preparation 1 of the antireflection member, the same procedure was followed except that the antireflection coating composition 19 was used and the bar coater to be applied was changed from (# 10) to (# 6). An antireflection member was prepared.

[Preparation of antireflection member 3]
For the preparation 1 of the antireflection member, the same procedure was followed except that the antireflection coating composition 20 was used and the bar coater to be applied was changed from (# 10) to (# 18). An antireflection member was prepared.

[Preparation of antireflection member 4]
After the coating composition 19 is applied using a bar coater (# 6) on the surface of the supporting base material formed by the above-mentioned method on which the hard coat layer is formed, the drying shown below is performed with a drying apparatus. went.
Hot air temperature 130 ℃
Hot air wind speed 5m / s
Wind direction Vertical drying time with respect to the coated surface 2 minutes After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² , It was cured by irradiation under an oxygen concentration of 0.1% by volume.

Further, after applying the coating composition 18 on the surface on which the coating composition 19 is applied, dried and cured, using a bar coater (# 4), a sensor for measuring the liquid film thickness and a sensor for measuring the film surface temperature. The drying shown below was carried out using a drying apparatus equipped with.
Hot air temperature 130 ℃
Hot air wind speed 5m / s
Wind direction Vertical drying time with respect to the coated surface 2 minutes After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² , It was cured by irradiation under an oxygen concentration of 0.1% by volume. Thereby, the antireflection member of Comparative Example 4 was produced.

[Surface roughness Ra (nm)]
Using a surface roughness meter (SURFCORDER ET4000A: manufactured by Kosaka Laboratory Ltd.), measurement was performed under the following measurement conditions based on JIS-B-0601: 2001. Ra (surface roughness) is a profile curve (roughness curve) obtained by cutting a long wavelength component with a high-pass filter having a cutoff value λc from a measured cross-sectional curve, and the reference length of the curve. It is the average value of the absolute value of the height (the distance from the average line to the measurement curve). In addition, the measurement was performed on the surface A which is the surface of the support base on which the coating composition is applied.
<Measurement conditions>
Measurement speed: 0.1 mm / S
Evaluation length: 10mm
Cut-off value λc: 0.1 mm
Filter: Gaussian filter low cut [Surface tension γ _F (mN / m)]
The surface tension γ _F of the fluorine compound B in the present invention is measured with an automatic contact angle meter (DM-501, manufactured by Kyowa Interface Science Co., Ltd.) under a 25 ° C. environment from a Teflon (registered trademark) syringe. Compound B is extruded, and the shape of the droplet formed on the tip of the syringe is calculated using the attached FAMAS integrated multifunctional software according to the method described in the FAMAS Instruction Manual. did.

  As a parameter necessary for the calculation, the density of the compound is necessary. The density of the compound is a value measured using a density hydrometer (manufactured by Kyoto Electronics Industry Co., Ltd., DA-130N) in an environment of 25 ° C. Using.

[Viscosity η _F (mPa / s) by vibration viscometer]
The viscosity η _F of the fluorine compound B in the present invention by a vibration viscometer is passed through a circulating water jacket as an option using a tuning fork type vibration viscometer (SV-10, manufactured by A & _D Co., Ltd.). Then, under an environment of 25 ° C., the viscosity η _F was measured according to the method described in the “vibrating viscometer instruction manual”.

[Number average molecular weight]
The number average molecular weight of the fluorine compound B in the present invention was determined by measurement with a gel permeation chromatograph (GC-2010, Shimadzu Corporation) using tetrahydrofuran as a solvent and monodisperse polystyrene having a known molecular weight as a standard substance.

[Viscosity change Δη]
The shear viscosity η ₁ and η ₂ of the coating composition were measured as follows. A rheometer AR1000 manufactured by TA Instruments Japan Co., Ltd. was used as the measuring device, and a cone and plate having a diameter of 40 mm and an angle of 2 ° was used as the measuring geometry.

