TW201832919A - Low refractive index layer-containing adhesive sheet, method for producing low refractive index layer-containing adhesive sheet, and optical device - Google Patents

Abstract

The purpose of this invention is to provide a low refractive index layer-containing adhesive sheet, which is thin and which has a low refractive index. In order to achieve this purpose, this low refractive index layer-containing adhesive sheet is characterized by being obtained by laminating, in the following order, a first adhesive layer, a low refractive index layer, and a second adhesive layer, the refractive index of the low refractive index layer not exceeding 1.25.

Description

Adhesive sheet with low refractive index layer, method for manufacturing adhesive sheet with low refractive index layer, and optical component

The invention relates to an adhesive sheet with a low refractive index layer, a method for manufacturing an adhesive sheet with a low refractive index layer, and an optical component.

In the optical component, for example, a total reflection layer is formed by using an air layer having a low refractive index. Specifically, for example, each optical film member (such as a light guide plate and a reflection plate) in a liquid crystal module is laminated with an air layer interposed therebetween. However, once the members are separated by an air layer, problems such as deflection of the members may occur particularly when the members are large. In addition, due to the trend of thinner components, the integration of various components is expected. Therefore, a method of integrating each member with an adhesive without an air layer (for example, Patent Document 1) has been implemented. However, if there is no air layer exhibiting the total reflection effect, the optical characteristics such as light leakage may be deteriorated.

In response, a method of using a low refractive index layer instead of an air layer has been proposed. For example, Patent Document 2 describes that a layer having a lower refractive index than the light guide plate is inserted between the light guide plate and the reflection plate.

Prior Art Literature Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. 2012-156082 Patent Literature 2: Japanese Patent Application Laid-Open No. 10-62626

Problem to be Solved by the Invention A low refractive index layer is formed on a substrate and used. Therefore, when a low-refractive-index layer is disposed between various components of the optical component, the aforementioned substrate is also disposed, which results in an increase in the thickness of the optical component. If there is only a low refractive index layer, the strength is insufficient, so it is easy to suffer physical damage and difficult to handle.

Therefore, an object of the present invention is to provide a thin and low-refractive-index adhesive sheet containing a low-refractive index layer, a method for manufacturing an adhesive sheet including a low-refractive index layer, and an optical component.

Means for solving the problem In order to achieve the foregoing object, the adhesive sheet with a low refractive index layer of the present invention is characterized in that a first adhesive layer, a low refractive index layer, and a second adhesive layer are sequentially laminated, and the foregoing The refractive index of the low refractive index layer is 1.25 or less.

The first method for manufacturing a low-refractive index layer-containing adhesive sheet of the present invention is the aforementioned method for manufacturing the low-refractive index layer-containing adhesive sheet of the present invention, which includes the following steps: a low-refractive index layer forming step Forming the low-refractive index layer on the transfer resin film substrate; and a transferring step of transferring the low-refractive index layer to the adhesive layer.

The second method for manufacturing a low-refractive-index-containing adhesive sheet of the present invention is the aforementioned method for manufacturing the low-refractive-index-containing adhesive sheet of the present invention, which includes the following steps: a coating step, Directly coating the coating liquid that is the raw material of the low refractive index layer on the adhesive layer; and drying the coating liquid on the step of drying.

The optical component of the present invention is characterized by comprising an adhesive sheet including a low refractive index layer, a first optical function layer and a second optical function layer, and the first optical function layer is attached to the first adhesive layer. The position is on the side opposite to the low refractive index layer, and the second optical function layer is attached to the second adhesive layer on the side opposite to the low refractive index layer.

Effects of the Invention According to the present invention, it is possible to provide a thin, low-refractive-index adhesive sheet containing a low-refractive index layer, a method for manufacturing an adhesive sheet including a low-refractive index layer, and an optical component.

The following examples further illustrate the present invention. However, the present invention is not limited in any way by the following description.

In the adhesive sheet with a low refractive index layer of the present invention, for example, the total thickness of the first adhesive layer and the second adhesive layer is larger than that of the first adhesive layer and the low refractive index layer. The total thickness of the second adhesive layer may be, for example, 85% or more, 88% or more, 90% or 92% or more, and may be, for example, 99.9% or less, 99.5% or less, 99.3% or less, or 99.2% or less.

In the adhesive sheet with a low refractive index layer of the present invention, for example, the light transmittance of the laminated body of the first adhesive layer, the low refractive index layer, and the second adhesive layer may be 80%. the above. For another example, the haze of the laminated body of the first adhesive layer, the low refractive index layer, and the second adhesive layer may be 3% or less. The light transmittance may be, for example, 82% or more, 84% or more, 86% or more, or 88% or more. The upper limit is not particularly limited, and is preferably 100%, and may be, for example, 95% or less, 92% or less, and 91% or less. Or below 90%. The measurement of the haze of the laminated body can be performed by the same method as the haze measurement of the low-refractive index layer described later, for example. The light transmittance of the light having a wavelength of 550 nm can be measured by, for example, the following measurement method.

(Measurement method of light transmittance) Using a spectrophotometer U-4100 (trade name of Hitachi, Ltd.) in a state where the adhesive sheet with a low refractive index layer is not attached with a separator (the aforementioned first adhesive bond Layer, the low-refractive index layer, and the second laminated body) were used as samples for measurement. Then, the total light transmittance (light transmittance) of the aforementioned sample at a total light transmittance of 100% of air was measured. The 値 of the total light transmittance (light transmittance) refers to the 以 measured at a wavelength of 550 nm.

In the adhesive sheet with a low refractive index layer of the present invention, for example, the aforementioned low refractive index layer may also be a void layer.

In the adhesive sheet with a low refractive index layer of the present invention, for example, at least one of the first adhesive layer and the second adhesive layer may be on a surface opposite to the low refractive index layer. Separate pieces are attached.

The first manufacturing method of the low-refractive-index-containing adhesive sheet of the present invention is, as described above, the aforementioned method of manufacturing the low-refractive-index-containing adhesive sheet of the present invention, which includes the following steps: A step of forming a refractive index layer forms the aforementioned low refractive index layer on the transfer resin film substrate; and a step of transferring the aforementioned low refractive index layer onto the adhesive layer. In addition, the lower thickness is often referred to as a "film" and the higher thickness is often referred to as a "sheet" to distinguish between them. However, in the present invention, the term "film" and "sheet" are considered to have no special difference.

In the present invention, the first method for manufacturing a low-refractive index adhesive sheet may further include, for example, a step of attaching a separator: adding the foregoing to the adhesive layer on a surface opposite to the low-refractive index layer Separate pieces.

In the present invention, the first method for producing a low-refractive-index-adhesive sheet may further include, for example, a transfer resin film substrate peeling step: after the separation member attaching step, the transfer resin film base材 peeling. In this case, the peeling force of the separator and the adhesive layer should preferably be greater than the peeling force of the transfer resin film substrate and the low refractive index layer.

In the first method for producing an adhesive sheet with a low refractive index layer according to the present invention, for example, the aforementioned resin film substrate for transfer may be formed of a resin containing an alicyclic structure or a resin containing an aliphatic structure. From the viewpoint of durability such as heat-drying when forming a low refractive index layer, an alicyclic structure-containing resin excellent in heat resistance is particularly desirable. The aforementioned aliphatic structure-containing resin is not particularly limited, and examples thereof include polyolefin, polypropylene, and polymethylpentene. The resin having an alicyclic structure is not particularly limited, and examples thereof include polynorbornene and a cyclic olefin copolymer.

The optical component of the present invention is not particularly limited, and examples thereof include a liquid crystal display, an organic EL (Electro-Luminescence) display, a micro LED (Light Emitting Diode) display, and organic EL lighting.

As mentioned above, if the low refractive index layer is fixed to the substrate for direct operation, the total thickness of the low refractive index layer will be greatly increased due to the thickness of the substrate. When the package is used in a module, the thickness of the key component that is thinner is increased.

On the other hand, the low-refractive-index-layer-containing adhesive sheet of the present invention can be made thinner without containing a substrate, for example. Specifically, for example, by not including the base material, the function of the low refractive index layer can be introduced into the device without increasing the thickness other than the thickness of the adhesive layer itself. In addition, since the low-refractive index layer-containing adhesive sheet of the present invention has the aforementioned adhesive layer directly laminated on one or both sides of the low-refractive index layer of the present invention, the low-refractive index layer is subjected to the aforementioned adhesive layer. Protected from physical damage. Therefore, the fragility of the low refractive index layer can be prevented from becoming a fatal problem. In particular, the abrasion resistance of the low-refractive index layer can be compensated by the adhesive layer, and the low-refractive index layer can be protected from abrasion. In addition, the adhesive sheet with a low refractive index layer of the present invention can be attached to other members by using the adhesive layer, so it is easy to introduce the low refractive index layer itself into a component. That is, according to the adhesive sheet with a low refractive index layer according to the present invention, for example, it is easy to maintain a low refractive index layer that originally had a high porosity to enable thinning and physical protection of the low refractive index layer. Further, the functions of the low refractive index layer can be introduced into other components while maintaining the original high transparency.

[Adhesive Adhesive Sheet with Low Refractive Index Layer and Manufacturing Method thereof] The method for producing the adhesive sheet with low refractive index layer of the present invention is not particularly limited. For example, the first low refractive index containing low refractive index of the present invention can be used. The manufacturing method of the adhesive layer of the index layer, or the aforementioned method of manufacturing the second adhesive layer of the low refractive index layer of the present invention. Here are some examples. In addition, hereinafter, the method for producing the first adhesive sheet with a low refractive index layer of the present invention and the method for producing the second adhesive sheet with a low refractive index layer of the present invention will be collectively referred to as "the content of the present invention "Manufacturing method of adhesive sheet of low refractive index layer". In addition, the low-refractive-index layer which is a component in the adhesive sheet containing the low-refractive-index layer of this invention is called a "low-refractive-index layer of this invention" hereafter. Furthermore, the method of manufacturing the low refractive index layer of the present invention will be referred to as "the manufacturing method of the low refractive index layer of the present invention".

[1. Low-refractive index layer and manufacturing method thereof] The low-refractive index layer of the present invention can be formed of, for example, a silicon compound. The low-refractive index layer of the present invention may be, for example, a low-refractive index layer formed by chemically combining fine-pored particles with each other. For example, the aforementioned fine pore particles may be a pulverized product of a gel.

In the method for producing a low-refractive index layer of the present invention, for example, the gel pulverization step for pulverizing the gel of the aforementioned porous body may be one step, but it may be performed by dividing into a plurality of pulverization steps. The number of the pulverization stages is not particularly limited, and may be, for example, two stages or three or more stages.

In the method for manufacturing a low-refractive index layer of the present invention, for example, the plurality of pulverization stages may include a first pulverization stage and a second pulverization stage for pulverizing the gel, wherein the first pulverization stage is to condense the coagulation The gum is pulverized into particles having a volume average particle diameter of 0.5 to 100 μm, and the second pulverizing step is a step of further pulverizing the particles into particles having a volume average particle diameter of 10 to 1000 nm after the first pulverizing step. In this case, the plurality of pulverization stages may or may not include pulverization stages other than the first pulverization stage and the second pulverization stage.

In addition, in the present invention, the shape of "particles" (for example, particles of a pulverized product of the gel described above) is not particularly limited, and may be, for example, spherical or non-spherical. In the present invention, the particles of the pulverized material may be, for example, sol-gel rosary particles, nano particles (hollow nano silica, nano balloon particles), nano fibers, and the like.

In the present invention, for example, the gel is preferably a porous gel, and the pulverized material of the gel is preferably porous, but is not limited thereto.

In the present invention, the pulverized gel may have a structure having at least one of a particulate shape, a fibrous shape, and a flat shape, for example. The particle-like and plate-like constituent units may be made of, for example, an inorganic substance. The constituent element system of the particulate constituent unit may contain, for example, at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr. The particle-like structure (constituting unit) may be solid particles or hollow particles. Specifically, such as polysilicon particles or polysilicon particles with fine pores, hollow silica particles or silica nanoparticles. Balloons, etc. The fibrous structural unit is, for example, a nanofiber having a diameter of nanometer, and specifically, cellulose nanofiber or alumina nanofiber can be mentioned. The flat-shaped constituent unit is, for example, nano clay, and concretely, such as nano-sized bentonite (for example, Kunipia F [trade name]) and the like. The aforementioned fibrous structural unit is not particularly limited, and may be selected from the group consisting of carbon nanofiber, cellulose nanofiber, alumina nanofiber, chitin nanofiber, chitin nanofiber, and polymer At least one fibrous substance in the group consisting of nano-fiber, glass nano-fiber and silica nano-fiber.

