JP2011065028A - Method for manufacturing antireflection member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an antireflection member, by which an antireflection layer having scratch resistance, wear resistance and low reflectance and being uniform within the plane can be formed on a support substrate in the minimum number of coating processes. <P>SOLUTION: The method aims to manufacture an antireflection member having an antireflection layer comprising two layers having different refractive indices on at least one surface of a support substrate, and the method includes steps of applying a coating liquid once on at least one surface of the support substrate to form one layer of a liquid film and of drying the liquid film, in this sequence. A period of constant rate drying in the step of drying the liquid film includes the time period of 7 seconds or longer when a Peclet number is smaller than 1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Anti-reflection members, particularly anti-reflection films, are generally used in image display devices such as cathode ray tube display devices (CRT), plasma display panels (PDP), and liquid crystal display devices (LCD). In order to prevent reflection, it is placed on the outermost surface of the display so as to reduce reflectivity using the principle of optical interference.

  As such an antireflection member, Patent Document 1 discloses (1) a hard coat layer, (2) a high refractive index layer made of a substance having a high refractive index, and (3) a substance having a low refractive index, on a supporting substrate. A three-layer structure in which a low refractive index layer is provided in order, Patent Document 2 discloses (1) a high refractive index hard coat layer having two functions of a hard coat layer and a high refractive index layer on a supporting substrate, (2) A two-layer structure in which a low refractive index layer is provided in order has been proposed.

  For further simplification of the manufacturing process, Patent Documents 3 to 6 disclose two layers having different refractive indexes by one coating, or an antireflection member for forming unevenly distributed parts of particles in the coating layer and its layers Manufacturing methods have been proposed.

  Patent Document 3 states that “a cured layer containing low refractive index fine particles, high refractive index fine particles and a binder is formed on a transparent plastic film substrate, and the low refractive index fine particles are unevenly distributed on the surface side of the cured layer. In addition, an optical film characterized in that high refractive index fine particles are unevenly distributed on the substrate side is described.

  Patent Document 4 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, the low refractive index fine particles are unevenly distributed in the upper part to the middle part of the coating film due to the difference in specific gravity, and in the middle part to the lower part. "An antireflection laminate characterized in that high refractive index fine particles are unevenly distributed" is described.

  In Patent Document 5, “a method for producing an antireflection film having two layers having different refractive indexes on at least one side of a supporting substrate, the coating composition is applied and dried and cured once on at least one side of the supporting substrate. The coating composition contains two or more kinds of inorganic particles, and at least one kind of inorganic particles in the two or more kinds of inorganic particles is an inorganic particle surface-treated with a fluorine compound, and further a metal chelate compound The manufacturing method of the anti-reflective film characterized by including this is described.

  Patent Document 6 states that “a hard coat layer mainly composed of an active energy ray-curable resin is formed on a transparent film support, the surface of the hard coat layer has a fine uneven shape, and the hard coat layer” Anti-glare antireflection film in which a low refractive index layer is formed on the surface of the fine concavo-convex shape, and the low refractive index layer is a hollow spherical silica-based fine particle having an outer shell layer and being porous or hollow inside And an antiglare antireflection film characterized in that a large amount of the hollow spherical silica-based fine particles are present on the surface side of the low refractive index layer.

On the other hand, as a method for producing an antireflection member having a constant thickness distribution of the optical functional layer and excellent antireflection performance, Patent Document 7 discloses that “at least 1 having a refractive index different from that of the transparent support on the transparent support”. In the method for producing an antireflection film for coating an optical functional layer, at least one layer of the optical functional layer is produced by a production method including the following steps (1) and (2): "Production method of antireflection film" is described.
(1) containing a heat and / or ionizing radiation curable compound, inorganic fine particles and an organic solvent,
Step of applying a coating composition having a solid content concentration of 3 to 15% by mass and a viscosity at 25 ° C. of 0.5 to 3.5 mPa · s at a wet coating amount of 2.5 to 5 ml / m ² (2) Drying A drying step (A) for drying at a temperature of 15 ° C. to less than 35 ° C. and a drying rate of 0.05 to 1.0 g / m ² · sec, and a drying step (B) for drying at a drying temperature of 50 ° C. to 130 ° C. And drying process

Japanese Patent Laid-Open No. 9-254324 Japanese Patent Laid-Open No. 9-226062 JP 2007-133236 A JP 2007-272132 A JP 2009-058954 A JP 2006-154200 A JP 2006-126799 A

  The antireflection member manufacturing method targeted by the present invention can be manufactured by a simplified manufacturing process to enable low-cost manufacturing, and is disposed on the outermost surface of the display and directly used by the user. In order to touch the eyes, it is required to achieve a high antireflection function, scratch resistance, and wear resistance uniformly over the entire screen. Therefore, the problems to be solved by the invention are the following two.

  The first problem is to provide a production method capable of forming a uniform antireflection layer in the surface with the smallest possible number of coatings on a supporting substrate.

  The second problem is to provide a method for producing an antireflection member having scratch resistance, wear resistance, and low reflectance with the smallest possible number of coatings on a supporting substrate.

  In particular, for the first problem, in the manufacturing method in which the high refractive index layer and the low refractive index layer are simultaneously formed by a single coating shown in Patent Documents 3 to 6, there is a merit in terms of simplifying the manufacturing process. On the other hand, in order to control the thickness and uniformity of the layer in the coated surface in order to express the antireflection function by spontaneously forming two layers or unevenly distributed parts of particles after coating. In addition, a device is required for the drying and curing processes.

  With respect to the first and second problems, the above-described known techniques are in the following situations.

  In patent document 3, with respect to the above-mentioned problem, as a manufacturing condition for causing segregation of particles stably, in Example, “Coating under the condition of a conveyance speed of 15 m / min, conveying at 25 ° C. for 60 seconds, and then at 60 ° C. Although there is a description of “drying for 150 seconds”, the present inventor confirmed that sufficient effects cannot be obtained with this content alone, and the antireflection function has the lowest average reflectance of 450 to 650 nm. It is about 1.2%, which is inferior to the currently required minimum reflectance of about 0.5% or less.

  In Patent Documents 4 and 5, in order to obtain scratch resistance that can withstand use, a hard coat layer is provided on a base material, and an anti-reflection layer is provided by simultaneous coating of one coat and two layers. The total number of coatings on the substrate is two times, the technique described in Patent Document 2 and the number of manufacturing steps are not changed, and the effect as a simplified manufacturing step is reduced.

  Furthermore, in Patent Document 4, regarding the drying and curing processes, after applying at a desired coating amount, it is usually described as drying with heating means such as an oven, and the present inventors have confirmed. With this content alone, a stable and uniform antireflection layer cannot be obtained.

  In addition, Patent Document 5 describes that it is preferable to dry at a low temperature as low as possible in order to ensure a sufficient time for the movement of the inorganic particles forming the two layers. Is not marked.

  Patent Document 6 states that “after applying a low refractive index layer coating solution containing medium spherical silica-based fine particles and a diluting organic solvent, the coated surface is kept in a state of being a lower surface in the horizontal direction and dried and solidified. The distribution of silica-based fine particles can be unevenly distributed by gravity, and the uneven distribution can be controlled by the temperature during drying and the amount of dry air (wind speed). " The obtained antireflection function is about 1.5% at the lowest at an average reflectance of 450 to 650 nm, which is inferior to the currently required luminous reflectance of about 0.5%.

Further, in general antireflection members, the thickness and uniformity of the layer within the coated surface are devised. In Patent Document 7, the solid content concentration of the coating solution at the time of coating is 25 ° C. In this manufacturing method, the high refractive index layer and the low refractive index layer are simultaneously formed by a single coating. Not enough effect,
In any of Patent Documents 3 to 7, the method of the present invention described later has not been conceived.

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) A method for producing an antireflection member having an antireflection layer composed of two layers having different refractive indexes on at least one surface of a support substrate,
On at least one side of the supporting substrate, the coating liquid is applied once to form a single layer liquid film, and the liquid film is dried in this order,
A method for producing an antireflective member, characterized in that, in the constant rate drying period of the step of drying the liquid film, a time during which the Peclet number is smaller than 1 is provided for 7 seconds or more.
2) The coating liquid contains at least two kinds of particles and at least one kind of binder component,
At least one of the two or more types of particles is a particle that has been surface-treated with a fluorine compound A (hereinafter, the particles that have been surface-treated with a fluorine compound A are referred to as fluorine-treated particles). The method for producing an antireflection member according to 1) above.
3) The method for producing an antireflection member according to 1) or 2) above, wherein the thickness of the second layer from the outermost layer on the antireflection layer side is 500 nm or more and 2000 nm or less.
4) Either of 2) or 3) above, wherein the median value of the volume reference distribution by dynamic light scattering at 25 ° C. of at least one kind of particles in the coating liquid is 50 nm or less. The manufacturing method of the reflection preventing member as described in any one of.
5) The coating liquid according to any one of 1) to 4), wherein the coating liquid contains a fluorine compound B having a fluoroalkyl group and a reactive site and having a number average molecular weight of 300 or more and 4000 or less. Manufacturing method of antireflection member.
6) 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 as described in 5) 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, A Is a reactive double bond group.)
7) The above-mentioned 1) to 6), wherein the drying rate during the constant rate drying period in the drying step is 0.1 g / (m ² .s) or more and 1.4 g / (m ² .s) or less. The manufacturing method of the antireflection member in any one of.

According to the present invention, the manufacture of an antireflection member having scratch resistance, abrasion resistance, low reflectance, and uniform antireflection performance in the surface with the minimum number of coatings on the support substrate. A method can be provided.

Examples of antireflection members Examples of antireflection members Parameter calculation flow for calculating Peclet number Example of Peclet number change behavior during drying process Example of Peclet number change behavior during drying process Example of Peclet number change behavior during drying process

  Before describing a specific embodiment, the mechanism of the present invention will be described.

  First, the reason why the above-mentioned first to second problems cannot be achieved with respect to the known technology will be considered.

  The reason why sufficient antireflection performance cannot be obtained in Patent Document 3 is that low refractive index particles are unevenly distributed on the surface side and high refractive index particles are unevenly distributed on the substrate side. A clear layer structure of only the refractive index particles cannot be formed, and the difference in refractive index between the low refractive index particles and the high refractive index particles is not sufficiently obtained, or between the low refractive index particles and the high refractive index particles. It is considered that because the interface is unclear, the film thickness of the unevenly distributed part of the particles cannot be made constant and the optical interference effect is not obtained.