The measurement was performed at a measurement temperature of 25 ° C. and a steady flow measurement in which the shear rate was changed stepwise. Specifically, after preliminary shearing at a shear rate of 100 s ⁻¹ (for 30 seconds), a total of 16 points (1000 s ⁻¹ , 10 s ⁻¹ , 0.1 s) at logarithmic intervals from a shear rate of 1000 s ⁻¹ to 0.01 s ^{−1. -1} and 16 points including 4 points of 0.01 s ^-1 ). The viscosity at a shear rate of 0.1s ^-1 from the data η ₁ (mPa · s), and determine the viscosity η ₂ (mPa · s) at ^{10s -1.} Then, a viscosity change Δη (= η ₁ −η ₂ ), which is a difference between the viscosity η ₁ and the viscosity η ₂ , was obtained.

[Abrasion resistance]
The steel wool (# 0000), which is 250 g / cm ² load, is placed vertically on the anti-reflection member side of the anti-reflection member, and the approximate number of scratches that are visually observed when the length of 1 cm is reciprocated 10 times is described below. Classification was made and 3 or more points were accepted.
5 points: 0 4 points: 1 or more, less than 5
3 points: 5 or more, less than 10
2 points: 10 or more and less than 20
1 point: 20 or more [Abrasion resistance]
Shiranell (manufactured by Kowa Co., Ltd.) is attached to the tip (tip area 1 cm ² ) of an eraser abrasion tester manufactured by Honko Seisakusho, and a load of 500 g is applied on the antireflection layer of the antireflection member, and 5000 at 5 cm. The reciprocating friction was performed, and the following classification was made, and 3 or more points were accepted.
5 points: no scratch 4 points: 1 to 10 scratches
3 points: 11-20 scratches
2 points: 21 or more scratches
1 point: Anti-reflective layer in the test part peeled off entirely [Transparency]
Transparency was determined by measuring haze values. The measurement of the haze value is based on JIS K 7136 (2000). Using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., light is applied from the side opposite to the support base of the antireflection member sample (antireflection layer side). The measurement was carried out by placing it in the apparatus so as to pass through, and a haze value of less than 2% was regarded as acceptable.

[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, the minimum reflectance (bottom reflectance) was measured, and less than 0.8% was accepted.

[Interference fringes]
The surface of the antireflection member on which the antireflection layer is not formed (the surface on the side of the supporting substrate) is uniformly applied with a matte black spray paint. About this sample, a three-wavelength fluorescent lamp (FL20SS · EX- The sample surface was irradiated with N / 18 (a table lamp equipped with Matsushita Electric Industrial Co., Ltd.), and the interference fringes visible at that time were visually evaluated. The following classification was made and 3 or more points were accepted.
5 points: There is no interference unevenness and looks clean 3 points: Interference unevenness can be confirmed, but there is no problem in use Level 1 point: Interference unevenness can be confirmed, and there is a problem in use [Evaluation of reflection]
The surface of the anti-reflective member cut out to A4 size and having the anti-reflective layer formed is fixed to the screen surface of the PDP television (TH-42PX500: manufactured by Matsushita Electric Corp.) with cellophane tape. The interior lighting is set to 400 to 500 lx, and without turning on the TV, an image of himself / herself reflected on the front of the TV is observed from a distance of 1.5 m from the TV. The following classification was made, and a score of ○ or higher was accepted.
Compare the film affixed part and the unapplied part,
The outline of the observer's eyes cannot be seen: ◎
The outline of the observer's eyes can be seen somehow, but the map is not clear compared to the unattached case: ○
The outline of the observer's eyes can be seen: ×
[Layer thickness of two layers]
By observing the cross section using a transmission electron microscope (TEM), the thickness of each of the two layers on the support substrate was measured. The thickness of each layer was measured according to the following method. The thickness of each layer was read from an image taken with a TEM at a magnification of 200,000 times. A total of 10 layer thicknesses were measured and averaged.

  Table 4 summarizes the evaluation results of the antireflection member. About the evaluation item, even if one item did not pass, it was judged that the problem was not achieved.