In the method for producing a low-refractive index layer of the present invention, the gel pulverization step (for example, the plurality of pulverization stages, such as the first pulverization stage and the second pulverization stage) may be performed, for example, in the aforementioned "other solvent". In addition, the detailed description of the "other solvent" mentioned above is explained later.

The "solvent" (for example, a solvent for producing a gel, a solvent for producing a low-refractive index layer, a solvent for replacement, etc.) in the present invention may not dissolve the gel or its pulverized matter, or may dissolve the gel or The pulverized material or the like is dispersed or precipitated in the aforementioned solvent.

After the first pulverization step, the volume average particle diameter of the gel may be, for example, 0.5 to 100 μm, 1 to 100 μm, 1 to 50 μm, 2 to 20 μm, or 3 to 10 μm. After the second pulverization step, the volume average particle diameter of the gel may be, for example, 10 to 1000 nm, 100 to 500 nm, or 200 to 300 nm. The volume-average particle diameter refers to the particle size deviation of the pulverized material in the gel-containing liquid (gel-containing liquid). The volume average particle diameter can be measured by, for example, a particle size distribution evaluation device such as a dynamic light scattering method or a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

In addition, immediately after the first pulverization stage, the shear viscosity of the liquid may be, for example, 50 mPa / s or more, 1000 mPa.s or more, 2000 mPa.s or more, or 3000 mPa.s or more at a shear rate of 10001 / s, and It may be, for example, 100 Pa.s or less, 50 Pa.s or less, or 10 Pa.s or less. Immediately after the second crushing stage, the shear viscosity of the liquid may be, for example, 1 mPa.s or more, 2 mPa.s or more, or 3 mPa.s or more, and may be, for example, 1000 mPa.s or less, 100 mPa.s or less, or 50 mPa.s. the following. The method for measuring the shear viscosity is not particularly limited, but it can be measured using, for example, a vibration viscosity measuring machine (manufactured by Sekonic Corporation, trade name FEM-1000V) as described in the examples described later.

After the first pulverization stage, for example, the shear viscosity of the liquid containing the particles may be 50 mPa.s or more, and the volume average particle diameter of the particles may be 0.5 to 50 μm.

In the manufacturing method of the low-refractive index layer of the present invention, for example, after the aforementioned solvent replacement step and before the initial pulverization stage starts, it is preferable to include a concentration adjustment step for adjusting the concentration of the liquid containing the aforementioned gel, but it does not include can. In the case where the aforementioned concentration adjustment step is included, for example, after the initial pulverization stage is started, it is desirable not to perform the concentration adjustment on the liquid containing the aforementioned gel.

In the foregoing concentration adjustment step, the gel concentration of the gel-containing liquid may be adjusted to, for example, 1% by weight or more, 1.5% by weight or more, 1.8% by weight or more, 2.0% by weight or 2.8% by weight or more; and may be adjusted to For example, 5 wt% or less, 4.5 wt% or less, 4.0 wt% or less, 3.8 wt% or less, or 3.4 wt% or less. In the foregoing concentration adjustment step, the gel concentration of the liquid containing the gel can be adjusted to, for example, 1 to 5 wt%, 1.5 to 4.0 wt%, 2.0 to 3.8 wt%, or 2.8 to 3.4 wt%. From the standpoint of the ease of operation of the gel pulverization step, the aforementioned gel concentration should not be too high to prevent the viscosity from becoming too high. From the viewpoint of use as a coating solution to be described later, the gel concentration should not be too low to prevent the viscosity from becoming too low. For example, the gel concentration of the gel-containing liquid can be determined by, for example, measuring the weight of the liquid and the weight of the solid component (gel) after deducting the solvent of the liquid, and then measuring the latter (excluding the former measurement). Calculated.

In addition, the foregoing concentration adjustment step may, for example, be able to appropriately adjust the gel concentration of the liquid containing the gel, by adding a solvent to reduce the concentration or by evaporating the solvent to increase the concentration. Alternatively, for the aforementioned concentration adjustment step, for example, if the measurement result of the gel concentration of the liquid containing the aforementioned gel is an appropriate gel concentration, the operation of reducing the concentration or increasing the concentration (concentration adjustment) may not be performed. The liquid containing the aforementioned gel is directly sent to the next step. Alternatively, for the foregoing concentration adjustment step, for example, if the gel concentration of the liquid containing the above-mentioned gel is obviously suitable although not measured, the measurement and the concentration adjustment may be performed without sending the liquid containing the above-mentioned gel directly. Go to the next step.

In the aforementioned gel pulverization step, from the beginning of the initial pulverization stage to the end of the final pulverization stage, the weight% concentration change of the gel-containing liquid may be, for example, within ± 3%, within ± 2.8%, ± Within 2.6%, within ± 2.4%, or within ± 2.2%.

In the method for manufacturing a low-refractive index layer of the present invention, it is further preferable to include a gel morphology control step before the solvent replacement step to control the shape and size of the gel. In the aforementioned gel morphology control step, it is desirable to control so that the gel size does not become too small. This is to easily prevent when the gel size becomes too small, a large amount of solvent adheres to the finely pulverized gel, which will cause the measurement of the solvent concentration to be lower than the actual concentration, and the solvent remaining to become higher than the actual concentration. And the measurement deviation is high. It is also based on that before the solvent replacement step, if the gel size is not too large, the solvent replacement efficiency will be good. In addition, after the aforementioned gel morphology controlling step, it is desirable to control the size of each gel to a nearly uniform state. This is because if the size of each gel is nearly uniform, it is possible to suppress differences in the particle size and gel concentration of the gel pulverized material between batches of the liquid containing the pulverized gel, and it is easy to obtain a gel containing extremely excellent uniformity. Liquid of pulverized gel.

In the gel morphology control step, the short diameter of the gel can be controlled to be, for example, 0.5 cm or more, 0.6 cm or more, 0.7 cm or more, or 0.8 cm or more, and can be controlled to be, for example, 15 cm or less, 13 cm or less, 10 cm or less, or 8 cm. the following. In the gel shape control step, the long diameter of the gel may be controlled to be, for example, 30 cm or less, less than 30 cm, 28 cm or less, 25 cm or less, or 20 cm or less, and may be controlled to be 1 cm or more, 2 cm or more, and 3 cm or more , 4cm or more or 5cm or more. In addition, in the present invention, the "short diameter" of a three-dimensional object (three-dimensional body) means a length measured at a position where the length is the shortest among the positions where the length of the three-dimensional object can be measured. In the present invention, the "long diameter" of the three-dimensional object (three-dimensional body) refers to a length measured at a position where the length of the three-dimensional object is the longest at a position where the length of the three-dimensional object can be measured.

After the gel shape control step, the shape of the gel is not particularly limited, and can be controlled into, for example, a rectangular parallelepiped (including a cube), a cylindrical, polygonal three-dimensional object (such as a triangular column, a hexagonal column, or a polygonal column), a spherical shape, or An oval ball (like a shape like a rugby ball) and the like. After the gel morphology control step, it is preferable that the shape of the gel is controlled to a rectangular parallelepiped or a shape close to a rectangular parallelepiped. In the gel shape control step, when the gel is controlled into a rectangular parallelepiped, the short side can be controlled to be, for example, 0.5 cm or more, 0.6 cm or more, 0.7 cm or more, or 0.8 cm or more, and for example, 15 cm or less, 13 cm or less, 10 cm or less, or 8 cm or less. In the gel morphology control step, when the gel is controlled into a rectangular parallelepiped, the long side can be controlled to be, for example, 30 cm or less, less than 30 cm, 28 cm or less, 25 cm or 20 cm, or 1 cm. Above, above 2cm, above 3cm, above 4cm, or above 5cm. In the present invention, the "short side" of the cuboid refers to the shortest side, and the "long side" refers to the longest side.

The gel morphology control step may be performed, for example, after the gel manufacturing step for manufacturing the gel, or may be performed during the gel manufacturing step (simultaneously with the gel manufacturing step). More specifically, it is as follows, for example.

In the gel morphology control step, for example, the gel can be cut in a state where the gel is fixed, thereby controlling the gel to form the three-dimensional object. When the gel is extremely brittle, the gel may disintegrate unevenly regardless of the cutting direction when the gel is cut. Therefore, by fixing the periphery of the gel, the pressure in the compression direction applied at the time of cutting is uniformly applied to the gel itself, so that the gel can be uniformly cut in the cutting direction. For example, the shape of the gel before the solvent replacement step is a cuboid, and in the gel shape control step, 5 of the 6 faces of the gel surface of the cuboid are in contact with other substances so that The gel is fixed and the gel is cut by inserting a cutting jig from the exposed surface with the remaining one surface exposed. The cutting jig is not particularly limited, but examples thereof include a cutter, a linear thin jig, and a thin and sharp plate jig. The gel may be cut in, for example, the other solvent.

In addition, for example, in the gel manufacturing step, the raw material of the gel can be cured in a mold (container) corresponding to the shape and size of the three-dimensional object to control the gel into the three-dimensional object. With this, even when the gel is extremely brittle, the gel can be controlled to a predetermined shape and size without cutting the gel, so that the gel and the gel can be avoided when the gel is cut. A case where the fracture direction disintegrates unevenly.

In the method for producing a low-refractive index layer of the present invention, for example, the gel of the gel-containing liquid (gel-containing liquid) can be measured after the end of the first pulverization stage and before the end of the final pulverization stage. Concentration, and only the aforementioned liquid having the aforementioned gel concentration within a predetermined range is used for the subsequent pulverization stage. In addition, it is necessary to make a uniform liquid when measuring the gel concentration. Therefore, it is desirable to form a liquid with a high degree of viscosity that is not easy to separate solid and liquid after the end of the aforementioned pulverization stage. As mentioned above, from the viewpoint of ease of handling of gel-containing liquids, the gel concentration should not be too high to avoid excessively high viscosity; and from the viewpoint of use as a coating solution, the gel concentration should not be too low to avoid Too low viscosity. From these viewpoints, only the liquid having the gel concentration within a predetermined range may be continuously supplied until the end of the final pulverization stage. The predetermined range of the gel concentration may be, for example, 2.8% by weight or more and 3.4% by weight or less as described above, but is not limited thereto. The gel concentration measurement (concentration management) is performed as described above, and may be performed after the end of the first pulverization stage and before the end of the final pulverization stage, or may be added or replaced, and the gel may be pulverized after the solvent replacement step One or both of these steps are performed before the step and after the final pulverization step (for example, the aforementioned second pulverization step). Therefore, after the gel concentration is measured, for example, only the aforementioned liquid having the gel concentration within a predetermined range is supplied to the subsequent pulverization stage, or it is used as a liquid finished product containing the pulverized gel. To supply. When the gel concentration measurement is performed before the gel pulverization step after the solvent replacement step, the concentration adjustment step may be performed thereafter if necessary.

In addition, in the concentration management before the gel pulverization step after the solvent replacement step, since the amount of the solvent attached to the gel is unstable, the deviation value of the concentration measurement and each measurement may increase. Therefore, it is preferable to control the shape and size of the gel to an almost uniform state by the gel shape control step before the concentration management before the gel pulverization step after the solvent replacement step. This enables stable concentration measurement. In addition, for example, the gel concentration of the gel-containing liquid can be uniformly and accurately managed.

In the method for manufacturing a low-refractive index layer of the present invention, it is preferable that at least one of the plurality of pulverization stages is different from the other at least one pulverization stage by a different pulverization method. The pulverization methods in the plurality of pulverization steps may all be different, but may be pulverization steps performed in the same pulverization method. For example, when the aforementioned multiple crushing stages are three stages, all three stages may be performed in different ways (that is, using three crushing ways), or any two crushing stages may be performed in the same crushing way, and only one other The comminution stage is carried out in different comminution ways. The pulverization method is not particularly limited, and examples thereof include a cavitation method and a mediumless method which will be described later.

In the method for producing a low-refractive index layer of the present invention, the gel-containing pulverized material-containing liquid system contains, for example, a sol liquid obtained by pulverizing the gel (particles pulverized).