  Further, the reason why sufficient antireflection performance cannot be obtained in Patent Document 6 is that the low refractive index particles are unevenly distributed in the hard coat layer, so that the refractive index difference is small and the effect is considered insufficient. .

  Next, the reason why a uniform antireflection effect cannot be obtained in the surface by the methods of Patent Documents 3, 5, and 6 is that the method described in these documents is to ensure the formation of a layered structure or an unevenly distributed structure. It is thought that the drying speed is slowed down by lowering the wind speed and temperature in the drying process, but conversely, because the drying speed was reduced, the fluctuation of the wind in the drying process near the liquid film surface and the drying It is considered that there is a trade-off relationship under the influence of non-uniformity of the drying rate due to conduction heat transfer from the pass roll in the process.

  As a result, all of the first and second problems cannot be achieved by the known technology.

  Next, the reason why the present invention can solve the above first and second problems will be described.

  In the manufacturing method in which the present inventors simultaneously form a high refractive index layer and a low refractive index layer by one coating, the formation of the layer structure from the coating liquid film is performed during the constant rate drying period of the drying process. We found that it depends on the degree of Brownian motion of the particles in the liquid film, and the Brownian motion of the particles in the liquid film is dominant to the flow generated by the shrinkage of the liquid film during the drying process as an indicator. Has been found to correspond to the appearance of a stable antireflection effect. As an index for stably and spontaneously forming a layered structure, attention was paid to the time when the Peclet number during the constant rate drying period is smaller than 1. Here, Brownian motion is the motion of particles caused by thermal motion, and is a phenomenon in which particles in a solution and solvent molecules randomly move due to random collision, and the particles diffuse into the solution. Is a dimensionless number representing the ratio of the flow generated by the contraction of the liquid film during the Brownian motion and the drying process, and is expressed by Equation 1.

  In Equation 1, Pe is the Peclet number (dimensionless), μ is the viscosity (Pa.s), R is the particle diameter (m), E is the liquid film shrinkage rate (m / s), and H is the liquid film thickness (m). , K represents Boltzmann constant (J / K), and T represents temperature (K). The contents of these parameters and how to obtain them will be described later.

  The state in which the value of the Peclet number is larger than 1 in the drying process of the liquid film is a state in which the movement of particles due to the flow caused by the contraction of the liquid film is dominant, and the state smaller than 1 is the liquid film. It shows the state in which the particle motion due to the Brownian motion is dominant.

  From Equation 1, since the Peclet number is composed of the liquid film shrinkage rate, the liquid film thickness, the particle diameter, and the temperature, each parameter has a complementary relationship when trying to obtain the same Peclet number. Therefore, while the known technology relied solely on the drying speed in the formation of the layer structure, by introducing this concept, it can also be controlled using other parameters that constitute the Peclet number. It is possible to avoid the influence of the nonuniformity of the drying rate that occurs when the drying rate is lowered as in the known art. As a result, it has become possible to form a layer separation structure in which a uniform antireflection layer can be obtained in one plane by a single coating.

  Furthermore, in order to further reduce the total number of coatings according to the present invention, as described in Patent Documents 4 and 5 of the publicly known technology, a hard coat layer is provided on a support substrate, and one coat and two layers are simultaneously applied to prevent reflection. A high refractive index hard coat layer that achieves the functions of two layers, a hard coat layer and a high refractive index layer, on a supporting substrate that does not have sufficient scratch resistance, and a low refractive index. This is also effective when a layer structure is spontaneously formed by a single coating.

  This is because when a high refractive index hard coat layer that requires a thick film thickness is used to spontaneously form a layer structure by a single coating, the liquid film thickness H is increased by increasing the film thickness. Since it becomes thicker, the formation of the layer structure becomes impossible if the formation of the layer structure depends only on the drying speed as in the known technique, whereas the formation of the layer structure becomes impossible by using the manufacturing method of the present invention as shown in Formula 1. Since it can be controlled using parameters other than speed, for example, the region where spontaneous layer structure formation is possible can be substantially expanded by reducing the particle diameter R or decreasing the viscosity μ. Made possible.

  As a result, a low refractive index layer and a high refractive index hard coat layer can be spontaneously formed on a supporting substrate having no scratch resistance by a single coating, resulting in scratch resistance, abrasion resistance, and low reflection. The total number of coatings can be reduced while achieving the rate.

As a result, the first and second problems described above can be solved by the present invention. Hereafter, embodiments of the present invention will be specifically described.
[Antireflection member]
The antireflection member, which is an object of the present invention, is a member having an antireflection layer composed of two layers having different refractive indexes on at least one surface of various supporting substrates. When the substrate is a plastic film, it is generally called an antireflection film. The necessity and required performance are supported by 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. It is the aspect comprised by making it laminate | stack on a base material. Moreover, it is preferable that the refractive index difference of two layers on a support base material 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 outermost layer (first layer) on the antireflection layer side is a low refractive index layer, and the second layer from the outermost layer on the antireflection layer side (that is, the first layer) A low reflectance can be realized because the layer between the layer and the supporting substrate is a high refractive index layer.

  FIG. 1 shows an example of the structure of the antireflection member of the present invention. In the antireflection member 1, an antireflection layer composed of two layers having different refractive indexes is formed on one side of a support base 2. The antireflection layer is composed of a low refractive index layer 4 (the first layer described above) on the outermost surface side, and then a high refractive index layer 3 (the second layer from the outermost layer on the antireflection layer side described above). The

  Further, when the high refractive index layer imparts scratch resistance in addition to the function of the high refractive index to the support substrate, it is called a high refractive index hard coat layer, and the configuration in that case is shown in FIG. The high refractive index hard coat layer 5 may also have a function of strengthening the adhesion between the support base 2 and the low refractive index layer 4. 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.

  The thickness of the second layer from the outermost layer on the antireflection layer side of the antireflection member, that is, the thickness of the high refractive index layer or the high refractive index hard coat layer is preferably 500 nm or more and 2000 nm or less, more preferably 600 nm or more and 2000 nm. Hereinafter, it is particularly preferable that the thickness is 600 nm or more and 1500 nm or less. By setting the thickness of the second layer from the outermost layer on the antireflection layer side to 500 nm or more and 2000 nm or less, scratch resistance, wear resistance, curl and reflectance of the antireflection member, improvement of transmittance, coating film It is desirable because the occurrence of cracks on the surface can be suppressed.

  The above-described method for producing an antireflection member has, in this order, a step of applying a coating liquid composed of a single layer of liquid film on at least one surface of a support substrate, and a step of drying in this order. An antireflection layer comprising two layers having different refractive indexes can be formed on the material. And the above-mentioned coating liquid is a particle containing at least two or more kinds of particles and at least one or more kinds of binder components, and at least one of the two or more kinds of particles is surface-treated with a fluorine compound. It is preferable that particles (hereinafter referred to as particles treated with a fluorine compound are referred to as fluorine-treated particles). The coating solution can naturally contain a solvent. According to the production method of the present invention, it is possible to produce an antireflection member having scratch resistance, abrasion resistance, and antireflection properties that are uniform in the plane.

  Here, the step of applying the coating liquid once to form a single-layer liquid film means that one type of coating liquid is applied only once to the base material. It refers to the formation of a liquid film. Multi-layer simultaneous coating that simultaneously forms a liquid film composed of a plurality of layers by a single coating, or a single layer of liquid film applied multiple times during one coating, It means that continuous sequential coating to dry, wet-on-wet coating, etc., in which a single layer of liquid film is applied a plurality of times at the time of one application, are not performed.

  In the present invention, it is important that the time for the Peclet number in the constant rate drying period to be less than 1 is set to 7 seconds or longer in the drying step. The Peclet number in the constant rate drying period is preferably 10 seconds or more, more preferably 12 seconds or more.

  When the time when the Peclet number is less than 1 is shorter than 7 seconds, it becomes impossible to form an antireflection structure by spontaneous formation of a layer structure, particularly to form a clear interface uniformly in a plane, Two layers having different refractive indexes cannot be clearly formed on the antireflection member, and the antireflection function is deteriorated. On the other hand, when the time when the Peclet number is less than 1 is 7 seconds or more, there is no effect on the spontaneous formation of the layer structure, but when the Peclet number is decreased by lowering the drying speed. , Cost increase due to lower productivity, fluctuation of air on the surface of the liquid film, disturbance of entrained airflow accompanying the transport of the support substrate, uneven heat transfer from the pass roll for transporting the substrate, from equipment in the dryer Due to unevenness such as radiant heat, it becomes difficult to keep the drying speed uniform within the coating surface, and as a result, uniform antireflection performance cannot be obtained within the surface. In addition, there is a limit to the adjustment of the particle diameter and the viscosity, and the time when the Peclet number becomes smaller than 1 is actually considered to be about 60 seconds.

  Here, the Peclet number is as described above. The constant rate drying period refers to the state in which the drying of the liquid film is controlled by the diffusion of the solvent from the surface of the liquid film to the atmosphere. In this process, the drying rate is governed by external conditions regardless of the structure of the liquid film. In this process, it becomes constant.

The drying rate in this constant rate drying period represents the amount of solvent evaporation per unit time and unit area, and has a dimension of g / (m ² .s).

There is also a preferable range for the drying rate during this constant rate drying period, and it is preferably 0.1 g / (m ² .s) or more and 1.4 g / (m ² .s) or less, 0.3 g / (m ² .S) to 0.9 g / (m ² .s) or less.

  By setting the drying speed in the constant rate drying period within this range, it is possible to prevent unevenness due to non-uniformity of the drying speed and to sufficiently secure the time required to cause a spontaneous layer structure.

  In the present invention, the coating liquid is applied once to form a liquid film of one layer and dried to form two layers having different refractive indexes. Particles move in the liquid film by Brownian motion, and particles that have reached the gas-liquid / solid-liquid interface are moved to the atmosphere side by the surface free energy difference. We believe that by fixing, a spontaneous layer structure can be formed.

  When the coating liquid used in the production method of the present invention contains particles, the median value of the volume-based distribution by dynamic light scattering at 25 ° C. of at least one kind of particles in the coating liquid is 50 nm or less. It is preferable that it is 20 nm. This is because, when the median value of the volume reference distribution by the dynamic light scattering method is 50 nm or less, the Brownian mobility of the particles in the liquid film is improved, and the movement of the particles to the surface becomes easy. is there. More preferably, the median value of the volume reference distribution by dynamic light scattering method at 25 ° C. of all kinds of particles in the coating liquid is preferably 50 nm or less, more preferably 20 nm.