  As shown in Table 4, the examples of the present invention passed both in the prevention of glare and low reflectivity, high transparency, low interference fringes, and simplification of the manufacturing process, and the present invention tried to solve them. Has achieved the task.

  In the antireflection member of Example 13 in which the viscosity change (Δη) of the coating composition was larger than the preferred range of the present invention, the transparency and antireflection properties were slightly inferior, but were in an acceptable range.

  In Examples 14 and 15 in which the hydrophobic compound B contained in the coating composition is a long-chain hydrocarbon compound B or a silicone compound, the abrasion resistance, transparency and antireflection properties were slightly inferior, but acceptable. It was in range.

  In Example 18 in which the hydrophobic compound B contained in the coating composition is a fluorine compound B and the number average molecular weight of the fluorine compound B is smaller than the preferred range of the present invention, transparency and antireflection properties are slightly inferior. However, it was within an acceptable range.

  Further, in the antireflection member of Example 17 in which the hydrophobic compound B contained in the coating composition is a fluorine compound B and the number average molecular weight of the fluorine compound B is larger than the preferable range of the present invention, the transparency and reflection are improved. Although the prevention was somewhat inferior, it was in an acceptable range.

DESCRIPTION OF SYMBOLS 1 Antireflection member 2 Support base material 3 Antireflection layer 4 Low refractive index layer 5 High refractive index layer 6 Hard coat layer or easy-adhesion layer 7 Plastic film

Claims (7)

By applying the coating composition only once on at least one surface of the supporting substrate (hereinafter, the surface on the supporting substrate on which the coating composition is applied only once is referred to as “surface A”), the refractive index is different. A method for producing an antireflection member, characterized by forming an antireflection layer comprising layers,
The method for producing an antireflection member, wherein the surface A has a surface roughness (JIS-B-0601: 2001) of 8 nm or more and 40 nm or less. The coating composition comprises two or more inorganic particles, one or more binder components, and a metal chelate;
The method for producing an antireflection member according to claim 1, wherein at least one of the two or more types of inorganic particles is an inorganic particle treated with a hydrophobic compound A. The method for producing an antireflection member according to claim 1, wherein a change in viscosity (Δη) of the coating composition is 0.1 mPa · s or more and 10 mPa · s or less.
(Where Δη and represents the viscosity eta ₁ at a shear rate of 0.1s ^-1, the difference in viscosity eta ₂ at a shear rate of ^{10s -1} and (η ₁ -η _2).) The said coating composition contains the following hydrophobic compound B, The manufacturing method of the antireflection member in any one of Claim 1 to 3 characterized by the above-mentioned.
The hydrophobic compound B is at least one compound selected from the group consisting of a fluorine compound B, a long-chain hydrocarbon compound B, and a silicone compound B.
The fluorine compound B is a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site.
The long-chain hydrocarbon compound B is a compound having a hydrocarbon group having 8 or more carbon atoms and a reactive site.
Silicone compound B is a compound having a siloxane group and a reactive site. The hydrophobic compound B includes a fluorine compound B,
The method for producing an antireflection member according to claim 4, wherein the fluorine compound B has a number average molecular weight of 300 or more and 4000 or less. 6. The antireflection according to claim 5, wherein the fluorine compound B has a viscosity η _F measured by a vibration viscometer of 1 to 100 mPa / s and a surface tension γ _{F of 6} to 26 mN / m. Manufacturing method of member. The fluorine compound B is composed of a monomer represented by the following general formula (A), a monomer represented by the general formula (B), an oligomer derived from the monomer represented by the general formula (A), and an oligomer derived from the monomer represented by the general formula (B). The method for producing an antireflective member according to claim 5, wherein the method is at least one compound selected from the group consisting of:
^{_{H 2 C = C (R 1}} ) -COO-R 2 -R f1 ··· formula (A)
^{AR 3} -R ^f1 ... General formula (B)
(Wherein R ¹ is a hydrogen atom or a methyl group, R ^f1 is a linear or branched fluoroalkyl group having 4 to 7 carbon atoms, R ² and R ³ are alkyl groups having 1 to 10 carbon atoms, and A is Reactive site.)

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