In the method for manufacturing a low-refractive index layer of the present invention, the plurality of pulverization stages may include a coarse pulverization stage and a current pulverization stage. After obtaining the massive sol particles by using the coarse pulverization stage, the porous coagulation retention is obtained by using the foregoing pulverization stage. Colloidal network of sol particles.

The manufacturing method of the low-refractive index layer of the present invention, for example, further includes a step after at least one of the pulverizing stages of the foregoing multiple stages (for example, at least one of the aforementioned first pulverizing stage and the aforementioned second pulverizing stage). A classification step for classifying the aforementioned gel particles.

The method for producing a low-refractive index layer of the present invention includes, for example, a gelation step, and gelatinizing a porous body in a solvent to form the aforementioned gel. In this case, for example, in the pulverization stage of the plurality of stages, the gel that is gelled through the gelation step is used in the first pulverization stage (for example, the first pulverization stage).

The method for producing a low-refractive index layer of the present invention includes, for example, a ripening step, and the gelatinized gel is aged in a solvent. At this time, for example, in the pulverization stage of the plurality of stages, the gel after the aging step is used in the first pulverization stage (for example, the first pulverization stage).

The method for producing a low-refractive index layer according to the present invention is, for example, performing the solvent replacement step after the gelation step, and replacing the solvent with another solvent. At this time, for example, in the first pulverization stage (for example, the first pulverization stage) among the pulverization stages of the plurality of stages, the gel in the other solvent is used.

In the method for manufacturing a low-refractive index layer of the present invention, at least one of the pulverization stages of the plurality of stages (for example, at least one of the first pulverization stage and the second pulverization stage), for example, the shear of the liquid is measured. The pulverization of the porous body was controlled while cutting viscosity.

In the method for producing a low-refractive index layer of the present invention, at least one of the pulverization stages of the plurality of stages (for example, at least one of the first pulverization stage and the second pulverization stage) is performed using, for example, high-pressure non-media pulverization.

In the method for producing a low-refractive index layer according to the present invention, the gel is, for example, a gel of a silicon compound containing at least a trifunctional or less saturated bond functional group.

In addition, in the method for producing a low-refractive index layer of the present invention, the gel-containing liquid obtained by using the step including the aforementioned gel-pulverizing step is also referred to as "the gel-containing liquid of the present invention" ".

According to the gel-containing pulverized liquid of the present invention, for example, by forming a coating film thereof and chemically combining the pulverized materials in the coating film with each other, the above-mentioned text as a functional porous body can be formed. Invented low refractive index layer. According to the liquid containing a pulverized gel according to the present invention, the aforementioned low refractive index layer of the present invention can be provided to various objects, for example. Therefore, the pulverized gel-containing liquid of the present invention and the method for producing the same are particularly useful for the production of the low refractive index layer of the present invention, for example.

The gel-containing liquid of the present invention has, for example, extremely excellent homogeneity. Therefore, when the low-refractive index layer of the present invention is used in an optical member or the like, the appearance can be improved.

The gel-containing pulverized material liquid of the present invention can be obtained by, for example, coating (coating) the aforementioned gel-containing pulverized liquid on a substrate and further drying to obtain a layer having a high porosity (low Refractive index layer) A liquid containing a pulverized gel. The gel-containing pulverized substance liquid of the present invention may be, for example, a gel-containing pulverized substance-containing liquid for obtaining a porous body having a high porosity (a thick or massive block). The block system can be obtained, for example, by integrally forming a film using the gel-containing pulverized liquid.

As before, the low refractive index layer of the present invention may be a void layer. Hereinafter, the low-refractive index layer of the present invention, which is a void layer, may be referred to as "a void layer of the present invention". For example, the aforementioned voided layer of the present invention having a high porosity can be produced by a manufacturing method including the steps of: a step of producing the gelled liquid containing the present invention; A step of applying a liquid on a substrate to form a coating film, and a step of drying the aforementioned coating film.

For another example, a laminated film roll can be manufactured by a manufacturing method including the following steps: the step of manufacturing the gel-containing liquid of the present invention, the step of outputting the rolled resin film, and the output of the resin. A step of thin-film coating the liquid containing the pulverized gel to form a coating film, a step of drying the coating film, and forming the low-refractive index layer of the present invention on the resin film after the drying step Steps of taking up the laminated film. Hereinafter, such a manufacturing method is sometimes referred to as "the manufacturing method of the laminated film roll of this invention." In addition, the laminated film roll produced by the manufacturing method of the laminated film roll of this invention may be hereafter called "the laminated film roll of this invention."

[2. Liquid containing gel pulverized material and production method thereof] The liquid system containing gel pulverized material of the present invention includes, for example, the aforementioned gel pulverization step (for example, the first pulverization phase and the second pulverization phase) have been used. The pulverized product of the pulverized gel and the other solvents mentioned above.

The manufacturing method of the low-refractive-index layer of the present invention is, for example, the aforementioned gel pulverization step for pulverizing the gel (for example, a porous body gel), which may include a plurality of stages, or may include the first pulverization, for example. Stage and the aforementioned second crushing stage. Hereinafter, a case where the method for producing a gel-pulverized liquid containing the present invention includes the first pulverization stage and the second pulverization stage will be described as an example. Hereinafter, the case where the gel is a porous body (porous body gel) will be mainly described. However, the present invention is not limited to this. In addition to the case where the gel is a porous body, the explanation that the gel is a porous body (porous body gel) can be applied analogously. The plurality of pulverization stages (for example, the first pulverization stage and the second pulverization stage) in the method for producing a low-refractive index layer of the present invention may be collectively referred to as a "gel pulverization step" hereinafter.

The liquid containing the pulverized gel of the present invention can be used to produce a functional porous body that exhibits the same function as the air layer (for example, low refractive index). The functional porous body may be, for example, the low refractive index layer of the present invention. Specifically, the pulverized gel-containing liquid obtained by the production method of the present invention is a pulverized product containing the porous body gel, and the three-dimensional structure of the unpulverized porous body gel is destroyed in the pulverized product. Instead, a new three-dimensional structure can be formed which is different from the above-mentioned pulverized porous body gel. Therefore, for example, a coating film (precursor of a functional porous body) formed by using the above-mentioned gel-containing pulverized liquid will become a layer having a new pore structure (new void structure). A layer formed using the aforementioned unpulverized porous body gel cannot be obtained. Thereby, the said layer can exhibit the same function (for example, the same low refractive property) as an air layer. In addition, the gel-containing pulverized material liquid of the present invention, for example, contains a silanol group remaining from the pulverized material, and a new coating film (precursor of a functional porous body) has been formed into a new one. After the three-dimensional structure, the crushed materials can be chemically combined with each other. Thereby, although the formed functional porous body has a structure having voids, sufficient strength and flexibility can be maintained. Therefore, according to the present invention, a functional porous body can be easily and simply provided to various objects. The pulverized gel-containing liquid obtained by the production method of the present invention is very useful for producing the aforementioned porous structure which can be used as a substitute for the air layer. In addition, in the case of the aforementioned air layer, for example, it is necessary to form an air layer between the members by laminating them by providing a gap between the member and the member via a spacer or the like. However, the functional porous body formed by using the gel-pulverized liquid of the present invention can exhibit the same function as the air layer only by disposing the porous body at a target portion. Therefore, as described above, it is possible to more easily and simply impart the same functions as the air layer to various objects than to form the air layer.

The gel system-containing liquid system of the present invention can be used, for example, as a solution for forming the aforementioned functional porous body or as a solution for forming a low refractive layer. In the gel-containing pulverized material liquid of the present invention, the porous body is a pulverized material.

In the gel-containing pulverized material liquid of the present invention, the volume average particle diameter range of the pulverized material (particles of the porous body gel) is, for example, 10 to 1000 nm, 100 to 500 nm, and 200 to 300 nm. The above-mentioned volume average particle diameter indicates a particle size deviation of the above-mentioned pulverized material in the gel-containing pulverized liquid of the present invention. The volume average particle diameter is the same as that described above, and it can be performed, for example, by a particle size distribution evaluation device such as a dynamic light scattering method or a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Determination.

In the gel-containing pulverized material liquid of the present invention, the gel concentration of the pulverized material is not particularly limited. For example, particles having a particle size of 10 to 1000 nm occupy 2.5 to 4.5% by weight, 2.7 to 4.0% by weight, and 2.8 to 3.2% by weight. %.

In the gel-containing liquid of the present invention, the gel (for example, a porous body gel) is not particularly limited, and examples thereof include a silicon compound.

The silicon compound is not particularly limited, and examples thereof include a silicon compound containing at least a trifunctional saturated bond functional group. The aforementioned “functional group containing a saturated bond with a trifunctional or less function” means that the silicon compound has 3 or less functional groups, and these functional groups form a saturated bond with silicon (Si).

The silicon compound is, for example, a compound represented by the following formula (2).

[Chemical Formula 1] In the foregoing formula (2), for example, X is 2, 3, or 4, R ¹ and R ² are each a linear or branched alkyl group, R ¹ and R ² may be the same or different, and X is 2 In this case, R ¹ may be the same as or different from each other, and R ² may be the same or different from each other.

The X and R ^{1 are,} for example, the same as X and R ^{1 in the} formula (1). The R ² can be exemplified by R ¹ in the formula (1) described later.

Specific examples of the silicon compound represented by the formula (2) include compounds represented by the following formula (2 ′) in which X is 3. In the following formula (2 '), R ¹ and R ² are the same as those in the formula (2). When R ¹ and R ² are methyl, the silicon compound is trimethoxy (methyl) silane (hereinafter also referred to as “MTMS”).

[Chemical Formula 2] In the gel-containing pulverized material liquid of the present invention, the pulverized material concentration of the porous body gel in the solvent is not particularly limited, and is, for example, 0.3 to 50% (v / v), 0.5 to 30% (v / v). v), 1.0 to 10% (v / v). If the concentration of the pulverized material is too high, for example, the fluidity of the gel-containing pulverized material liquid may be significantly reduced, which may cause coagulation or coating marks during coating. On the other hand, if the concentration of the pulverized material is too low, for example, not only does it take a considerable amount of time to dry the solvent, but also the residual solvent immediately after drying also increases, and the porosity may decrease.

The physical properties of the liquid containing the pulverized gel of the present invention are not particularly limited. The shear viscosity of the gel-containing pulverized material is, for example, 1 mPa‧s to 1 Pa‧s, 1 mPa‧s to 500 mPa‧s, 1 mPa‧s to 50 mPa‧s, 1 mPa at a shear rate of 1000 l / s. ‧S to 30mPa‧s, 1mPa‧s to 10mPa‧s, 10mPa‧s to 1Pa‧s, 10mPa‧s to 500mPa‧s, 10mPa‧s to 50mPa‧s, 10mPa‧s to 30mPa‧s, 30mPa‧s The range is from 1Pa‧s, 30mPa‧s to 500mPa‧s, 30mPa‧s to 50mPa‧s, 50mPa‧s to 1Pa‧s, 50mPa‧s to 500mPa‧s, or 500mPa‧s to 1Pa‧s. If the shear viscosity is too high, for example, coating marks may be generated, and defects such as a reduction in the transfer rate of gravure coating may occur. Conversely, if the shear viscosity is too low, for example, the thickness of the wet coating during coating may not be increased, and the desired thickness may not be obtained after drying.

In the liquid containing the pulverized gel of the present invention, the solvent may be, for example, a dispersion medium. The dispersion medium (hereinafter also referred to as "coating solvent") is not particularly limited, and examples thereof include a gelling solvent and a pulverizing solvent described later, and the pulverizing solvent is preferably used. The coating solvent includes an organic solvent having a boiling point of 70 ° C. or higher and lower than 180 ° C. and a saturated vapor pressure at 20 ° C. of 15 kPa or less.

Examples of the organic solvent include carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, isobutanol, isopropanol, isoamyl alcohol, 1 -Pentyl alcohol (butyl methanol), ethanol (alcohol), ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, Xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, cyclohexanol, cyclohexanone 1,4-two Alkane, N, N-dimethylformamide, styrene, tetrachloroethylene, 1,1,1-trichloroethane, toluene, 1-butanol, 2-butanol, methyl isobutyl ketone, Methyl ethyl ketone, methyl cyclohexane, methyl cyclohexanone, methyl-n-butyl ketone, isoamyl alcohol, and the like. In addition, the dispersion medium may contain an appropriate amount of a perfluoro-based surfactant, a silicon-based surfactant, or the like that reduces the surface tension.