  Here, the dynamic light scattering method measures the diffusion coefficient from fluctuations in the scattering intensity, etc., by applying a laser beam to particles in Brownian motion and detecting the scattered light with a photomultiplier tube. Further, the particle diameter is obtained, and this is a method suitable for measuring the dispersion state of particles of several nm to several μm in a liquid in a concentrated system. Volume reference distribution is one of the methods for expressing particle size distribution, and indicates the ratio of the volume occupied by particles of each particle size to the total volume of particles.

  Further, the median value is also referred to as a 50% diameter or a median diameter, and the number or mass of particles having a particle size larger than a certain particle size in the particle size distribution is 50% of that (number or mass) of all particles. It refers to the particle diameter when That is, the median value of the volume-based distribution refers to a particle diameter in which the volume of particles having a particle diameter larger than the particle diameter occupies 50% of the total particle volume.

  On the other hand, although the median value of the volume-based distribution is small, there is not much influence, but due to the limit of the size of crystal nuclei in particle formation, the volume of particles in the coating solution by dynamic light scattering at 25 ° C. The lower limit of the median value of the reference distribution is about 5 nm, which is a practically available particle.

  Moreover, it is preferable that the coating liquid used for the manufacturing method of this invention contains the fluorine compound B which has a fluoroalkyl group and a reactive site | part, and whose number average molecular weight is 300-4000. This fluorine compound B is adsorbed by the affinity of the fluorine compound B with respect to the above-mentioned fluorine-treated particles, suppresses the interparticle interaction between the fluorine-treated particles, and decreases the viscosity of the coating liquid. This has the effect of ensuring the mobility of the material and facilitating the formation of a spontaneous layer structure.

  In addition, the fluoroalkyl group as used in the field of this invention is a substituent in which all the hydrogen which an alkyl group has was substituted with the fluorine, and is a substituent comprised only from a fluorine atom and a carbon atom.

  Moreover, the reactive site as used in this invention refers to the site | part which reacts with other components, such as a binder 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.

  The two layers having different refractive indexes in the antireflection member obtained by the production method of the present invention were measured for the reflectance in the range of 300 to 800 nm with a reflection spectral film thickness meter, and the software [FE-Analysis included with the apparatus was used. ] Refers to two layers having different refractive indexes.

Specifically, the reflectance is measured in the range of 300 to 800 nm using a reflection spectral film thickness meter (FE-3000, manufactured by Otsuka Electronics Co., Ltd.), and the film thickness measuring device general catalog P6 (manufactured by Otsuka Electronics Co., Ltd. Non-linear least square method)], the optical constants (C ₁ , C ₂ , C ₂ , C ₂ , C ₂ , The refractive index can be measured by calculating C ₃ ). 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.

  Examples of the measuring device capable of measuring the refractive index of each layer include a reflection spectral film thickness meter (FE-3000, manufactured by Otsuka Electronics Co., Ltd.), a high-precision refractive index measuring device (manufactured by Film Tec Scientific Computing International), and the like. Not as long.

  In addition, in the antireflection member obtained by such a manufacturing method of the present invention, a high refractive index layer (or a high refractive index hard coat layer) that is two layers having different refractive indexes and a low refractive index layer are provided. It is preferable that there is a clear interface due to the arrangement of the particles.

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

  An image taken with a TEM at a magnification of 200,000 times was adjusted with software (Easy Access) so that the white balance was within the 8-bit tone curve in the brightest and darkest areas. Furthermore, the contrast was adjusted so that two types of particles could be clearly distinguished.

  At this time, when a clear boundary could be drawn at the interface between one layer and the other layer, it was considered that there was a clear interface.

  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 even more preferably 0% or more in spectroscopic measurement. It is 0.6% or less, and particularly preferably 0% or more and 0.5% or less.

  Moreover, in order to exhibit good properties as an antireflection member, it is further desirable that the transparency is high. 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 obtained by the production method of the present invention. 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 3.0% or less, more preferably less than 2.0%, still more preferably less than 1.0%, 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 is 3.0% or more, there is a high possibility that image degradation will occur.

  In order to exhibit good properties as an antireflection member, it is desirable that the thickness of the high refractive index layer and the low refractive index is a specific thickness. The thickness of the low refractive index layer which is the outermost layer (first layer) on the antireflection layer side of the antireflection member is preferably 50 nm or more and 200 nm or less, more preferably 70 nm or more and 150 nm or less, and particularly preferably 90 nm or more. It is desirable that it is 130 nm or less. If the thickness of the 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 becomes large. Further, when the thickness of the low refractive index layer, which is the outermost layer (first layer) on the antireflection layer side of the antireflection member, exceeds 200 nm, the effect of light interference cannot be obtained, so that the reflection of the image is increased. Therefore, it is not preferable.

The antireflection member of the present invention 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.
[Calculation method of each parameter composing Peclet number and change behavior of Peclet number]
Each parameter constituting the Peclet number is as described in Equation 1 above.

  In Equation 1, Pe is the Peclet number, μ is the viscosity (Pa.s) of the liquid film at time t after coating, E is the liquid film shrinkage rate (m / s) at time t after coating, and H is Liquid film thickness (m) at time t after coating, T is the liquid film temperature (K) at time t after coating, k is Boltzmann's constant (J / K), R is the particle size in the coating liquid ( m). The calculation flow of each of these parameters is shown in FIG.

  The liquid film thickness H at time t after coating is obtained by continuously measuring the liquid film thickness at each instant of the drying process. The measurement may be obtained by measuring the change in the thickness of the liquid film during the drying process by continuously measuring the distance to the coated liquid film by non-contact measurement, or by measuring the mass change during the coating and drying process. Although it may be obtained by converting it to the thickness of the liquid film, non-contact measurement is preferred from the viewpoint of measurement accuracy.

  The liquid film contraction speed E at time t after coating indicates the liquid film contraction speed at each instant of the drying process, and can be obtained from the change per minute time of the liquid film thickness H as shown in Equation 3. .

The viscosity μ of the liquid film at time t after coating refers to the viscosity of the liquid film at a shear rate of 0.1 s ⁻¹ at each instant of the drying process. Since it is practically difficult to directly measure the viscosity of the liquid film at each moment in the drying process, measure the coating liquid with the solid content concentration changed by changing only the solvent amount in advance at each temperature, And a viscosity calibration curve with respect to the solid content concentration, the solid content concentration of the liquid film at each moment obtained from the measured value of the change in the thickness of the liquid film at each moment of the drying process, and the film surface temperature at each moment of the drying process From this, the viscosity μ of the coating liquid at each moment can be determined.

  Calibration curves for viscosity, solid content concentration, and film surface temperature can be approximated by the following approximate expression:

In Equation 4, μ is the viscosity (mPa.s) at time t after coating, x is the solid content concentration (%) at time t after coating, T is the temperature (° C.) at time t after coating, a ₁ , a ₂ , a ₃ , a ₄ , b ₁ , b ₂ , b ₃ , b ₄ represent temperature-solid content concentration indexes determined by experiments.

  The solid content concentration x at time t after coating in the drying process required here can be obtained by the following equation.

In Equation 5, x is the solid content concentration (%) of the liquid film at time t after coating, x ₀ is the solid content concentration (%) of the coating liquid, and H ₀ is the liquid film thickness (m) immediately after coating. , H is the liquid film thickness (m) at time t, d _liq is the coating liquid density (kg / m ³ ), d _solid is the apparent density of the antireflection layer (kg / m ³ ), and d _solv is the solvent density. (Kg / m ³ ) is shown.

  The density of the coating liquid and solvent can be measured with various liquid density measuring instruments such as a float and a vibration type density meter based on JISK0061: 2001, and the apparent density of the antireflection layer is applied to a petri dish or the like. The liquid is dried and cured to produce a sheet-like solid, which is determined by measuring with a solid density measuring device such as a specific gravity bottle method based on JISK0061: 2001.

  Furthermore, from the solid content concentration of the coating film at time t after coating, the solvent evaporation amount of the coating film at time t after coating can be determined, and the drying speed v can be determined from the change per minute time. Furthermore, the average drying speed in the constant rate drying period is a value obtained by averaging the drying speed v in the constant rate drying period.

In Equation 6, s is the amount of solvent evaporation at time t after coating, H ₀ is the thickness of the liquid film immediately after coating (m), d _liq is the density of the coating solution (kg / m ³ ), and x is the coating. The solid content concentration (%) of the liquid film at time t from the beginning, x ₀ indicates the solid content concentration (%) of the coating solution.

  The particle diameter R described in Equation 1 represents the representative diameter of the particles in the coating liquid, and specifically represents the median value of the volume reference distribution by the dynamic light scattering method of the coating liquid. The dynamic light scattering method, the volume reference distribution, and the median value are as described above.

  Specifically, the temperature T can be measured continuously with a non-contact thermometer at the instant film surface temperature in the drying process.

  An example of the behavior of the change in the Peclet number during the drying process determined using these parameters is shown in FIG.

  FIG. 4 shows a liquid film thickness change curve 6 and a Peclet number change curve 7. In the liquid film thickness change curve 6, a section showing a linear decrease in the first half is a constant rate drying period 8, a section showing a gradual decrease in the latter half is a reduced rate drying period 9, and the change point is a critical drying point 10. Applicable. The behavior of the change curve 7 of the Peclet number at this time is that the value of the Peclet number is larger than 1 immediately after coating, becomes smaller than 1 with the progress of drying, further proceeds with drying, and the constant rate drying period It rises rapidly with the end and exceeds 1 again. The time 11 when the Peclet number becomes smaller than 1 at this time corresponds to a period during which the change curve of the Peclet number is smaller than 1, as shown in FIG.

  FIG. 5 shows the behavior of the change in the Peclet number when the drying speed is changed.

  In FIG. 5, when the drying speed is increased, the liquid film thickness change in the drying process becomes steep in the order of 12, 13, and 14 (the drying speed is in the order of 12 <13 <14). The change curve of the Peclet number becomes steep like 15, 16, and 17 (the change curve of the Peclet number corresponding to 12 corresponds to 15, and the change curve of the Peclet number corresponding to 12, 13 corresponds to 16, 14). The change curve of the Peclet number is 17, and the point where the Peclet number rises rapidly moves, and the period in which the Peclet number is smaller than 1 becomes shorter in the order of 18, 19, and 20.

Furthermore, FIG. 6 shows the behavior of the change in the Peclet number when the particle diameter and the coating solution viscosity are changed.
Even if the particle size and the coating solution viscosity are changed, if the drying speed is the same, there will be no difference in the change in the thickness of the liquid film during the drying process. By reducing the viscosity of the working fluid, the change curve of the Peclet number changes from 22 to 23, and the time when the Peclet number becomes smaller than 1 becomes longer in the order of 24 and 25.
[Composition of coating liquid]
The coating liquid used in the production method of the present invention preferably contains at least two kinds of particles. These particles may be either organic particles or inorganic particles. Here, the organic particles refer to particles formed of an organic compound, that is, a polymer compound, and the inorganic particles refer to particles formed of an inorganic compound.