The gel-containing pulverized substance liquid of the present invention may be, for example, a sol particle liquid, that is, the pulverized substance in the form of a sol dispersed in the dispersion medium. The liquid system containing the pulverized gel of the present invention can be formed into a void layer having a strength of a certain level or more continuously by coating and drying the substrate, and then performing chemical crosslinking through a bonding step described later. In addition, the "sol" in the present invention refers to a state where the three-dimensional structure of the gel is pulverized, and the pulverized material (particles of a porous body sol that maintains a nano-dimensional three-dimensional structure with a partial void structure) is dispersed in a solvent to exhibit fluidity .

The pulverized gel-containing liquid of the present invention may further contain, for example, a catalyst for chemically bonding the pulverized gels. The content rate of the catalyst is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the pulverized gel.

In addition, the gel-pulverized material-containing liquid of the present invention may further contain, for example, a crosslinking auxiliary agent for indirectly bonding the gel-pulverized materials to each other. The content rate of the said crosslinking adjuvant is not specifically limited, For example, it is 0.01 to 20 weight%, 0.05 to 15 weight%, or 0.1 to 10 weight% with respect to the weight of the said crushed gel.

In addition, in the liquid containing the pulverized gel of the present invention, among the functional groups of the constituent units of the gel, the functional group ratio that is not beneficial to the cross-linked structure in the gel may be, for example, 30 mol% or less, 25 mol% or less, 20 mol% or less, 15 mol% or less, and may be, for example, 1 mol% or more, 2 mol% or more, 3 mol% or more, and 4 mol% or more. The ratio of functional groups that is not beneficial to the cross-linked structure in the gel can be measured, for example, as follows.

(Measurement method of functional group ratio that is not conducive to cross-linking structure in the gel) After drying the gel, the solid state NMR (Si-NMR) is measured, and the residual silanol groups that are not conducive to the cross-linking structure are calculated from the peak ratio of NMR. The ratio of the functional groups of the crosslinked structure within the gel. When the functional group is other than a silanol group, the ratio of the functional group that is not beneficial to the crosslinked structure in the gel can be calculated from the NMR peak ratio according to this method.

The following is an example to explain the method for producing the gel-containing liquid of the present invention. Unless otherwise stated, the gel-containing pulverized liquid of the present invention can be referred to the following description.

In the method for producing a pulverized gel-containing liquid of the present invention, the mixing step is a step of mixing the particles (pulverized material) of the porous gel with the solvent, and it is optional. Specific examples of the aforementioned mixing step include a step of mixing a pulverized substance of a gel-like silicon compound (silicon compound gel) with a dispersion medium, and the pulverized substance of the aforementioned silicon compound gel is obtained from a substance containing at least three functions Saturated bond functional silicon compounds. In the present invention, the pulverized material of the porous body gel can be obtained from the porous body gel by a gel pulverization step described later. The pulverized product of the porous body gel can be obtained, for example, from the porous body gel that has been subjected to a aging process described later.

In the method for producing a gel-containing pulverized product of the present invention, the gelation step is, for example, a step of gelatinizing a porous body in a solvent into the aforementioned porous body gel, and a specific example of the aforementioned gelation step, For example, this step is a step of gelling a silicon compound containing a saturated bond functional group having at least three functions in a solvent to form a silicon compound gel.

Hereinafter, the case where the porous body is a silicon compound will be described as an example to explain the gelation step.

The gelation step is, for example, a step of gelling the silicon compound of the monomer by a dehydration condensation reaction in the presence of a dehydration condensation catalyst, thereby obtaining a silicon compound gel. The silicon compound gel system has, for example, a residual silanol group, and the residual silanol group should be appropriately adjusted so as to correspond to the chemical bonding between the pulverized products of the silicon compound gel described later.

In the aforementioned gelation step, the aforementioned silicon compound is not particularly limited as long as it can be gelated by a dehydration condensation reaction. By the aforementioned dehydration condensation, for example, the aforementioned silicon compounds are combined. The aforementioned bonding between silicon compounds is, for example, hydrogen bonding or intermolecular force bonding.

Examples of the silicon compound include a silicon compound represented by the following formula (1). Since the silicon compound of the formula (1) has a hydroxyl group, the silicon compound of the formula (1) may, for example, form a hydrogen bond or an intermolecular force bond through the respective hydroxyl group.

[Chemical Formula 3]

In the formula (1), for example, X is 2, 3, or 4, and R ¹ is a linear or branched alkyl group. The carbon number of the aforementioned R ¹ is, for example, 1 to 6, 1 to 4, or 1 to 2. Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl, and examples of the branched alkyl group include isopropyl and isobutyl. The X is, for example, 3 or 4.

Specific examples of the silicon compound represented by the aforementioned formula (1) include compounds represented by the following formula (1 ′) in which X is 3. In the following formula (1 ′), R ^{1 is the} same as the aforementioned formula (1), and is, for example, a methyl group. When R ¹ is a methyl group, the silicon compound is ginsyl (hydroxy) methyl silane. When X is 3, the silicon compound is, for example, a trifunctional silane having three functional groups.

[Chemical Formula 4]

Specific examples of the silicon compound represented by the formula (1) include compounds in which X is 4. In this case, the silicon compound is, for example, a tetrafunctional silane having four functional groups.

The silicon compound may be, for example, a precursor that forms the silicon compound of the formula (1) by hydrolysis. The precursor may be, for example, one that can form the silicon compound by hydrolysis, and a specific example is a compound represented by the formula (2).

When the silicon compound is a precursor represented by the formula (2), the manufacturing method of the present invention may include, for example, a step of hydrolyzing the precursor before the gelation step.

The aforementioned method of hydrolysis is not particularly limited, and may be performed, for example, by a chemical reaction in the presence of a catalyst. Examples of the catalyst include acids such as oxalic acid and acetic acid. The hydrolysis reaction proceeds, for example, at room temperature, an aqueous solution of oxalic acid is slowly dropped into the dimethylarsin solution of the silicon compound precursor, and the state is maintained for about 30 minutes. When hydrolyzing the aforementioned silicon compound precursor, for example, the alkoxy group of the aforementioned silicon compound precursor can be completely hydrolyzed in order to more efficiently exhibit subsequent gelation, maturation, and heating / fixation after formation of the void structure.

In the present invention, the silicon compound is, for example, a hydrolyzate of trimethoxy (methyl) silane.

The silicon compound of the aforementioned monomer is not particularly limited, and can be appropriately selected according to the purpose of the functional porous body to be produced, for example. In the production of the functional porous body, for example, in the case where the silicon compound emphasizes low refractive index properties, the trifunctional silane is preferred from the viewpoint of excellent low refractive index properties, and in addition, emphasis is placed on strength ( In the case of abrasion resistance, for example, the aforementioned tetrafunctional silane is preferred from the viewpoint of abrasion resistance. The silicon compound used as the silicon compound gel raw material may be used alone, or two or more kinds may be used in combination. As a specific example, the monomeric silicon compound may contain, for example, only the trifunctional silane, only the tetrafunctional silane, or both the trifunctional silane and the tetrafunctional silane, and may further include other Silicon compounds. When two or more silicon compounds are used as the silicon compound, the ratio is not particularly limited and can be appropriately set.

The gelation of the porous body such as the silicon compound can be performed, for example, by a dehydration condensation reaction between the porous bodies. The dehydration condensation reaction is preferably performed in the presence of a catalyst. The catalyst may be, for example, an acid catalyst and an alkaline catalyst, such as hydrochloric acid, oxalic acid, sulfuric acid, etc., and the alkaline catalyst. There are ammonia, potassium hydroxide, sodium hydroxide, and ammonium hydroxide. The dehydration condensation catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferred. In the aforementioned dehydration condensation reaction, the amount of the catalyst added to the porous body is not particularly limited, and the catalyst is, for example, 1 to 10 moles, 0.05 to 7 moles, and 0.1 to 1 mole of the porous body. To 5 moles.

The gelation of the porous body such as the silicon compound is preferably performed in a solvent, for example. The proportion of the porous body in the solvent is not particularly limited. Examples of the aforementioned solvent include dimethylsulfinium (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), γ- Butyrolactone (GBL), acetonitrile (MeCN), ethylene glycol ethyl ether (EGEE), etc. The said solvent system may be 1 type, and may use 2 or more types together, for example. The solvent used for the above-mentioned gelation is hereinafter also referred to as a "solvent for gelation".

The conditions for the aforementioned gelation are not particularly limited. The processing temperature of the solvent containing the porous body is, for example, 20 to 30 ° C, 22 to 28 ° C, or 24 to 26 ° C, and the processing time is, for example, 1 to 60 minutes, 5 to 40 minutes, or 10 to 30 minutes. When the aforementioned dehydration condensation reaction is performed, the treatment conditions are not particularly limited, and the exemplified conditions may be used. By performing the aforementioned gelation, in the case where the porous body is a silicon compound, for example, a siloxane bond will grow to form the original particles of the silicon compound, and by the reaction proceeding, the original particles will be Connects into a rosary and produces a three-dimensional structured gel.

The gel morphology of the porous body obtained in the gelation step is not particularly limited. Generally speaking, "gel" refers to a structure in which solutes have agglomerates that have lost their independent motility due to interactions, and have a solidified state. In addition, among the gels, generally, a wet gel refers to a person that contains a dispersion medium and has the same structure in the solute, and a xerogel refers to a solvent that removes the solvent and has a mesh structure with voids. In the present invention, the silicon compound gel is preferably a wet gel, for example. When the porous body gel is a silicon compound gel, the residual silanol group of the silicon compound gel is not particularly limited, and, for example, the remaining silanol group may be exemplified in a range described later.

The porous body gel obtained by the gelation may be directly supplied to the solvent replacement step and the first pulverization step, or the aging treatment in the aging step may be performed before the first pulverization step. . The maturing step is a step of maturing the gelled porous body (porous body gel) in a solvent. In the maturing step, the conditions for the maturing treatment are not particularly limited, and for example, the porous body gel may be cultured in a solvent at a predetermined temperature. According to the aforementioned aging treatment, for example, for a porous body gel having a three-dimensional structure obtained by gelation, the original particles can be further grown, thereby increasing the size of the particles themselves. Then, as a result, the neck contact state in which the aforementioned particles are in contact with each other can be increased from, for example, point contact to surface contact. The porous body gel subjected to the above-mentioned maturing treatment has its own strength, for example, and as a result, the strength of the three-dimensional structure of the pulverized material after pulverization can be further improved. Thereby, when the coating film is formed using the gel-containing pulverized substance liquid of the present invention, for example, it is possible to suppress the following cases: in the drying step after coating, the pores of the void structure of the three-dimensional basic structure are piled up. The size shrinks with the evaporation of the solvent in the coating film produced in the drying step.

The lower limit of the temperature for the ripening process is, for example, 30 ° C or higher, 35 ° C or higher, and 40 ° C or higher. The upper limits are, for example, 80 ° C or lower, 75 ° C or lower, and 70 ° C or lower. The ranges are, for example, 30 to 80 ° C, 35 to 75 ° C, 40 ~ 70 ℃. The aforementioned predetermined time is not particularly limited, and its lower limit is, for example, 5 hours or more, 10 hours or more, 15 hours or more, and its upper limit is, for example, 50 hours or less, 40 hours or less, and 30 hours or less, and its range is, for example, 5 to 50 hours, 10 To 40 hours, 15 to 30 hours. In addition, as for the most suitable conditions for the ripening, for example, the conditions for setting the size of the primary particles in the porous body gel to be increased and the neck contact area to be increased as described above are suitable. Moreover, in the said aging process, the temperature of the said aging process is the method which considered the boiling point of the solvent used, for example. For example, if the maturing temperature is too high, the coating solution may be concentrated due to excessive volatilization of the solvent, which may cause problems such as pores of the three-dimensional void structure being closed. On the other hand, if the ripening temperature is too low, for example, if the ripening temperature is too low, the effects brought about by the ripening cannot be fully obtained, the temperature deviation over time during the mass production process will increase, and products of poor quality will be produced. Possibility.

The ripening treatment system may use, for example, the same solvent as the gelation step, and specifically, it is preferable to directly process the reactant after the gelation treatment (that is, the solvent containing the porous gel). . In the case where the porous body gel is the silicon compound gel, the number of residual silanol groups contained in the silicon compound gel after the gelation and curing treatment is completed, for example, when the gel is used for gelation. The molar number of alkoxy groups of raw materials (such as the aforementioned silicon compounds or their precursors) is defined as the proportion of residual silanol groups at 100, and the lower limit is, for example, 50% or more, 40% or more, and 30% or more. The upper limit is, for example, It is 1% or less, 3% or less, and 5% or less, and the ranges are, for example, 1 to 50%, 3 to 40%, and 5 to 30%. For the purpose of increasing the hardness of the aforementioned silicon compound gel, for example, the lower the mole number of the residual silanol group, the better. When the molar number of the residual silanol group is too high, for example, when the functional porous body is formed, there is a possibility that the void structure cannot be maintained until the precursor of the functional porous body is crosslinked. On the other hand, if the molar number of the residual silanol group is too low, for example, in the bonding step, the precursor of the functional porous body may not be crosslinked, and sufficient film strength may not be provided. In addition, although the above is an example of a residual silanol group, for example, when the silicon compound modified with various reactive functional groups is used as a raw material of the silicon compound gel, the same phenomenon can be applied to each functional group.

The porous body gel obtained by the gelation may be subjected to, for example, the aging process, the solvent replacement step, and the pulverization step thereafter. The solvent replacement step is to replace the solvent with another solvent.

In the present invention, the pulverizing step is a step of pulverizing the porous body gel as described above. The pulverization may be performed, for example, on the porous body gel after the gelation step, and may also be performed on the porous body gel that has undergone the aging treatment.

In addition, as described above, before the solvent replacement step (for example, after the ripening step), a gel shape control step that controls the shape and size of the gel may be performed first. The shape and size of the gel to be controlled in the gel morphology controlling step are not particularly limited, and are the same as those described above, for example. The gel morphology control step can be performed, for example, by dividing (for example, cutting) the gel into three-dimensional objects (three-dimensional bodies) of an appropriate size and shape.

Further, as described above, the pulverization step is performed after the gel replacement step is performed on the gel. The solvent replacement step is to replace the solvent with another solvent. This is because if the aforementioned solvent is not replaced with the aforementioned other solvent, for example, the catalyst and solvent used in the gelation step will remain after the aforementioned ripening step, which may further cause gelation over time and affect the final result. The shelf life of the obtained gel-containing pulverized substance-containing liquid may reduce the drying efficiency of the coating film formed by using the gel-containing pulverized substance-containing liquid during drying. The other solvents in the gel pulverizing step are hereinafter also referred to as "solvents for pulverization".

The aforementioned pulverizing solvent (other solvents) is not particularly limited, and for example, an organic solvent can be used. Examples of the organic solvent include solvents having a boiling point of 140 ° C or lower, 130 ° C or lower, a boiling point of 100 ° C or lower, and a boiling point of 85 ° C or lower. Specific examples include, for example, isopropyl alcohol (IPA), ethanol, methanol, n-butanol, 2-butanol, isobutanol, pentyl alcohol, propylene glycol monomethyl ether (PGME), methylcellulose, and acetone. Wait. The pulverization solvent may be used singly or in combination of two or more kinds.

Further, in the case where the solvent for pulverization is low in polarity, for example, the solvent replacement step may be divided into a plurality of solvent replacement steps, and in the solvent replacement step, the hydrophilicity of the other solvents in the subsequent steps may be made hydrophilic. Sex is lower than the first stage. In this way, for example, the efficiency of solvent replacement is improved, and the residual amount of the gel-producing solvent (for example, DMSO) in the gel can be extremely low. As a specific example, for example, the solvent replacement step can be divided into three solvent replacement stages. First, the DMSO in the gel is replaced with water in the first solvent replacement stage, and then the aforementioned in the gel is replaced in the second solvent replacement stage. Water was replaced with IPA, and the aforementioned IPA in the gel was replaced with isobutanol in the third replacement stage.

The combination of the gelling solvent and the pulverizing solvent is not particularly limited, and examples thereof include a combination of DMSO and IPA, a combination of DMSO and ethanol, a combination of DMSO and isobutanol, a combination of DMSO and n-butanol, and the like. In this way, by changing the solvent for gelation to the solvent for pulverization, for example, a relatively uniform coating film can be formed in the coating film formation described later.

The said solvent replacement process is not specifically limited, For example, it can perform as follows. That is, first, a gel produced by the aforementioned gel manufacturing step (for example, the gel after the aging treatment) is immersed in or brought into contact with the other solvent, and the gel in the gel is dissolved in the other solvent. A catalyst, an alcohol component produced by a condensation reaction, water, and the like are used. Then, the solvent impregnated or contacted with the aforementioned gel is removed, and the aforementioned gel is impregnated with or brought into contact with a new solvent again. This is repeated until the residual amount of the gel-producing solvent in the gel reaches a desired amount. The immersion time per time is, for example, 0.5 hours or more, 1 hour or more, or 1.5 hours or more. The upper limit 値 is not particularly limited, and is, for example, 10 hours or less. The solvent impregnation may correspond to the continuous contact of the solvent with the gel. The temperature during the dipping is not particularly limited, and may be, for example, 20 to 70 ° C, 25 to 65 ° C, or 30 to 60 ° C. Once the heating is performed, the solvent replacement is accelerated, and the amount of the solvent required for the replacement is reduced. However, the solvent replacement may be easily performed at room temperature. For example, when the solvent replacement step is divided into a plurality of solvent replacement steps, the plurality of solvent replacement steps may be performed as described above.

In addition, for example, the aforementioned solvent replacement step may be divided into a plurality of solvent replacement stages, and the hydrophilicity of the aforementioned other solvents in the later stage may be lower than that in the earlier stage. In this way, by gradually changing the solvent for replacement (the other solvents mentioned above) from a solvent with a high hydrophilicity to a solvent with a low hydrophilicity (high hydrophobicity), the residual amount of the solvent for producing a gel in the gel can be changed. Very low. If this is done, a void layer having a higher porosity (for example, a lower refractive index) can be produced.

The residual amount of the solvent for producing the gel in the gel after the solvent replacement step has been performed is preferably 0.005 g / ml or less, more preferably 0.001 g / ml or less, and even more preferably 0.0005 g / ml or less. The lower limit of the residual amount of the residual amount of the solvent for producing a gel in the gel is not particularly limited, and is, for example, zero, or less than or lower than the detection limit.

The residual amount of the solvent for producing a gel in the gel after the solvent replacement step has been performed can be measured, for example, in the following manner.

(Method for measuring the remaining amount of a solvent for producing a gel in a gel) 0.2 g of the gel was added, and 10 ml of acetone was added, and the mixture was shaken at 120 rpm for 3 days at room temperature to perform extraction. 1 μl of the extract was injected into a gas chromatograph (manufactured by Aglent, trade name 7890A) and analyzed. In addition, in order to confirm the reproducibility of the measurement, for example, the measurement can be performed by sampling at a measurement number of n = 2 (the number of measurement times twice) or more. Then, a calibration curve was prepared from the standard product, and the amount of each component per 1 g of the gel was calculated, and the remaining amount of the gel-producing solvent per 1 g of the gel was calculated.

When the solvent replacement step is performed by dividing into a plurality of solvent replacement steps, and the hydrophilicity of the other solvent in the subsequent step is lower than that in the first step, the other solvent (the solvent for replacement) is not particularly limited. In the aforementioned solvent replacement step, the other solvent (solvent for replacement) is preferably a solvent for producing a void layer. Examples of the solvent for producing the void layer include solvents having a boiling point of 140 ° C or lower. Examples of the solvent for producing the void layer include alcohols, ethers, ketones, ester solvents, aliphatic hydrocarbon solvents, and aromatic solvents. Specific examples of alcohols having a boiling point of 140 ° C or lower include, for example, isopropyl alcohol (IPA), ethanol, methanol, n-butanol, 2-butanol, isobutanol (IBA), 1-pentanol, and 2-pentanol. Wait. Specific examples of the ether having a boiling point of 140 ° C or lower include propylene glycol monomethyl ether (PGME), methylcellulose, and ethylcellulose. Specific examples of the ketone having a boiling point of 140 ° C. or lower include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone. Specific examples of the ester-based solvent having a boiling point of 140 ° C. or lower include, for example, ethyl acetate, butyl acetate, isopropyl acetate, and n-propyl acetate. Specific examples of the aliphatic hydrocarbon-based solvent having a boiling point of 140 ° C. or lower include, for example, hexane, cyclohexane, heptane, and octane. Specific examples of the aromatic solvent having a boiling point of 140 ° C or lower include toluene, benzene, xylene, and anisole. In coating, from the viewpoint of not easily attacking the substrate (for example, a resin film), the solvent for producing the void layer is preferably an alcohol, an ether, or an aliphatic hydrocarbon-based solvent. Moreover, the said pulverization solvent system may be 1 type, and may use 2 or more types together, for example. Especially isopropyl alcohol (IPA), ethanol, n-butanol, 2-butanol, isobutanol (IBA), amyl alcohol, propylene glycol monomethyl ether (PGME), methylcellulose, heptane, octane In terms of low volatility at room temperature, this aspect is suitable. In particular, in order to suppress the scattering of gel material particles (for example, a silicon oxide compound), the saturation vapor pressure of the solvent for producing the interstitial layer should not be too high (the volatility is not too high). Such a solvent is preferably a solvent having an aliphatic group having 3 or more carbon atoms, for example, and a solvent having an aliphatic group of 4 or more carbon atoms is preferred. The aforementioned solvent having an aliphatic group having 3 or 4 carbon atoms may be, for example, an alcohol. Such solvents are specifically, for example, isopropyl alcohol (IPA), isobutanol (IBA), n-butanol, 2-butanol, 1-pentanol, 2-pentanol, and particularly preferably isobutanol ( IBA).

The other solvents (solvent for replacement) other than the solvent replacement step performed last are not particularly limited, and examples thereof include alcohols, ethers, and ketones. Specific examples of the alcohol include isopropyl alcohol (IPA), ethanol, methanol, n-butanol, 2-butanol, isobutanol (IBA), and pentanol. Specific examples of the ether include propylene glycol monomethyl ether (PGME), methylcellulose, and ethylcellulose. Specific examples of the ketone include acetone. The other solvent (solvent for replacement) may be substituted for the solvent for gel production or the other solvent (solvent for replacement) in the previous stage. In addition, the other solvents (replacement solvents) other than the solvent replacement stage performed last are preferably solvents that do not remain in the gel eventually, or that they do not easily attack the substrate (such as a resin film) even if they remain. Solvent. From the viewpoint that the substrate is not easily eroded during coating, the other solvents (replacement solvents) other than the solvent replacement stage performed last are preferably alcohols. In this way, it is preferable to use alcohol as the other solvent in at least one of the plurality of solvent replacement stages.

In the aforementioned solvent replacement stage performed initially, the aforementioned other solvent may be, for example, water or a mixed solvent containing water at an arbitrary ratio. If it is water or a mixed solvent containing water, since it has high compatibility with a highly hydrophilic gel-producing solvent (for example, DMSO), it is easy to replace the above-mentioned gel-producing solvent, and it is also excellent in terms of cost.

The plurality of solvent replacement stages may include a stage in which the other solvent is water, a stage in which the other solvent is a solvent having an aliphatic group having a carbon number of 3 or less, and a stage in which the other solvent is a carbon Stages of 4 or more aliphatic solvent. In addition, at least one of the solvent having an aliphatic group with a carbon number of 3 or less and the solvent having an aliphatic group with a carbon number of 4 or more may be an alcohol. The alcohol having an aliphatic group having a carbon number of 3 or less is not particularly limited, and examples thereof include isopropyl alcohol (IPA), ethanol, methanol, and n-propanol. The alcohol having an aliphatic group having 4 or more carbon atoms is not particularly limited, and examples thereof include n-butanol, 2-butanol, isobutanol (IBA), and pentanol. For example, the aforementioned solvent having an aliphatic group with a carbon number of 3 or less may be isopropanol, and the aforementioned solvent having an aliphatic group with a carbon number of 4 or more may be isobutanol.

The present inventors, for example, have found that it is important to focus on the remaining amount of the above-mentioned gel-forming solvent in order to form a void layer having film strength under relatively mild conditions of 200 ° C or lower. This knowledge has not been found in the prior art, including the aforementioned patent documents and non-patent literatures, but is a knowledge discovered by the present inventors and others alone.