  The number of types of 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 type of particle is determined by the type of element constituting the particle. (For fluorine-treated particles to be described later, it depends on the type of elements constituting the particles before being surface-treated). For example, titanium oxide (TiO ₂ ) is different from nitrogen-doped titanium oxide (TiO _2−x N _x ) in which part of oxygen in titanium oxide is replaced by nitrogen as an anion because the elements constituting the particles are different. It is a kind of particle. In addition, if particles (ZnO) consisting only of the same element, for example, Zn or O, even if there are a plurality of particles having different particle diameters or the composition ratio of Zn and O is different, these are The same type of particles. Even if there are a plurality of Zn particles having different oxidation numbers, as long as the elements constituting the particles are the same (in this example, all elements other than Zn are the same), these are the same kind of particles. .

  And in the manufacturing method of this invention, the coating liquid of the high refractive index layer and also the low refractive index layer component are mixed, and, thereby, the coating liquid of this invention is applied only once. By the step and the step of drying, an antireflection member having an antireflection layer composed of two layers having different refractive indexes, such as a high refractive index layer and a low refractive index layer, on a supporting substrate can be obtained.

It is preferable that the low refractive index layer constituent component and the high refractive index layer constituent component in the coating liquid used in the production method of the present invention are each composed of different types of particles.
[Low refractive index layer component]
First, the particles suitably used as the low refractive index layer component will be described. At least one of the two or more types of particles of the coating liquid used in the production method of the present invention is a particle surface-treated with the fluorine compound A (the particle surface-treated with the fluorine compound A is a fluorine-treated particle). It is important that this fluorinated particle is suitable as a component of the low refractive index layer. (The fluorine compound A will be described later.) The particles (the particles before being treated with the fluorine compound A) suitable for producing the fluorine-treated particles are selected from Si, Na, K, Ca, and Mg. Inorganic particles containing elements are preferably exemplified, and more preferably selected from silica particles (SiO ₂ ), alkali metal fluorides (NaF, KF, etc.), and alkaline earth metal fluorides (CaF ₂ , MgF _2, etc.). Silica particles are particularly preferred from the viewpoints of durability, refractive index and the like, which are inorganic particles containing a compound. The silica particles surface-treated with the fluorine compound A are hereinafter referred to as fluorine-treated silica particles.

The silica particles preferably used as the inorganic particles of the constituent material of the fluorine-treated particles refer to particles comprising a composition comprising either a silicon compound or a polymerized (condensed) organic silicon compound. As a general example, SiO ₂ It is a general term for particles derived from silicon compounds such as

  The shape of the particles constituting the fluorine-treated particles before the surface treatment is not particularly limited, but the refractive index of the antireflection layer formed on the antireflection member obtained by the production method of the present invention is not limited. From the viewpoint, a spherical shape is preferable. More preferably, the particle that is a constituent material of the fluorinated particle is a silica particle, and the silica particle preferably has a hollow and / or porous shape (the hollow silica particle has a cavity inside the particle). It is a silica particle, and the porous silica particle is a silica particle having pores on the surface and inside of the particle).

  Moreover, the effect of lowering the density of the obtained antireflection layer can be obtained by using inorganic particles such as hollow and / or porous silica particles. In particular, silica particles having cavities inside and / or silica particles having pores on the surface and inside are used as the particles that are constituent materials of the fluorinated particles. This is preferable because it is easily contained in the low refractive index layer (the outermost layer (first layer) on the antireflective layer side) of the antireflective member obtained by the above, and the low refractive index layer is suitably formed. The silica particles having porosity are hereinafter referred to as hollow particles.

  Then, the number average particle diameter of the particle | grains which are the constituent material of the fluorine treatment particle | grains suitable for a low refractive index layer is demonstrated. When the number average particle diameter of the particles (number average particle diameter of the particles before being surface-treated) is larger than 200 nm, it is not preferable because good transparency cannot be obtained due to light scattering. In addition, although there is no particular influence on the small particle size, the lower limit of the number average particle size of particles that can be obtained in a practically stable manner is about 1 to 5 nm.

  The particles surface-treated with the fluorine compound A in the coating liquid of the present invention preferably have a number average particle size (number average particle size before surface treatment) of 1 nm to 200 nm, more preferably 5 nm to 180 nm. More preferably, it is 5 nm to 100 nm.

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

  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.

  The fluorine-treated particles are preferably moved to the air side (the outermost layer) and can preferably form a low refractive index layer, so that at least one kind of particles of two or more kinds of particles used in the coating liquid is used. Are preferably fluorine-treated particles that have been surface-treated with the fluorine compound A. In addition, it is better to use a coating liquid containing both fluorine-treated particles and other particles that have not been surface-treated with the fluorine compound A, rather than all of the two or more types of particles being fluorine-treated particles. Since two layers having a large difference in refractive index can be obtained, it is preferable in terms of antireflection properties. That is, the coating liquid used in the production method of the present invention preferably contains at least one kind of both fluorinated particles and other particles other than fluorinated particles.

  Further, the particles subjected to the surface treatment with the fluorine compound A are silica particles such as hollow silica particles, that is, the fluorine-treated particles are particularly preferably fluorine-treated hollow silica particles.

  The surface treatment step with the fluorine compound A for particles such as hollow silica may be performed in one step or may be performed in multiple steps. Further, the fluorine compound A may be used in a plurality of stages, or the fluorine compound A may be used only in one stage.

  Moreover, the fluorine compound A preferably used in the surface treatment step of particles such as hollow silica may be a single compound or a plurality of different compounds.

  The surface treatment with the fluorine compound A refers to a step of chemically modifying particles such as hollow silica particles and introducing the fluorine compound A into particles such as hollow silica particles.

  As a method of directly introducing fluorine compound A into particles such as hollow silica particles, fluoroalkoxysilane having both a fluorine segment and a silyl ether group (including a silanol group obtained by hydrolyzing a silyl ether group) in one molecule There is a method in which at least one compound and an initiator are stirred together. However, when the fluorine 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 easily occur during coating after coating.

  Further, as a further method of chemically modifying particles such as hollow silica particles and introducing fluoroalkyl groups into the particles such as hollow silica particles, the particles such as hollow silica particles are treated with a crosslinking component, and a fluorine compound There is a method to connect with A. As the fluorine compound A having a functional group, fluoroalkyl alcohol, fluoroalkyl epoxide, fluoroalkyl halide, fluoroalkyl acrylate, fluoroalkyl methacrylate, fluoroalkyl carboxylate (including acid anhydrides and esters), and the like are used. Can do.

  The cross-linking component refers to a compound having no fluorine in the molecule but having at least one site capable of reacting with the fluorine compound A and one site capable of reacting with particles such as hollow silica particles. The site capable of reacting with the particles is preferably silyl ether or a hydrolyzate of silyl ether from the viewpoint of reactivity. These compounds are generally called silane coupling agents. For example, glycidoxyalkoxysilanes, aminoalkoxysilanes, acryloylsilanes, methacryloylsilanes, vinylsilanes, mercaptosilanes, etc. may be used. it can.

A more preferable form of the fluorine-treated particles suitable for the coating liquid used in the production method of the present invention is that silica particles (particularly hollow silica particles) are treated with a compound represented by the following general formula (I), and the following general formula ( Particles treated with the fluorine compound A represented by 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 a reactive double bond group, 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 an alkyl group having 1 to 4 carbon atoms, R ^f2 represents a fluoroalkyl group, n represents an integer of 0 to 2, and each may have a side chain in the structure.
The reactive double bond group in the present invention is a functional group that chemically reacts with radicals generated by receiving energy such as light or heat, and specific examples include vinyl group, allyl group, acryloyl group, methacryloyl group. Etc.

  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) having no fluoroalkyl group R ^f2 in the molecule, it becomes possible to modify the surface of silica particles such as hollow silica under simple reaction conditions. It is possible to introduce a functional group whose reactivity is easy to control on the surface of the silica particle, and as a result, the fluorine compound A having a reactive double bond and a fluoroalkyl group R ^f2 can be reacted on the surface of the silica particle. It becomes possible.

The coating liquid used in the production method of the present invention preferably contains fluorinated particles. It is because these particles can suitably form a low refractive index layer by including particles (fluorine-treated particles) surface-treated with the fluorine compound A in the coating liquid. Here, the silica particles, the compound represented by the general formula (I), and the compound represented by the general formula (II) are represented by the general formula (I) in the coating liquid used in the present invention. It is preferable to exist as a condensate and / or a polymer surface-treated with the compound represented by formula (II) and the compound represented by the general formula (II) because the low refractive index layer can be suitably formed.
[High refractive index layer component]
Subsequently, other particles excluding the fluorinated particles will be described. Other particles excluding the fluorinated particles are preferably used as a component of the high refractive index layer.

The other particles excluding the fluorinated particles are not particularly limited, but are preferably inorganic compounds, particularly metals, metalloid oxides, nitrides, borides, and Zr, Ti, Al, In, Zn, Sb. More preferably, it is oxide particles of at least one metal selected from the group consisting of Sn, Sn, and Ce. Further, as the particles suitably used as the high refractive index layer component, particles having a refractive index higher than that of silica particles are preferable. Specifically, zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ). At least one inorganic compound, or a solid solution between these inorganic compounds, and a solid solution in which some elements are substituted, intruded, or deficient, antimony-containing tin oxide (ATO) or titanium oxide (TiO ₂ ) are particularly preferable.

  In the present invention, it is preferable to include at least one kind of other particles (such as particles made of an inorganic compound) excluding these fluorinated particles. More preferably, it is an embodiment containing one or more and five or less other types of particles excluding the fluorinated particles, and an embodiment containing one type is particularly preferred.

  The number average particle diameter of particles suitable as a high refractive index hard coat layer constituent in the coating liquid, especially the average particle diameter of particles made of an inorganic compound having a higher refractive index than silica particles suitable as a low refractive index layer constituent Is preferably 150 nm or less, more preferably 20 nm or less. Although there is no problem if the number average particle diameter of the inorganic particles is small, the lower limit of the particle diameter that can be practically produced is about 1 nm. When the number average particle diameter of the inorganic particles is larger than 20 nm, it becomes difficult to form a spontaneous layer structure in the drying process.