In this way, the reason (mechanism) for producing a low-refractive void layer by reducing the remaining amount of the gel-producing solvent in the gel is still unknown, but it is speculated as follows, for example. That is, as described above, a solvent for producing a gel is preferably a high-boiling-point solvent (for example, DMSO) because the gelation reaction proceeds. In addition, when the sol solution made of the gel is coated and dried to produce a void layer, it is difficult to dissolve the high-boiling-point solvent at a general drying temperature and drying time (not specifically limited, for example, 1 minute at 100 ° C., etc.). Remove completely. If the drying temperature is too high or the drying time is too long, problems such as deterioration of the substrate may occur. It can be speculated that the high-boiling-point solvent remaining during the coating and drying will enter between the pulverized materials of the gel and cause the pulverized materials to slide with each other, resulting in the pulverized materials being closely packed with each other and reducing the porosity, so it is difficult Exhibits a low refractive index. That is to say, if the remaining amount of the high-boiling-point solvent is reduced on the contrary, such a phenomenon can be suppressed and a low refractive index can be exhibited. However, these are only examples of the speculative mechanism and do not limit the present invention in any way.

In the present invention, the "solvent" (for example, a solvent for producing a gel, a solvent for producing a void layer, a solvent for replacement, etc.) may not dissolve the gel or its pulverized substance, and may be, for example, the gel or its pulverized substance. Etc. dispersed or precipitated in the aforementioned solvent.

The solvent for producing the gel is as described above, and the boiling point may be, for example, 140 ° C or higher.

The solvent for producing the gel is, for example, a water-soluble solvent. In the present invention, the "water-soluble solvent" refers to a solvent that can be mixed with water at an arbitrary ratio.

When the aforementioned solvent replacement step is divided into a plurality of solvent replacement steps, the method is not particularly limited, and each solvent replacement step can be performed, for example, as follows. That is, the gel is first immersed or contacted with the other solvent, and the gel production catalyst in the gel, an alcohol component produced by the condensation reaction, water, and the like are dissolved in the other solvent. Then, the solvent impregnated or contacted with the aforementioned gel is removed, and the aforementioned gel is impregnated with or brought into contact with a new solvent again. This is repeated until the residual amount of the gel-producing solvent in the gel reaches a desired amount. The immersion time per time is, for example, 0.5 hours or more, 1 hour or more, or 1.5 hours or more. The upper limit 値 is not particularly limited, and is, for example, 10 hours or less. The solvent impregnation may correspond to the continuous contact of the solvent with the gel. The temperature during the dipping is not particularly limited, and may be, for example, 20 to 70 ° C, 25 to 65 ° C, or 30 to 60 ° C. Once the heating is performed, the solvent replacement is accelerated, and the amount of the solvent required for the replacement is reduced. However, the solvent replacement may be easily performed at room temperature. This solvent replacement step is performed multiple times, and the other solvent (the solvent for replacement) is gradually changed from a solvent having a high hydrophilicity to a solvent having a low hydrophilicity (high hydrophobicity). In order to remove a highly hydrophilic gel-producing solvent (for example, DMSO), for example, it is simple and efficient to use water as the solvent for replacement as described above. After removing DMSO and the like with water, the water in the gel is replaced in the order of, for example, isopropyl alcohol ⇒ isobutanol (solvent for coating). That is, since water has low compatibility with isobutanol, by replacing isopropyl alcohol once and then replacing with isobutanol as a coating solvent, solvent replacement can be performed efficiently. However, this is only an example, and as mentioned above, the other solvents (replacement solvents) are not particularly limited.

In the present invention, the method for producing the gel is as described above, and the solvent replacement stage may be performed multiple times, and the other solvent (solvent for replacement) may be slowly changed from a solvent with high hydrophilicity to a solvent with low hydrophilicity (high hydrophobicity). ) Solvent. By doing so, as described above, the residual amount of the gel-producing solvent in the gel can be extremely low. In addition, for example, the solvent amount can be reduced to a very low level and the cost can be reduced as compared with using only a solvent for coating in one stage.

Then, after the solvent replacement step, the gel is pulverized in the pulverization solvent to perform a gel pulverization step. For another example, as described above, after the solvent replacement step, the gel concentration measurement may be performed as required before the gel pulverization step, and the gel concentration adjustment step may be performed after that if necessary. The measurement of the gel concentration before the gel pulverization step after the solvent replacement step can be performed, for example, in the following manner. That is, first, after the solvent replacement step, the gel is taken out of the other solvent (solvent for pulverization). This gel is, for example, a gel block controlled to have an appropriate shape and size (for example, a block shape) by the gel shape control step. Next, the solvent adhering to the periphery of the gel block was removed, and then the solid content concentration in one gel block was measured by a weight drying method. At this time, in order to obtain the reproducibility of the measurement radon, the measurement is performed with a plurality of (for example, six) gel pieces taken out randomly, and the deviation between the average radon and the radon is calculated. The concentration adjustment step can reduce the gel concentration of the gel-containing liquid by, for example, further adding the other solvent (solvent for pulverization). In addition, the concentration adjustment step may conversely increase the gel concentration of the gel-containing liquid by evaporating the other solvent (solvent for pulverization).

The method for producing a gel-pulverized liquid according to the present invention is as described above, and the gel pulverization step may be performed in one stage or may be divided into a plurality of pulverization stages. Specifically, for example, the first pulverization stage and the second pulverization stage may be performed. The gel pulverization step may be performed in addition to the first pulverization step and the second pulverization step. That is, in the manufacturing method of the present invention, the gel pulverization step is not limited to the two-stage pulverization stage, and may include three or more pulverization stages.

Hereinafter, the first pulverization stage and the second pulverization stage will be described.

The first pulverization step is a step of pulverizing the porous body gel. The second pulverization step is a step of further pulverizing particles of the porous body gel after the first pulverization step.

The particle volume average particle diameter of the porous body gel obtained in the first pulverizing step and the particle volume average particle diameter of the porous body gel obtained in the second pulverizing step are, for example, the same as described above. The method for measuring the volume average particle diameter is, for example, the same as described above.

The shear viscosity of the gel-pulverized material-containing liquid immediately after the first pulverization stage and immediately after the second pulverization stage are as described above. The method for measuring the shear viscosity is, for example, the same as described above.

In addition, for example, as described above, the gel concentration of the gel-containing liquid can be measured immediately after the first pulverization stage, and only the liquid whose gel concentration is within a predetermined range is supplied to the second pulverization stage. This performs the concentration control of the aforementioned gel-containing liquid.

The method for pulverizing the porous body gel is not particularly limited. For example, a high-pressure medium-free pulverizer, an ultrasonic homogenizer, a high-speed rotating homogenizer, a high-pressure extrusion pulverizer, and a wet-type medium-free pulverizer using other cavitation phenomena And so on. The first pulverization stage and the second pulverization stage may be performed by the same pulverization method or different pulverization methods, but it is preferable to implement pulverization methods different from each other.

As the pulverization method, it is preferable to perform at least one of the first pulverization step and the second pulverization step by a method of pulverizing the porous body gel by controlling energy. The method of pulverizing the porous body gel by controlling energy may be a method performed by a high-pressure medium-free pulverizing device or the like.

Although the method for pulverizing the porous body gel by ultrasonic waves has strong pulverization strength, it is difficult to control (monitor) the degree of pulverization. In contrast, if the porous body gel is pulverized by controlling energy, the pulverization can be performed while controlling (monitoring) the pulverization. Thereby, a uniform gel-containing pulverized liquid can be produced in a limited workload. Therefore, the above-mentioned gel-containing pulverized liquid can be produced on a mass production basis, for example.

Compared to a device for pulverizing a medium, such as a ball mill that physically destroys the gel structure during pulverization, a cavitation pulverizing device such as a homogenizer can use a medium-free method, for example, so that the three-dimensional structure of the gel can be encapsulated. The porous particles have a relatively weak binding force, and they are peeled off with high-speed shear stress. In this way, a new sol three-dimensional structure is obtained by pulverizing the porous body gel. The three-dimensional structure can maintain a void structure with a certain range of particle size distribution when forming a coating film, and can be formed again by coating and drying. The void structure obtained from the accumulation of time. The aforementioned pulverization conditions are not particularly limited, and for example, it is preferable to pulverize the gel in such a manner that the solvent is not volatilized by instantaneously imparting a high-speed flow. For example, it is preferable to grind | pulverize so that it may become the grind | pulverized material of the particle size deviation (for example, volume average particle diameter or particle size distribution) as mentioned above. It is assumed that when the workload such as pulverization time and strength is insufficient, for example, coarse particles may remain, dense pores may not be formed, appearance defects may increase, and high quality may not be obtained. On the other hand, when the workload is excessive, for example, sol particles may be formed with a finer particle size distribution than desired, and the size of the voids formed after coating and drying may become fine, and the desired void ratio may not be achieved.

In at least one of the first pulverization stage and the second pulverization stage, it is preferable to control the pulverization of the porous body while measuring the shear viscosity of the liquid. Specific methods include, for example, a method of adjusting a sol solution having desired shear viscosity and excellent uniformity at the midway stage of the aforementioned pulverization phase, monitoring the shear viscosity of the liquid in-line, and feeding back to the foregoing Method of crushing stage. This makes it possible to produce a gel-containing pulverized liquid having both a desired shear viscosity and extremely excellent uniformity. Therefore, for example, the characteristics of the aforementioned gel-containing pulverized liquid can be controlled in accordance with its use.

After the pulverization stage, when the porous body gel is the silicon compound gel, the ratio of the residual silanol groups contained in the pulverized material is not particularly limited. For example, it can be related to the silicon compound gel after the aging treatment. The ranges illustrated are the same.

In the manufacturing method of the present invention, a classification step may be performed after at least one of the above-mentioned pulverization steps (the first pulverization step and the second pulverization step). The classification step is to classify particles of the porous gel. The "classification" refers to, for example, an operation of classifying particles of the porous body gel according to the particle diameter. The classification method is not particularly limited and can be performed using a sieve. By performing the pulverization treatment in multiple stages in this way, the uniformity is extremely excellent as described above. Therefore, when used in applications such as optical parts, the appearance can be made good. By further performing a classification treatment, the appearance can be changed. Better.

After the gel pulverization step and any of the classification steps, the proportion of the pulverized material in the solvent containing the pulverized material is not particularly limited. For example, it can be exemplified in the gel pulverized material-containing liquid of the present invention described above. conditions of. The aforementioned ratio may be, for example, a condition of the solvent itself containing the pulverized substance after the gel pulverizing step, or may be adjusted before the gel pulverized substance-containing liquid is used after the gel pulverizing step. conditions of.