  The refractive index of particles suitable as a constituent component of the high refractive index layer in the coating liquid, particularly the refractive index of particles made of an inorganic compound having a higher refractive index than silica particles is preferably 1.58 to 2.80, and more. Preferably it is 1.60-2.50. When the refractive index of the particles is smaller than 1.58, the refractive index of the high refractive index hard coat layer may be lowered. When the refractive index of the particles is larger than 2.80, the high refractive index hard coat layer and the support are supported. The difference in refractive index with the base material increases, resulting in poor antireflection performance, and a slight change in film thickness causes a change in interference color. May get worse.

The particles used as the high refractive index layer constituting component in the coating liquid are as described above. However, when the particles subjected to the surface treatment with the fluorine compound A are silica particles, the particles having a higher refractive index than the silica particles. It is particularly preferable that an inorganic compound having a number average particle diameter of 20 nm or less and a refractive index of 1.60 to 2.80 is preferably used as such particles having a higher refractive index than the silica particles. Specific examples of such inorganic compounds include antimony-containing tin oxide (ATO), zirconium oxide (ZrO ₂ ), and / or titanium oxide (TiO ₂ ), and the refractive index is particularly high from the viewpoint of antireflection properties. Titanium oxide is more preferable.

In the coating liquid used in the production method of the present invention, when the particles subjected to the surface treatment with the fluorine compound A are silica particles, and the other particles are particles having a higher refractive index than the silica particles, By coating and drying the coating liquid once on at least one surface, a low refractive index layer containing fluorinated silica particles and a high refractive index layer containing particles having a higher refractive index than the silica particles, Since it can form suitably in order of a support base material, a high refractive index layer, and a low refractive index layer, it is a preferable aspect.
[Fluorine compound B]
The coating liquid used in the production method of the present invention contains a fluorine compound B having a fluoroalkyl group and a reactive site and having a number average molecular weight of 300 or more and 4000 or less in addition to the two or more kinds of particles described above. Is preferred.

  By including the fluorine compound B, the fluorine compound B is adsorbed on the surface of the fluorine-treated particles due to the affinity of the fluorine compound B, and the interaction between the fluorine-treated particles is suppressed. As a result, by improving the fluidity of the coating liquid during drying, it is possible to form two layers with a large difference in refractive index as a uniform layer structure in the surface, and exhibit excellent antireflection properties. Therefore, the fluorine compound B is preferably included.

  As described above, the number average molecular weight of the fluorine compound B is preferably 300 or more and 4000 or less. By setting the number average molecular weight of the fluorine compound B within the above range, both the mobility in the liquid film and the effect of suppressing the interaction between particles can be achieved, and the antireflection property can be improved.

The above-mentioned number average molecular weight is obtained by measurement by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodisperse polystyrene having a known molecular weight as a standard substance. In addition, it can be obtained by freezing point depression, boiling point rise, osmotic pressure, vapor pressure osmometry of terminal group determination. The number average molecular weight is defined by M _n = ΣM _i N _i / ΣN _i where N _i is the number of molecules of the molecular weight M _i .

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 8 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 double bond group.)
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.

  The oligomer derived from the monomer of the general formula (A) refers to a compound having an average degree of polymerization of about 2 to 10 obtained by a polymer reaction such as radical polymerization of the monomer of the specific example (A).

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

The oligomer derived from the monomer of the general formula (B) is a compound obtained by reacting while adding a predetermined amount of water to the above-mentioned fluoroalkylsilane and distilling off the alcohol produced as a by-product in the presence of an acid catalyst. is there. 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.
[solvent]
The coating liquid used in the method for producing an antireflection member of the present invention preferably further contains a solvent in addition to the two or more kinds of particles described above. A solvent here refers to the liquid which can evaporate almost most in the drying process after coating. By including a solvent in the coating liquid, it is easy to spread the liquid film, so the film thickness control accuracy is improved, and the fluorinated particles are reflected on the air side (because it is easy to move to the outermost surface layer. Prevention performance is improved.

  The 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 dispersion stability of the 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.
[Binder component]
The coating liquid used in the method for producing an antireflection member of the present invention preferably contains at least one binder component. That is, the low refractive index layer and the high refractive index layer of the antireflection member obtained by the coating liquid of the present invention may contain a binder component derived from the binder component in the coating liquid in addition to the aforementioned substances. . Although it does not specifically limit as a binder component in a coating liquid, 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 is one kind. It may be present, or two or more kinds may be mixed and used.

In addition, from the viewpoint of retaining the fluorinated particles in the present invention and other particles other than the fluorinated particles in the film, alkoxysilane, a hydrolyzate of alkoxysilane, or a reactive double bond is included in the molecule. It is preferable that it is a binder component. In the case of curing with UV rays, it is preferable that the oxygen concentration is as low as possible because oxygen inhibition can be prevented, and it is more preferable to cure in an anaerobic atmosphere. By reducing the oxygen concentration, the cured state of the outermost surface is improved and the alkali resistance may be improved. As the binder component in such a coating liquid, it is preferable to use a polyfunctional acrylate, 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. In addition, 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 Chemical Co., Ltd. (Product name “NK Ester” series, etc.), DIC Corporation; (Product name “UNIDIC”, etc.), Toa Gosei Chemical Industry Co., Ltd. (“Aronix” series, etc.), Nippon Oil & Fats Corporation; (“Blemmer” series) Etc.), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” series, etc.), Kyoeisha Chemical Co., Ltd. (trade name “light ester” series, etc.), etc., and these products can be used. .
[Initiator, curing agent, other additives]
It is preferable that the coating liquid used for the manufacturing method of the antireflection member of this invention contains an initiator, a hardening | curing agent, and a catalyst further. The initiator and the catalyst are used for accelerating the reaction between the fluorinated silica particles, which are fluorinated 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, etc. in the coating liquid are preferable.

  Various initiators and curing agents and catalysts can be used. A plurality of initiators may be used at the same time or may be used alone. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of 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-methylphenyl) Nyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenylketone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2- Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like.

  In addition, the addition 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 liquid. It is a mass part, More preferably, it is 0.1 mass part-10 mass parts.

In addition, the coating liquid used in the production method of the present invention further requires additives such as a surfactant, a thickener, a leveling agent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, and a pH adjuster. You may add suitably according to it.
[Content of each component in coating liquid]
When the particles excluding the fluorinated particles are used as other particles, the content ratio (mass ratio) of the fluorinated particles / other particles is fluorinated particles / other particles = 1/30 to 1/1. Is preferred.

  By setting the content ratio (mass ratio) of the fluorinated particles / other particles within the above range, it becomes possible to ensure scratch resistance and wear resistance while maintaining excellent antireflection properties.

  Preferably, in 100% by mass of the coating liquid of the present invention, all the particles (including the fluorine-treated particles) (all the particles here are bonded to the particles in the fluorine-treated particles by the surface treatment with the fluorine compound A). The total mass of the fluorine-treated particles including the organic compound such as the fluorine compound A is also included.) Is 0.2 to 40% by mass, the organic solvent is 40 to 98% by mass, and the fluorine compound B is 1% by mass to 30% by mass, an aspect including 0.1% by mass to 20% by mass of other components such as a binder component, an initiator, a curing agent, and a catalyst, and more preferably all particles (including fluorinated inorganic particles) Is 1 to 35% by mass, the solvent is 50 to 97% by mass, the fluorine compound B is 2 to 25% by mass, and other components are 1 to 15% by mass.

  In a more preferred embodiment, two or more kinds of particles are inorganic compound particles and fluorinated silica particles, and the total of these is 2 to 30% by mass in 100% by mass of the coating liquid of the present invention, and the organic solvent is 60 to 95% by mass. %, Fluorine compound B is 3 to 20% by mass, and other components are 2 to 10% by mass.

  Fluorine-treated particles can be suitably fixed to the air side (outermost surface layer) when a coating liquid containing the same is applied to a support substrate and dried to form a low refractive index layer. Therefore, it is important that at least one kind of particles (particularly silica particles) of two or more kinds used in the coating liquid of the present invention is surface-treated with the fluorine compound A.

In addition, the surface treatment with the fluorine compound A (particularly silica particles) and the surface treatment with the fluorine compound A are not performed compared to the case where all of the two or more types of particles are subjected to the surface treatment with the fluorine compound A. The use of a coating liquid containing both particles (particularly metal oxide) is preferable in terms of antireflection properties because two layers having a large refractive index difference can be obtained.
[Supporting substrate]
Except for the case where the antireflection member is provided directly on the CRT image display surface or the lens surface, it is important that the antireflection member has a supporting base material. Although there is no limitation in particular in a support base material, a plastic film is more preferable than a glass plate. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethene Tacrylate and polyetherketone are included, but among these, triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are particularly preferable.

  In a preferred embodiment of the production method of the present invention, since a plastic having insufficient scratch resistance as described above can be directly used as a support substrate, scratch resistance can be imparted in addition to antireflection properties. Thus, it is not necessary to provide a hard coat layer on the support substrate. 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.

An infrared absorber or an ultraviolet absorber may be added to the support substrate. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass and more preferably 0.05 to 10% by mass with respect to 100% by mass of all the components of the support substrate. As a slip agent, particles of an inert inorganic compound may be added to the support substrate. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. Furthermore, the support substrate may be subjected to a surface treatment.

Various surface treatments can be applied to the surface of the support substrate. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.
[Method for producing antireflection member using coating liquid of the present invention]
In the production method of the present invention, the refractive index is formed on the supporting base material by performing a coating step consisting of a single layer of liquid film once and a drying step in this order on at least one surface of the supporting base material. Can be formed simultaneously.

  Here, the process of applying the coating liquid consisting of one layer of liquid film once means that the liquid film of one layer consisting of one kind of coating liquid is applied to the base material once in the coating process. This refers to coating only once. Multi-layer simultaneous coating in which multiple layers of liquid film are applied at the same time in a single coating process, and multiple layers of liquid film at the same time. It means that wet-on-wet coating or the like is not performed, in which one layer of liquid film is applied a plurality of times at the time of one coating, followed by drying.

  First, a coating solution containing components for forming each layer is prepared as described above, and this coating solution is prepared by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, Coating is carried out on a supporting substrate by a gravure coating method or a die coating method (see US Pat. No. 2,681,294).

  Of these coating methods, the gravure coating method or the die coating method is preferable as the coating method. The gravure coating method is excellent for coating a coating solution with a small coating amount, such as an antireflection layer, with a uniform film thickness. Among the gravure coating methods, the direct gravure method is a small-diameter gravure with a small gravure roll diameter. It is more preferable to use a roll from the viewpoint of securing the stability of the meniscus portion. As such a coating method, a microgravure method has been proposed.

  In addition, the die coating method requires a device when the coating amount is small, such as an antireflection layer, but the film thickness can be controlled by the amount of liquid supplied to the coating die because of the pre-measuring method, In principle, since there is no staying part or evaporation part of the coating liquid, it is also excellent in terms of the stability of the coating liquid.

  Next, the liquid film coated on the support substrate is dried. In addition to completely removing the solvent from the resulting antireflective member, the drying process also heats the liquid film from the viewpoint of promoting the movement of particles in the liquid film to spontaneously form a layer structure. Is preferably accompanied.

This drying process is generally divided into (A) constant rate drying period and (B) reduced rate drying period. In the former, diffusion of solvent molecules into the atmosphere on the liquid film surface is the rate-limiting rate of drying. Therefore, the drying speed is constant in this section, the drying speed is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the wind speed and the temperature, and the film surface temperature is a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. It becomes constant. In the latter, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a constant value in this section and continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature is To rise. Here, the drying rate represents the amount of solvent evaporation per unit time and unit area, and has a dimension of g / (m ² · s).

In the production method of the present invention, it is presumed that the formation of the spontaneous layer structure occurs during the constant rate drying period, and there is a preferred range for the drying rate in this section, 1.4 g / (m ² .S) or less, more preferably 0.9 g / (m ² .s) or less, and preferably 0.1 g / (m ² .s) or more. By setting the drying speed in the constant rate drying period within this range, it is possible to prevent unevenness due to non-uniformity of the drying speed and to sufficiently secure the time required to cause a spontaneous layer structure.

As long as a drying rate in the range of 0.1 g / (m ² .s) or more and 1.4 g / (m ² .s) or less can be obtained, the wind speed and temperature are not particularly limited.

  In the production method of the present invention, the layer structure is densified by the arrangement of particles during evaporation of the remaining solvent and the evaporation of the residual solvent. In this process, because of the arrangement of particles, it takes time for the arrangement along with the mobility of the particles. Therefore, there is a preferable range for the film surface temperature increase rate during the decremental drying period, and it is 5 ° C./second or less. Preferably, it is 1 ° C./second or less.

  Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared rays), and others (microwave, induction heating). Among these, in the production method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform in the width direction. In order to achieve a uniform drying rate, in the case of drying by convective heat transfer, as a method that can reduce the overall mass transfer coefficient during drying while maintaining a controllable wind speed, A method of blowing hot air in a direction that is parallel and parallel or perpendicular to the conveyance direction of the substrate is desirable.

  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. When curing with heat in the curing step, the temperature is preferably from room temperature to 200 ° C, more preferably from 100 ° C to 200 ° C, and even more preferably from 130 ° C to 200 ° C, from the viewpoint of the activation energy of the curing reaction. It is as follows.

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. When the discharge lamp type to ultraviolet cured using a high pressure mercury lamp is, illuminance 100~3000mW / cm ² of ultraviolet, ultraviolet irradiation under the conditions preferably 200~2000mW / cm ^2, further preferably a 300~1500mW / cm ² preferably performing, integrated light quantity of ultraviolet 100~3000mJ / cm ^2, preferably 200~2000mJ / cm ^2, more preferably it is more preferable to carry out ultraviolet irradiation under the condition that the 300~1500mJ / cm ^2. 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.

[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-15)]
For the high refractive index layer constituent component (A-8), the high refractive index layer constituent component (A-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
(ELCOM JGC Catalysts & Chemicals Co., Ltd .: solid content 30% by mass, number average particle size 15 nm)
[Adjustment of high refractive index layer component (A-25)]
The high refractive index layer constituent component (A-15) 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 (A-40)]
The high refractive index layer constituent component (A-40) 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). ATO particle dispersion
(ELCOM JGC Catalysts & Chemicals Co., Ltd .: solid content 30% by mass, number average particle size 38 nm)
[Adjustment of High Refractive Index Layer Component (A-50)]
The following materials were mixed, and ATO dispersion liquid was obtained by dispersing ATO particles in the liquid using a media disperser (using zirconia beads having a diameter of 0.1 mm).
20 parts by mass of conductive fine particles ATO (antimony-doped tin oxide T-1 manufactured by Mitsubishi Materials Corporation)
Tetraalkoxysilane 3.0 parts by mass Methyl isobutyl ketone 77 parts by mass Furthermore, Kayrad DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass), which is a polyfunctional acrylate, is mixed with the ATO dispersion at a mass ratio of 8: 2. And the high refractive index layer structural component (A-50) was obtained.

[Adjustment of high refractive index layer component (A-70)]
The high refractive index layer constituent component (A-8) was obtained in the same manner except that the titanium dioxide particle dispersion was changed to the following PTO particle dispersion with respect to the high refractive index layer constituent component (A-8). .
80 parts by mass of PTO particle dispersion
(ELCOM JGC Catalysts & Chemicals Co., Ltd .: solid content 30% by mass, average particle size 70 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 the high refractive index layer constituent component (A-8) except that the binder component A was changed to the following material.
Binder component B
(Aronix M405 manufactured by Toa Gosei Co., Ltd .: solid content 100% by mass)
[Adjustment of high refractive index layer component (B-50)]
A high refractive index layer constituent component (B-50) was obtained in the same manner except that the binder component A was changed to the following material with respect to the high refractive index layer constituent component (A-50).
Binder component B
(Aronix M405 manufactured by Toa Gosei Co., Ltd .: solid content 100% by mass)
[Adjustment of high refractive index layer component (B-15)]
A high refractive index layer constituent component (B-15) was obtained in the same manner as in the high refractive index layer constituent component (A-15) except that the binder component A was changed to the following material.
Binder component B
(Aronix M405 manufactured by Toa Gosei Co., Ltd .: solid content 100% by mass)
[Adjustment of high refractive index layer component (C-15)]
The high refractive index layer constituent component (A-15) was obtained in the same manner as the high refractive index layer constituent component (A-15) except that the binder component A was changed to the following material.
Binder component C
(Aronix M350 manufactured by Toagosei Co., Ltd .: solid content 100% by mass)
[Adjustment of high refractive index layer component (X)]
The following materials were mixed to obtain a high refractive index layer component (X).

Opstar TU4005 (JSR Corporation) 1.0 part by mass 2-propanol 1.0 part by mass ethylene glycol monobutyl ether 0.11 part by mass [adjustment of low refractive index layer components]
[Adjustment of low refractive index layer component (a)]
1.37 g of methacryloxypropyltrimethoxysilane and 0.17 g of 10% by mass aqueous formic acid solution were mixed with 15 g of through silica 4110 (manufactured by JGC Catalysts & Chemicals Co., Ltd .: solid content concentration 20% by mass), which is hollow silica, at 70 ° C. Stir for 1 hour. Next, 1.38 g of H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F and 0.057 g of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C. for 60 minutes. . 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.

[Coating fluid 1]
The following materials were mixed and the coating liquid 1 was obtained.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (A-25) 29 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.36 parts by mass 7.6 parts by mass of fluorine compound B-1 (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F number average molecular weight: 518)
2-Propanol 57 parts by mass [Coating fluid 2]
A coating liquid 2 was obtained in the same manner as in the coating liquid 1, except that the high refractive index layer constituent (A-25) was replaced with the high refractive index layer constituent (A-15).

[Coating fluid 3]
A coating liquid 3 was obtained in the same manner as in the coating liquid 1, except that the high refractive index layer constituent component (A-25) was replaced with the high refractive index layer constituent component (B-15).

[Coating fluid 4]
A coating liquid 4 was obtained in the same manner as in the coating liquid 1, except that the high refractive index layer constituent (A-25) was replaced with the high refractive index layer constituent (C-15).

[Coating fluid 5]
A coating liquid 5 was obtained in the same manner as in the coating liquid 1, except that the high refractive index layer constituent component (A-25) was replaced with the high refractive index layer constituent component (A-8).

[Coating fluid 6]
The following materials were mixed and the coating liquid 6 was obtained.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (A-15) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass 4.8 parts by mass of fluorine compound B-1 (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F number average molecular weight: 518)
2-Propanol 70.3 parts by mass [Coating fluid 7]
The following materials were mixed and the coating liquid 7 was obtained.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-15) 49.8 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.63 Parts by mass fluorine compound B-1 13.1 parts by mass (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F number average molecular weight: 518)
2-300 parts by mass of 2-propanol [Coating liquid 8]
The following materials were mixed and the coating liquid 8 was obtained.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (A-15) 14 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.18 parts by mass 3.8 parts by mass of fluorine compound B-1 (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F number average molecular weight: 518)
7.5 parts by mass of 2-propanol [Coating liquid 9]
The following materials were mixed and the coating liquid 9 was obtained.
Low refractive index layer constituent (a) 7.1 parts by mass High refractive index layer constituent (A-15) 75 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.95 parts by mass Fluorine compound B-1 13 parts by mass (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F number average molecular weight: 518)
2-propanol 5 parts by mass [Coating solution 10]
A coating liquid 10 was obtained in the same manner as in the coating liquid 6, except that the high refractive index layer constituent component (A-15) was replaced with the high refractive index layer constituent component (A-40).

[Coating liquid 11]
A coating liquid 11 was obtained in the same manner as in the coating liquid 6, except that the high refractive index layer constituent (A-15) was replaced with the high refractive index layer constituent (B-50).