As described above, a liquid (for example, a suspension) containing the fine pores (a pulverized product of a gel-like compound) can be prepared. In addition, after the liquid containing the fine pore particles is prepared or during the manufacturing process, a catalyst containing the fine pore particles to chemically bond with each other can be added to prepare a liquid containing the fine pore particles and the catalyst. . The addition amount of the catalyst is not particularly limited, and may be, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight with respect to the weight of the pulverized product of the gelatinous silicon compound. The catalyst may be, for example, a catalyst that promotes cross-linking and bonding of the microporous particles. The chemical reaction for chemically combining the aforementioned fine pore particles with each other should preferably utilize a dehydration condensation reaction of the residual silanol groups contained in the silica sol molecules. By the aforementioned catalyst promoting the reaction of the hydroxyl groups of the silanol group, continuous film formation that hardens the void structure in a short time can be achieved. Examples of the catalyst include a photoactive catalyst and a thermally active catalyst. According to the photoactive catalyst, for example, in the step of forming the void layer, the fine pore particles can be chemically bonded (eg, crosslinked) to each other without relying on heating. Accordingly, for example, in the step of forming the void layer, it is difficult for the entire void layer to shrink due to heating, so that a high void ratio can be maintained. In addition, in addition to the aforementioned catalyst, a catalyst-generating substance (catalyst generating agent) may be reused or replaced with the aforementioned catalyst. For example, in addition to the aforementioned photoactive catalyst, a substance (photocatalyst generating agent) that generates a catalyst by light may be used or replaced; or in addition to the aforementioned thermally active catalyst, a catalyst generated by heat may also be used Substance (thermal catalyst generator) or replace it. The aforementioned photocatalyst generator is not particularly limited, and examples thereof include a photobase generator (a substance that generates an alkaline catalyst by irradiating light), a photoacid generator (a substance that generates an acidic catalyst by irradiating light), and the like, and a photobase The generating agent is preferred. Examples of the aforementioned photobase generator include: 9-anthrylmethyl-N, N-diethylcarbamate (9-anthrylmethyl N, N-diethylcarbamate, trade name WPBG-018), (E) -1- [3- (2-hydroxyphenyl) -2-propenyl] piperidine ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, trade name WPBG-027), 1- (Anthraquinone-2-yl) ethyl imidazole carboxylate (1- (anthraquinon-2-yl) ethyl imidazole carboxylate, trade name WPBG-140), 2-nitrophenylmethyl-4-methacryloxy Piperidine-1-carboxylic acid ester (trade name WPBG-165), 1,2-diisopropyl-3- [bis (dimethylamino) methylene] fluorene-2- (3-benzidine Propyl) propionate (trade name WPBG-266), 1,2-dicyclohexyl-4,4,5,5-tetramethylbisfluorene-n-butyltriphenylborate (trade name WPBG-300) And 2- (9-oxadibenzopiperan-2-yl) propanoic acid-1,5,7-triazabicyclo [4.4.0] dec-5-ene (Tokyo Chemical Industry Co., Ltd.), Compound containing 4-piperidinemethanol (trade name HDPD-PB100: manufactured by Heraeus) and the like. In addition, the aforementioned trade names containing "WPBG" are trade names of Wako Pure Chemical Industries, Ltd. Examples of the photoacid generator include an aromatic sulfonium salt (trade name SP-170: ADEKA), a triarylsulfonium salt (trade name CPI101A: San-Apro Ltd.), and an aromatic sulfonium salt (trade name Irgacure250: Ciba Japan). KK) and so on. The catalyst for chemically bonding the fine pore particles to each other is not limited to the photoactive catalyst and the photocatalyst generating agent, and may be, for example, a thermally active catalyst or a thermal catalyst generating agent. Examples of the catalyst for chemically bonding the fine pore particles to each other include alkaline catalysts such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid, and oxalic acid. Among them, alkaline catalysts are preferred. The catalyst or catalyst generator for chemically bonding the fine pore particles to each other is, for example, a sol particle liquid (for example, a suspension) containing the pulverized material (fine pore particles) before being coated. It is used in the manner of, or is used in the manner of mixing the catalyst or the catalyst generator into a solvent mixture. The mixed liquid is, for example, a coating liquid directly added to the sol particle liquid and dissolved, a solution in which the catalyst or catalyst generator is dissolved in a solvent, or the catalyst or catalyst generator may be dispersed in Solvent dispersion. The aforementioned solvent is not particularly limited, and examples thereof include water and a buffer solution.

In addition, for example, after the liquid containing the fine pore particles is prepared, a small amount of a high boiling point solvent can be added to the liquid containing the fine pore particles to improve the appearance of the film during coating. The amount of the high-boiling-point solvent is not particularly limited, and it is, for example, 0.05 to 0.8 times the amount, 0.1 to 0.5 times the amount, and particularly 0.15 to 0.4 times the mass ratio of the solid content of the liquid containing the fine pores. The high-boiling point solvent is not particularly limited, and examples thereof include dimethylsulfinium (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N- Methylpyrrolidone (NMP), γ-butyl lactone (GBL), ethylene glycol ethyl ether (EGEE), and the like. A solvent having a boiling point of 110 ° C or higher is particularly preferred, and is not limited to the foregoing specific examples. The above-mentioned high-boiling-point solvent is considered to function as a leveling agent when a film in which particles are formed side by side is formed. The above-mentioned high-boiling-point solvents are also preferably used in gel synthesis. However, the method of adding the aforementioned high-boiling-point solvent after preparing the liquid containing the fine pore particles after completely removing the solvent used in the synthesis can easily and effectively function, but the detailed reason is unknown. However, these mechanisms are examples and do not limit the present invention in any way.

[3. Manufacturing method of low refractive index layer and manufacturing method of adhesive sheet containing low refractive index layer] Hereinafter, the manufacturing method of the low refractive index layer of the present invention and the adhesive sheet containing low refractive index layer will be described by examples. Of manufacturing method. Hereinafter, the case where the low-refractive index layer of the present invention is a polysilicon porous body formed of a silicon compound will be mainly described. However, the low-refractive index layer of the present invention is not limited to a polysilicon porous body. In the case where the low-refractive index layer of the present invention is other than a polysilicon porous body, the following description can be used unless otherwise specified.

The method for manufacturing a low-refractive index layer of the present invention includes, for example, the following steps: a precursor forming step, which uses the gel-containing pulverized liquid of the present invention to form the low-refractive index layer precursor; And a combining step of chemically bonding the pulverized materials of the gel-containing liquid containing the precursor to the pulverized materials. The precursor may be referred to as a coating film, for example.

According to the method for producing a low-refractive index layer of the present invention, for example, a porous structure exhibiting the same function as the air layer is formed. The reason can be presumed as follows, but the present invention is not limited by this presumption. Hereinafter, a case where the low refractive index layer of the present invention is a polysilicon porous body will be described as an example.

The gel-containing pulverized liquid of the present invention used in the method for producing a polysilicone porous body is a three-dimensional structure of the gel-like silicon dioxide compound because the pulverized product containing the silicon compound gel is contained in the liquid, It is in a state of being dispersed in a three-dimensional basic structure. Therefore, in the method for manufacturing the polysilicon porous body, for example, the precursor (for example, a coating film) is formed using the gel-containing liquid, and the three-dimensional basic structure is stacked to form a void structure based on the three-dimensional basic structure. . That is, according to the method for producing a polysilicon porous body, a three-dimensional structure different from the three-dimensional structure of the silicon compound gel is formed from the pulverized material of the three-dimensional basic structure. In addition, in the method for manufacturing the polysilicon porous body, the pulverized materials are further chemically bonded to each other, so that the new three-dimensional structure is fixed. Therefore, although the aforementioned polysiloxane porous body obtained by the method for producing the aforementioned polysiloxane porous body has a structure having voids, it can still maintain sufficient strength and flexibility. The low-refractive index layer (for example, a polysilicon porous body) obtained by the present invention can be used, for example, as a member using a gap, and is widely used in heat-insulating materials, sound-absorbing materials, optical members, and ink receiving layers. Products in the field, and furthermore, laminated films having various functions can be produced.

As long as the manufacturing method of the low-refractive index layer of the present invention is not specifically described, the above description of the gel-containing pulverized liquid of the present invention can be referred to.

In the step of forming the precursor of the porous body, for example, the gel-containing pulverized material-containing liquid of the present invention is applied to the substrate. The gel-containing pulverized material liquid of the present invention is, for example, after being coated on a substrate and drying the coating film, the pulverized materials are chemically bonded (for example, cross-linked) to each other through the bonding step. A low refractive index layer having a film strength above a certain level is continuously formed.

The coating amount of the gel-containing pulverized liquid on the substrate is not particularly limited, and can be appropriately set according to the thickness of the low-refractive index layer of the present invention and the like. In a specific example, when forming the aforementioned polysiloxane porous body having a thickness of 0.1 to 1000 μm, the coating amount of the gel-containing pulverized material to the substrate is, for example, 0.01 to 60,000 μg per 1 m ^{2 of the} substrate area. , 0.1 to 5000 μg, 1 to 50 μg. The ideal coating amount of the aforementioned gel-containing pulverized liquid is related to, for example, the liquid concentration or the coating method, so it is difficult to generalize. If productivity is considered, it should be coated in a thin layer as much as possible. When the coating amount is excessive, for example, the possibility of drying in a drying furnace before the solvent is evaporated is increased. Therefore, before the nano-pulverized sol particles are deposited and accumulated in a solvent to form a void structure, the drying of the solvent may hinder the formation of voids, and the porosity may decrease significantly. On the other hand, if the coating amount is too thin, the risk of coating cissing due to unevenness of the substrate, variation in hydrophilicity and hydrophobicity, and the like may increase significantly.

After the liquid containing the pulverized gel is applied to the substrate, the precursor (coating film) of the porous body may be dried. With the aforementioned drying treatment, for example, not only the aforementioned solvent (the solvent contained in the aforementioned gel-containing liquid containing the pulverized gel) in the porous body precursor can be removed, but also the purpose is to settle and accumulate the sol particles during the drying process. A void structure is formed. The temperature of the drying process is, for example, 50 to 250 ° C, 60 to 150 ° C, or 70 to 130 ° C. The time of the drying process is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes. Regarding the drying treatment temperature and time, for example, continuous productivity or a correlation exhibiting a high porosity is preferably a lower temperature and a shorter time. If the conditions are excessively severe, for example, when the substrate is a resin film, the substrate will stretch in a drying furnace due to its approach to the glass transition temperature of the substrate, and may form voids immediately after coating. Defects such as cracks in the structure. On the other hand, if the conditions are excessively mild, residual solvents may be contained at the time of leaving the drying furnace, for example, and there may be appearance defects such as scratches when rubbing with the roller in the next step.

The drying treatment system may be, for example, natural drying, heating drying, or drying under reduced pressure. The drying method is not particularly limited, and for example, a general heating mechanism can be used. Examples of the heating means include a hot air heater, a heating roller, and a far-infrared heater. Among them, under the premise of industrial continuous production, heating and drying should be used. In addition, the solvent used is preferably a solvent having a low surface tension for the purpose of suppressing shrinkage stress caused by evaporation of the solvent during drying and cracking of the void layer (the aforementioned polysiloxane porous body) caused by the solvent. Examples of the aforementioned solvent include lower alcohols such as isopropyl alcohol (IPA), hexane, and perfluorohexane, but are not limited thereto.

The substrate is not particularly limited. For example, a substrate made of a thermoplastic resin, a substrate made of glass, an inorganic substrate typified by silicon, a plastic such as a thermosetting resin, a semiconductor element, etc. Carbon fiber materials such as rice carbon tubes are representative, but not limited thereto. Examples of the form of the substrate include a film and a plate. Examples of the thermoplastic resin include polyethylene terephthalate (PET), acrylic resin, cellulose acetate propionate (CAP), cycloolefin polymer (COP), triacetate (TAC), and polynaphthalene. Ethylene diformate (PEN), polyethylene (PE), polypropylene (PP), etc.

In the method for producing a low-refractive index layer according to the present invention, the bonding step is a step of chemically bonding the pulverized materials contained in the porous body precursor (coating film) to each other. For example, the three-dimensional structure of the pulverized material in the precursor of the porous body is fixed by the foregoing bonding step. When the conventional sintering is used for immobilization, for example, the dehydration condensation of the silanol group is excited by performing a high-temperature treatment at 200 ° C. or higher to form a siloxane bond. In the foregoing bonding step of the present invention, for example, when the substrate is a resin film, various additives that can catalyze the above-mentioned dehydration condensation reaction are reacted, so that the substrate can be compared at about 100 ° C without damaging the substrate. A low drying temperature and a short processing time of less than a few minutes continuously form a void structure and fix it.

The aforementioned method of chemically bonding is not particularly limited, and it may be appropriately determined according to the type of the gel (for example, a silicon compound gel). As a specific example, the chemical bonding system can be performed, for example, by chemically crosslinking the pulverized materials with each other. Other considerations include, for example, adding inorganic particles such as titanium oxide to the pulverized materials. A method of chemically crosslinking the ground product. In addition, in the case of providing a biocatalyst such as an enzyme, it is possible to chemically crosslink the site different from the active point of the catalyst with the crushed product. Therefore, the present invention is not only a low-refractive index layer formed by the aforementioned sol particles, but it is conceivable that the present invention can be extended to applications such as an organic-inorganic mixed low-refractive index layer and a host-guest low-refractive index layer, but is not limited thereto.