[Coating fluid 12]
The following materials were mixed and the coating liquid 12 was obtained.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (B-8) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass Hydroxylpropyl acrylate 4.8 parts by mass 2-propanol 70.3 parts by mass [Coating liquid 13]
The following materials were mixed to obtain a coating liquid 13.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (B-8) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass 4.8 parts by mass of fluorine compound B-2 (Megafac F408 DIC Corporation)
70.3 parts by mass of 2-propanol [Coating liquid 14]
The following materials were mixed and the coating liquid 14 was obtained.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-15) 29 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.36 parts by mass 7.6 parts by mass of fluorine compound B-3 (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₄ F number average molecular weight: 318)
2-Propanol 57 parts by mass [Coating fluid 15]
The following materials were mixed to obtain a coating solution 15.
Low Refractive Index Layer Component (a) 7.1 parts by mass High Refractive Index Layer Component (A-15) 29 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.36 parts by mass Fluorine compound B-4 7.6 parts by mass (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OH) ₃ 7-mer oligomer
Number average molecular weight: 4000)
2-Propanol 57 parts by mass [Coating fluid 16]
The following materials were mixed to obtain a coating liquid 16.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (B-8) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass 4.8 parts by mass of fluorine compound B-5 (H ₂ C═CH—COO—CH ₂ —CF ₃ number average molecular weight 150)
2-Propanol 70.3 parts by mass [Coating fluid 17]
The following materials were mixed to obtain a coating liquid 17.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (B-8) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass 4.8 parts by mass of fluorine compound B-6 (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OH) ₃ 9-mer oligomer
Number average molecular weight: 4500)
2-Propanol 70.3 parts by mass [Coating fluid 18]
The following materials were mixed to obtain a coating liquid 18.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (B-8) 18 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.22 parts by mass 4.8 parts by mass of fluorine compound B-1 (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F number average molecular weight: 518)
70.3 parts by mass of 2-propanol [Coating liquid 19]
The following materials were mixed to obtain a coating liquid 19.
Low refractive index layer component (a) 7.1 parts by mass High refractive index layer component (x) 7.1 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.10 parts by mass 2-Propanol 85.8 parts by mass [Coating fluid 20]
The following materials were mixed to obtain a coating liquid 20 (low refractive index layer coating liquid).
Low Refractive Index Layer Constituent (a) 7.1 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.10 parts by mass polyfunctional acrylate 18 parts by mass (Kayarad DPHA Nippon Kayaku Co., Ltd. (Product: Solid content 100% by mass)
2-propanol 65 parts by mass [Coating fluid 21]
The following materials were mixed to obtain a coating liquid 21 (high refractive index layer coating liquid).
High refractive index layer component (A-25) 29 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.36 parts by mass 2-propanol 65 parts by mass [Coating liquid 22]
A coating liquid 22 was obtained in the same manner except that the high refractive index layer constituent (A-25) was replaced with the high refractive index layer constituent (A-70) for one coating liquid.

[Coating fluid 23]
The following materials were mixed to obtain a coating solution 23 (hard coat coating solution).
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 [Coating liquid 24]
A coating liquid 24 was obtained in the same manner as in the coating liquid 5, except that the low refractive index layer constituent component (a) was replaced with the low refractive index layer constituent component (b).

Hereinafter, a method for producing an antireflection member will be described. The composition of each sample is summarized in Table 1.

[Preparation of antireflection member 1]
U46 (manufactured by Toray Film Co., Ltd.) in which an easy-adhesive paint was coated on a PET resin film was used as a support substrate. After applying the coating liquid onto the surface of the supporting substrate on which the easy-adhesive paint is applied using a bar coater (# 10), a liquid film thickness measurement sensor and a film surface temperature measurement sensor The first stage of drying shown below was performed using a drying apparatus equipped with a, and then the second stage of drying was performed.
1st stage Hot air temperature 25 ℃
Hot air speed 0.5m / s
Wind direction Parallel to coated surface Drying time 2 minutes 2nd stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 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.

  Using the coating liquids 1, 10, 11, 12, 13, and 17, antireflection members of Examples 1, 12, 13, 14, 15, and 19 were prepared.

[Preparation of antireflection member 2]
An antireflective member was prepared in the same manner as in Preparation 1 of the antireflective member, except that the drying conditions at the first stage were changed to the following conditions.

Hot air temperature 35 ℃
Hot air speed 1m / s
Wind direction Parallel to coating surface Drying time 1.5 minutes Coating liquids 1, 2, 4, 6, 7, 8, 9, 14, 15, 16, 22, 24, Examples 2, 3, 6, 8, 9, 10, 11, 16, 17, 18, 22, and the antireflection member of Comparative Example 4 were prepared.

[Preparation of antireflection member 3]
An antireflection member was prepared in the same manner as in Preparation 1 of the antireflection member, except that the drying conditions at the first stage were changed to the following conditions.

Hot air temperature 40 ℃
Hot air speed 2m / s
Wind direction Parallel to coated surface Drying time 1 minute Here, the coating liquids 2 and 3 were used to prepare the antireflection members of Examples 4 and 5.

[Preparation of antireflection member 4]
An antireflection member was prepared in the same manner as in Preparation 1 of the antireflection member, except that the drying conditions at the first stage were changed to the following conditions.

Hot air temperature 60 ℃
Hot air speed 2m / s
Wind direction Parallel to coated surface Drying time 1 minute Here, the coating solution 5 was used to prepare the antireflection member of Example 7.

[Preparation of antireflection member 5]
An antireflection member was prepared in the same manner as in Preparation 1 of the antireflection member, except that the drying conditions at the first stage were changed to the following conditions.

Hot air temperature 25 ℃
Hot air wind speed 0.1m / s
Wind direction Parallel to the coating surface Drying time 3 minutes Here, the coating solution 2 was used to prepare the antireflection member of Example 20.

[Preparation of antireflection member 6]
An antireflection member was prepared in the same manner as in Preparation 1 of the antireflection member, except that the drying conditions at the first stage were changed to the following conditions.

Hot air temperature 70 ℃
Hot air wind speed 5m / s
Wind direction Parallel to the coated surface Drying time 1 minute Here, the antireflection member of Example 21 was prepared using the coating liquid 18.

[Preparation of antireflection member 7]
U46 (manufactured by Toray Film Co., Ltd.) in which an easy-adhesive paint was coated on a PET resin film was used as a supporting substrate. The coating liquid 23 (hard coat coating liquid) is applied on the surface of the supporting substrate on which the easy-adhesive coating is applied using a bar coater (# 16), and then the first step shown below. And then the second stage of drying.

1st stage Hot air temperature 70 ℃
Hot air speed 2m / s
Wind direction Parallel to the coating surface Drying time 1.5 minutes Second stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coated surface Drying time 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%. And cured.

  Next, after coating the coating liquid 19 on the surface on which the hard coat coating liquid is coated, dried and cured using a bar coater (# 10), a sensor for measuring the thickness of the liquid film and the film surface In a drying apparatus equipped with a temperature measurement sensor, the first stage of drying shown below was performed, followed by the second stage of drying.

First stage Hot air temperature 35 ℃
Hot air speed 1m / s
Wind direction Parallel to the coating surface Drying time 1.5 minutes Second stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 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 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured. Thereby, the antireflection member of Comparative Example 1 was prepared.

[Preparation of antireflection member 8]
U46 (manufactured by Toray Film Co., Ltd.) in which an easy-adhesive paint was coated on a PET resin film was used as a supporting substrate. After coating the coating liquid 21 on the surface of the supporting substrate on which the easy-adhesive paint is coated using a bar coater (# 10), a liquid film thickness measuring sensor and a film surface temperature measuring sensor are used. Drying was performed under the following conditions in a drying apparatus equipped with a sensor.

First stage Hot air temperature 35 ℃
Hot air speed 1m / s
Wind direction Parallel to the coating surface Drying time 1.5 minutes Second stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 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 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured.

Next, after coating the coating liquid 20 on the surface on which the coating liquid 21 is coated, dried and cured using a bar coater (# 10), the coating liquid is dried under the following conditions in the same drying apparatus. went.
First stage Hot air temperature 35 ℃
Hot air speed 1m / s
Wind direction Parallel to the coating surface Drying time 1.5 minutes Second stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 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 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured. Thereby, the antireflection member of Comparative Example 2 was prepared.

[Preparation of antireflection member 9]
An antireflection member was prepared in the same manner as for the preparation 1 of the antireflection member, except that the drying conditions at the first stage were changed to the following conditions.
Hot air temperature 100 ℃
Hot wind speed 10m / s
Wind direction Perpendicular to coated surface Drying time: 1 minute Coating solution 1 was used to prepare an antireflection member of Comparative Example 3.

[Parameter measurement method in the process of making anti-reflective members]
Table 1 shows parameters in the process of creating the antireflection member. The measurement method will be described below.

[Median value of volume-based distribution of particles in coating solution by dynamic light scattering method]
The median value of the volume reference distribution by the dynamic light scattering method at 25 ° C. of the particles in the coating solution was measured using a dynamic light scattering type particle size distribution measuring device (LB550, manufactured by Horiba, Ltd.). The solvent refractive index, which is a parameter of the coating liquid required in the measurement, was measured at 25 ° C. using an Abbe refractometer (Abego Co., Ltd., Abbe Refractometer NAR-3T). In addition, the particle refractive index, which is a parameter of the coating liquid required for the measurement, is based on Method B (immersion method using a microscope (Becke's line method)) in JIS K7142 “Method for measuring refractive index of plastic”. However, instead of the immersion liquid used in JIS K7142, a “contact liquid” manufactured by Shimadzu Device Manufacturing Co., Ltd. was used, and the temperature was measured at 15 to 20 ° C. As a microscope, a polarizing microscope “Optiphoto” (manufactured by Nikon) was used.
Using these values, the measurement was performed at 1000 times. The analysis of the measurement results was performed in the volume-based distribution mode, and the median value of the volume-based distribution was obtained.

[Number average molecular weight]
The number average molecular weight 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.

[Measurement of liquid film thickness and liquid film shrinkage rate at time t after coating]
The liquid film thickness was measured using a micro head type spectral interference laser displacement meter SI-F1000 manufactured by Keyence Corporation. In the measurement, the laser displacement meter was installed in the drying apparatus, and the distance between the sensor head and the coating liquid film was continuously measured to obtain the liquid film thickness in the drying process. Data was collected at a frequency of 1 KHz, and after a smoothing calculation for noise removal, a change in the liquid film thickness was output every 0.1 seconds, which was defined as the liquid film thickness.
Further, the liquid film contraction speed was linearly approximated including the liquid film thickness for 0.5 seconds before and after each point of the liquid film thickness, and the inclination was defined as the liquid film contraction speed at each point.

[Solid content concentration of coating liquid, apparent density of antireflection layer]
The solid content concentration x ₀ of the coating liquid is a value (x _l ) obtained by precisely weighing about 20 g of the coating liquid, and after drying this at 80 ° C. for 30 minutes, a 160 W / cm high-pressure mercury lamp lamp (eye graphics) The mass of the solid matter obtained by irradiating and curing 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 vol% (x) _{From s} ), it calculated | required according to Numerical formula 8.

The apparent density of the antireflective layer is measured by using a Gerysac type pycnometer based on JIS K 0061 (2001) for the solid material dried and cured by the above method, and the apparent density d _{solid of the} antireflective layer is measured. Asked.

[Measurement of coating liquid density d _liq ]
The coating liquid density was measured using a density specific gravity meter (manufactured by Kyoto Electronics Co., Ltd., DA-130N) under an environment of 25 ° C., and the density d _liq of the coating liquid was determined.

[Measurement of film surface temperature T]
The film surface temperature T was measured using a non-contact thermometer manufactured by Fluke. In the measurement, the non-contact thermometer was installed in the drying apparatus, and the film surface temperature was continuously measured. Data was measured every 0.1 seconds. The liquid film thickness measurement and the film surface temperature measurement described above were synchronized by connecting both measuring devices to a data logger and collecting data simultaneously.

[Measurement of viscosity μ of liquid film at time t after coating]
The viscosity of the liquid film was determined by the method described in the section of the calculation method of each parameter constituting the Peclet number and the change behavior of the Peclet number.

For this calculation, parameters a ₁ , a ₂ , a ₃ , a ₄ , b ₁ , b ₂ , b ₃ , and b ₄ used in Equation 4 were measured by the following method. A rheometer AR2000 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 is performed by changing the solvent addition amount (2-propanol addition amount) to make a coating solution with a solid content concentration adjusted by 10, 20, 30, 40%, and this is 25 ° C, 35 ° C, 45 ° C, 55 ° C. The measurement was performed at a steady flow with the shear rate changed stepwise at ° C. Specifically, after preliminary shearing at a shear rate of 100 s ⁻¹ , the shear viscosity was measured in steps of 3 points at a logarithmic interval per digit from the shear rate of 1000 s ⁻¹ to 0.01 s ⁻¹ . From this result, the viscosity of 0.1 s ⁻¹ at each representative composition, each temperature, and each concentration was obtained, plotted against the solid content concentration, and the result was approximated by a cubic curve of Formula 9, and further at each temperature. The parameters a ₁ , a ₂ , a ₃ , a ₄ , b ₁ , b ₂ , b are obtained by linearly approximating the temperature T for A, B, C, and D of Equation 9 obtained from the measured data of _3, was asked to _{b 4.} From this result and the solid content concentration x in the drying process and the temperature T, the viscosity μ of the liquid film at time t after coating was determined.

[Measurement of solid content concentration x at coating time t, liquid film viscosity μ, time when Peclet number is less than 1 and average drying rate during constant rate drying period]
From the liquid film thickness obtained by the above-mentioned method, a change curve of the liquid film thickness and time was prepared, and the period from the coating until the first inflection point appeared was defined as the constant rate drying period.
From the value of the change in the thickness of the liquid film described above, the solid content concentration x at time t after coating is determined by the method described in the above section [Calculation method of each parameter constituting the Peclet number and change behavior of the Peclet number]. The viscosity μ of the liquid film, the time when the Peclet number is smaller than 1, and the average drying rate during the constant rate drying period were determined.

[Evaluation of antireflection member]
The following performance evaluation was performed on the manufactured antireflection member, and the obtained results are shown in Tables 2 and 3. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[Thickness of each layer of the antireflection layer]
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.

[Individual refractive indexes of two layers on a supporting substrate]
The refractive index of each of the two layers on the supporting substrate in the present invention is measured by a reflectance spectral film thickness meter (trade name [FE-3000], manufactured by Otsuka Electronics Co., Ltd.), and the reflectance in the range of 300 to 800 nm is measured. Using the software [FE-Analysis] attached to the apparatus, the refractive index at 550 nm was determined according to the method described in [Film thickness measuring apparatus general catalog P6 (nonlinear least squares method)] manufactured by Otsuka Electronics Co., Ltd.

The optical constants (C ₁ , C ₂ , C ₃ ) are calculated by the least square method (curve fitting method) using Cauchy's dispersion formula (Formula 1) as an approximate expression of the wavelength dispersion of the refractive index, and the refractive index at 550 nm is calculated. It was measured.

[Formation of interface between two layers]
By observing the cross section using a transmission electron microscope (TEM), the presence or absence of the two-layer interface on the support substrate was determined. The presence / absence of the interface was determined according to the following method. An image taken with a TEM at a magnification of 200,000 times was adjusted with software (Easy Access) so that the white balance was within the 8-bit tone curve in the brightest and darkest areas. Furthermore, the contrast was adjusted so that two types of particles could be clearly distinguished.
At this time, when a clear boundary could be drawn at the interface between one layer and the other layer, it was considered that there was a clear interface.

When a clear boundary can be drawn
“×” when a clear boundary cannot be drawn
[Abrasion resistance]
Describe the approximate number of scratches that can be seen when steel wool (# 0000) with a load of 250 g / cm ² is placed vertically on the anti-reflective member and make 10 reciprocations of the length of 1 cm. The score was passed.

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]
At the tip of the eraser abrasion tester manufactured by Honko Seisakusho (tip part area 1 cm ² ), Shiranell (manufactured by Kowa Co., Ltd.) is attached, and a 500 g load is applied to the antireflection member 5 cm and rubbed back and forth 5000 times The following classification was made and 3 or more points were accepted.

5 points: other than the following “1 point”, no scratch 4 points: other than the following “1 point”, 1-10 scratches
3 points: Other than “1 point” below, 11 to 20 scratches
2 points: Other than “1 point” below, 21 or more scratches
1 point: Anti-reflective layer in the test part peels off [transparency]
Transparency was determined by measuring the haze value. The measurement is based on JIS K 7136 (2000), using a Nippon Denshoku Industries Co., Ltd. haze meter so that light is transmitted from the side opposite to the support base of the antireflection member sample (antireflection layer side). The measurement was performed by placing it on the apparatus, 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.

[Evaluation of in-plane uniformity]
Each of the five film surfaces was visually observed in the full width direction of the film, and the in-plane uniformity was evaluated by looking at unevenness according to the following five-stage evaluation criteria, and three or more points were accepted.

5 points: no unevenness is observed in all samples 4 points: slight unevenness is observed in some samples 3 points: slight unevenness is observed in all samples
2 points: Unevenness is observed in all samples, and strong unevenness is present in some samples 1 point: Strong unevenness is observed in all samples [Economic]
The total number of coatings on the supporting substrate, the total drying time required for one application, and the total coating thickness on the supporting substrate are evaluated based on the following criteria: (Score of total drying time) x (score of the number of coating times) was determined, and this value was 6 or more.

Total coating thickness: 1000 nm or less 3 points
3000nm or less 2 points
1 point or more Total drying time: 3 minutes or less 3 points
Less than 4 minutes 2 points
More than that 1 point Number of times of coating: Total number of times of coating on the support substrate is 2 times 1 point
The total number of coatings on the supporting substrate is 1 time 2 points Table 3 summarizes the evaluation results of the antireflection member. Regarding evaluation items that did not pass even one item, it was judged that the problem was not achieved.

  As shown in Table 3, in all of the scratch resistance, abrasion resistance, transparency, antireflection performance, in-plane uniformity, and economic efficiency, the examples have passed, and the first problem is “support base” To provide a production method capable of forming a uniform antireflection layer on the surface with the smallest possible number of coatings on the material, ”and the second issue,“ The smallest possible number of coatings on the support substrate And providing a method for producing an antireflection member having scratch resistance, abrasion resistance, and low reflectance ”.

  In the method for producing an antireflection member of Example 10 in which the thickness of the high refractive index layer of the antireflection member was thinner than the preferred range of the present invention, the scratch resistance was slightly inferior, but was in an acceptable range.

  In the antireflection member manufacturing method of Example 11, where the thickness of the high refractive index layer of the antireflection member is thicker than the preferred range of the present invention, in-plane uniformity and economy were slightly inferior, but within an acceptable range. there were.

  In the production method of the antireflection member of Example 13 in which the median value of the volume-based distribution of particles by the dynamic light scattering method of the coating liquid is larger than the preferred range of the present invention, the antireflection performance and in-plane uniformity are slightly higher. Although it was inferior, it was an acceptable range.

  In the method for producing an antireflection member of Examples 14 and 15, wherein the coating solution contains a compound having no fluoroalkyl group and a compound having no reactive site, which is a preferred embodiment of the present invention, The antireflection performance was slightly inferior, but was in an acceptable range.

  The coating liquid contains a compound having a fluoroalkyl group and a reactive site but having a small number average molecular weight, a compound having a fluoroalkyl group and a reactive site but having a large number average molecular weight, which is a preferred embodiment of the present invention. In the methods for producing the antireflection members of Examples 18 and 19, the transparency and antireflection performance were somewhat inferior, but were within an acceptable range.

In the production method of the antireflection member of Example 21 in which the average drying rate during the constant rate drying period is a preferable aspect of the present invention and exceeds 1.0 g / m ² · s, the transparency and the antireflection performance were slightly inferior. However, it was an acceptable range.

In the method for producing an antireflective member of Example 20 in which the average drying rate during the constant rate drying period is less than 0.1 g / m ² · s, which is a preferable aspect of the present invention, the in-plane uniformity is slightly inferior, It was an acceptable range.

DESCRIPTION OF SYMBOLS 1 Antireflection member 2 Support base material 3 High refractive index layer 4 Low refractive index layer 5 High refractive index hard coat layer 6, 12, 13, 14, 21 Liquid film thickness change curve 7, 15, 16, 17, 22, 23 Peclet number change curve 8 Constant rate drying period 9 Decrease rate drying period 10 Critical drying point 11, 18, 19, 20, 24, 25 Time when the Peclet number becomes less than 1

Claims (7)

A method for producing an antireflection member having an antireflection layer composed of two layers having different refractive indexes on at least one surface of a support substrate,
On at least one side of the supporting substrate, the coating liquid is applied once to form a single layer liquid film, and the liquid film is dried in this order,
A method for producing an antireflective member, characterized in that, in the constant rate drying period of the step of drying the liquid film, a time during which the Peclet number is smaller than 1 is provided for 7 seconds or more. The coating liquid contains at least two kinds of particles and at least one kind of binder component,
At least one of the two or more types of particles is a particle that has been surface-treated with a fluorine compound A (hereinafter, the particles that have been surface-treated with a fluorine compound A are referred to as fluorine-treated particles). The manufacturing method of the reflection preventing member of Claim 1.   The method for producing an antireflection member according to claim 1 or 2, wherein the thickness of the second layer from the outermost layer on the antireflection layer side is 500 nm or more and 2000 nm or less.   4. The median value of volume reference distribution by dynamic light scattering method at 25 ° C. of at least one kind of particles in the coating liquid is 50 nm or less, according to claim 2 or 3. Manufacturing method of antireflection member.   The antireflection member according to any one of claims 1 to 4, wherein the coating liquid contains a fluorine compound B having a fluoroalkyl group and a reactive site and having a number average molecular weight of 300 to 4000. Manufacturing method. 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 antireflection 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, A Is a reactive double bond group.) The drying rate during the constant rate drying period of the drying step is set to 0.1 g / (m ² .s) or more and 1.4 g / (m ² .s) or less. The manufacturing method of the reflection preventing member as described in any one of.

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