For example, the aforementioned bonding step may be performed through a chemical reaction in the presence of a catalyst in accordance with the type of pulverized matter of the aforementioned gel (for example, a silicon compound gel). The chemical reaction in the present invention is preferably a dehydration condensation reaction of residual silanol groups contained in the pulverized material of the aforementioned silicon compound gel. By the aforementioned catalyst promoting the reaction of the hydroxyl groups of the silanol group, continuous film formation that hardens the void structure in a short time can be achieved. Examples of the aforementioned catalyst include alkaline catalysts such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid, and oxalic acid. The catalyst for the aforementioned dehydration condensation reaction is particularly preferably a basic catalyst. In addition, a photoacid-generating catalyst or a photobase-generating catalyst that exhibits catalytic activity by irradiating light can also be suitably used. The photoacid-generating catalyst and the photobase-generating catalyst are not particularly limited, and are, for example, the same as described above. The catalyst is, for example, the same as described above, and is preferably added to the sol particle liquid containing the pulverized material just before coating, or it may be used as a mixed liquid in which the catalyst is mixed in a solvent. The mixed solution may be, for example, a coating solution dissolved in the sol particle liquid, a solution in which the catalyst is dissolved in a solvent, or a dispersion in which the catalyst is dispersed in a solvent. The aforementioned solvent is not particularly limited, and examples thereof include water, buffer, and the like.

In addition, for example, in the gel-containing liquid of the present invention, a cross-linking auxiliary agent for indirectly bonding the ground particles of the gel may be further added. This cross-linking auxiliary agent will enter between the particles (the above-mentioned pulverized material), and the particles and the cross-linking auxiliary agent interact or combine with each other, so that particles with a longer distance can also be combined with each other, and the strength can be effectively improved. The crosslinking assistant is preferably a polycrosslinking silane monomer. The polycrosslinked silane monomer specifically has, for example, an alkoxysilyl group of 2 or more and 3 or less, and the chain length between the alkoxysilyl groups may be 1 or more and 10 or less, and may contain elements other than carbon. Examples of the cross-linking auxiliary agent include: bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (Triethoxysilyl) propane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) butane, bis (trimethoxysilyl) butane, bis (triethoxysilyl) pentane, Bis (trimethoxysilyl) pentane, bis (triethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) -N-butyl-N-propyl-ethyl Alkane-1,2-diamine, ginseng (3-trimethoxysilylpropyl) trimer isocyanate, ginseng (3-triethoxysilylpropyl) trimer isocyanate, and the like. The amount of the crosslinking auxiliary to be added is not particularly limited, and is, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the pulverized silicon compound.

The aforementioned chemical reaction in the presence of a catalyst can be performed, for example, in the following manner: the aforementioned catalyst or catalyst generating agent has been previously added to the aforementioned gel-containing liquid, and The coating film of the generator is irradiated with light or heated; or the coating film is sprayed with the catalyst or catalyst generator and then irradiated or heated with light; or while the catalyst or catalyst generator is sprayed with the coating film Light irradiation or heating. For example, when the catalyst is a photoactive catalyst, the microporous particles can be chemically bonded to each other by irradiating light to form the polysiloxane porous body. In addition, when the catalyst is a thermally active catalyst, the microporous particles can be chemically bonded to each other by heating to form the polysilica porous body. The amount of light (energy) of the aforementioned light is not particularly limited, and may be, for example, 200 to 800 mJ / cm ² , 250 to 600 mJ / cm ² , or 300 to 400 mJ / cm ² in terms of @ 360nm. Under the insufficient irradiation amount, the decomposition effect of the light absorption by the catalyst generator will stagnate and the effect will be inadequate. From the viewpoint of avoiding the above situation, a cumulative light amount of 200 mJ / cm ² or more is preferable. In addition, from the viewpoint of avoiding damage to the base material under the low-refractive index layer and generating thermal wrinkles, a cumulative light amount of 800 mJ / cm ² or less is preferred. The wavelength of the light during the illumination is not particularly limited, and is, for example, 200 to 500 nm and 300 to 450 nm. The light irradiation time during the irradiation is not particularly limited, and is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, and 0.3 to 3 minutes. The conditions of the heat treatment are not particularly limited. The heating temperature is, for example, 50 to 250 ° C., 60 to 150 ° C., or 70 to 130 ° C., and the heating time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 3 minutes. In addition, the solvent used is, for example, a solvent having a low surface tension for the purpose of suppressing the shrinkage stress caused by the solvent volatilization during drying and the cracking of the void layer caused by the solvent. Examples include, but are not limited to, lower alcohols such as isopropyl alcohol (IPA), hexane, and perfluorohexane.

As described above, the low-refractive index layer (for example, a polysilicon porous body) of the present invention can be manufactured. However, the manufacturing method of the low-refractive-index layer of this invention is not limited to the said method. In addition, the low-refractive-index layer of this invention which is a polysiloxane porous body may be called the "polysiloxane porous body of this invention" hereafter.

In addition, in the production of the adhesive sheet with a low refractive index layer of the present invention, an adhesive layer is further formed on the low refractive index layer of the present invention (adhesive layer forming step). Specifically, for example, the aforementioned adhesive layer can be formed by applying (coating) an adhesive or an adhesive to the low refractive index layer of the present invention. In addition, the side of the adhesive layer such as an adhesive tape on which the aforementioned adhesive layer is laminated on the substrate may be laminated to the low refractive index layer of the present invention, thereby forming the aforementioned on the low refractive index layer of the present invention. Adhesive layer. At this time, the substrate such as the adhesive tape may continue to be in a bonded state, or may be peeled from the adhesive layer. In particular, as described above, by peeling off the base material to produce an adhesive sheet with a low refractive index layer without a base material (no base material), the thickness can be greatly reduced, and the increase in the thickness of components and the like can be suppressed. In the present invention, the "adhesive" and "adhesive layer" refer to, for example, an agent or a layer on the premise that the adherend can be peeled off again. In the present invention, the "adhesive" and "adhesive layer" mean, for example, an agent or a layer that does not require the adherend to be peelable again. However, in the present invention, "adhesive" and "adhesive" are not necessarily clearly distinguishable, and "adhesive layer" and "adhesive layer" are not necessarily clearly distinguishable. In the present invention, the adhesive or adhesive that forms the adhesive layer is not particularly limited, and for example, a general adhesive or adhesive can be used. Examples of the adhesive or adhesive include polymer-based adhesives such as acrylics, vinyl alcohols, polysiloxanes, polyesters, polyurethanes, and polyethers; and rubber-based adhesives. In addition, an adhesive such as a water-soluble cross-linking agent of a vinyl alcohol polymer such as glutaraldehyde, melamine, and oxalic acid may be used. As said adhesive agent, an acrylic adhesive agent is especially preferable from a viewpoint of transparency and adhesive force. Moreover, as said adhesive agent, it is preferable that it is an adhesive agent with a high storage elastic modulus from a viewpoint of durability. The storage elastic modulus (G ') of the aforementioned adhesive (for example, an acrylic adhesive) at 23 ° C may be, for example, 1.0 × 10 ⁵ or more, 1.1 × 10 ⁵ or more, or 1.2 × 10 ⁵ or more. The upper limit 値 is not particularly limited. It is limited, for example, 1.0 × 10 ⁷ or less. These adhesives and adhesives may be used singly or in combination (for example, mixing and laminating). As mentioned above, the adhesive layer can be used to protect the low refractive index layer from physical damage (especially abrasion). The adhesive layer is preferably one which is excellent in pressure resistance even when the adhesive sheet containing a low-refractive index layer without a substrate (no substrate) is formed and the low-refractive index layer is not damaged, but is not limited thereto. The thickness of the adhesive layer is not particularly limited, and is, for example, 0.1 to 100 μm, 5 to 50 μm, 10 to 30 μm, or 12 to 25 μm.

The low-refractive index layer of the present invention obtained in this manner can be further laminated with another film (layer) to form a laminated structure including the porous structure. At this time, in the laminated structure, each constituent element can be laminated through, for example, the adhesive layer (adhesive or adhesive).

Based on the efficiency, the lamination of each of the aforementioned constituent elements can be laminated by, for example, continuous processing using a long film (so-called roll to roll, etc.). When the base material is a molded article or element, it may be laminated. They are laminated after batch processing.

Hereinafter, a method of manufacturing the low-refractive index layer and the low-refractive index layer-containing adhesive sheet of the present invention using a transfer resin film substrate (hereinafter sometimes referred to as a "substrate") will be described with reference to FIGS. 1 to 3 as examples. In addition, the manufacturer of the illustration is just an example, and it is not limited to this.

The cross-sectional view of FIG. 1 schematically shows an example of steps for manufacturing the low-refractive index layer and the low-refractive index layer-containing adhesive sheet of the present invention using the aforementioned substrate. In FIG. 1, the method for forming the aforementioned low refractive index layer includes the following steps: a coating step (1), which coats the gel-containing liquid 20 ″ of the present invention on a substrate 10; The film forming step (drying step) (2) is a step of drying the gel-containing liquid 20 "to form a coating film 20 'as a precursor layer of the aforementioned low refractive index layer; and a chemical treatment step (such as crosslinking (Processing step) (3): The coating film 20 'is subjected to a chemical treatment (for example, a crosslinking treatment step) to form a low-refractive index layer 20. In this way, as shown in the figure, the low refractive index layer 20 can be formed using the substrate 10. In addition, the method for forming the low-refractive index layer may appropriately include or exclude steps other than the steps (1) to (3). The following steps can be further performed as shown in the figure: an adhesive layer coating step (4), applying an adhesive layer 30 on the surface of the low refractive index layer 20 on the side opposite to the substrate 10; and a coating step (5) The adhesive layer 30 is covered with a separating member 40; the peeling step (6) peels and removes the substrate 10 from the low-refractive index layer 20; the adhesive layer coating step (7), the peeled base of the low-refractive index layer 20 The other side of the material 10 is coated with another adhesive layer 30; in the coating step (8), the other another adhesive layer 30 is covered with another separating member 40 to produce an adhesive sheet containing a low refractive index layer, which One or both sides of the low refractive index layer 20 are directly laminated with a laminated body of the adhesive layer 30. In addition, FIG. 1 shows a method of separately performing an adhesive layer coating step (4) and a covering step (5), but it is also possible to attach the low-refractive index layer 20 to the adhesive that has been previously given to the separator 40. Then, the layer 30 (for example, the adhesive tape in which the separating member 40 and the adhesive layer 30 are integrated) is simultaneously subjected to the adhesive layer coating step (4) and the covering step (5). The same applies to the adhesive layer coating step (7) and the covering step (8). In addition, the method for forming the low-refractive index-containing adhesive sheet may include or not include steps other than the steps (1) to (8) as appropriate. In addition, when the adhesive sheet containing the low refractive index layer manufactured in FIG. 1 is used, for example, the separating member 40 covering and protecting the adhesive layer 30 can be removed to expose the adhesive layer 30 for use.

In the aforementioned coating step (1), the coating method of the gel-containing liquid 20 "is not particularly limited, and a general coating method can be adopted. The aforementioned coating method may be, for example, a slot die method, a reverse gravure coat method, a micro gravure method (micro gravure coat method), Dipping method (dip coating method), spin coating method, brush coating method, roll coating method, flexographic printing method, wire rod coating method, spray coating method, extrusion coating method, curtain coating method, reverse Coating method, etc. Among these, from the viewpoints of productivity and smoothness of the coating film, an extrusion coating method, a curtain coating method, a roll coating method, a micro gravure coating method, and the like are preferred. The coating amount of the gel-pulverized liquid 20 "is not particularly limited, and for example, it can be appropriately set so that the thickness of the porous structure (low-refractive index layer) 20 is appropriate. The thickness of the porous structure (low-refractive index layer) 20 is not particularly limited, and is, for example, the same as that described above.

In the aforementioned drying step (2), the gel-containing liquid 20 "is dried (that is, the dispersion medium contained in the gel-containing liquid 20" is removed) to form a coating film (precursor layer) 20 '. The conditions for the drying treatment are not particularly limited, as described above.

Furthermore, in the aforementioned chemical processing step (3), a coating film containing the aforementioned catalyst (for example, a photoactive catalyst, a photocatalyst generating agent, a thermally active catalyst, or a thermal catalyst generating agent) added before coating is applied. 20 ', irradiate with light or heat to chemically combine (for example, cross-link) the aforementioned pulverized materials in the coating film (precursor) 20' to form a low refractive index layer 20. The irradiation or heating conditions of the aforementioned chemical processing step (3) are not particularly limited, as described above.

Next, FIG. 2 schematically shows an example of a coating device of a slit die coating method and a method of forming the aforementioned low refractive index layer using the device. In addition, although FIG. 2 is a cross-sectional view, hatching is omitted for readability.

As shown in the figure, each step of the method using the apparatus is performed while the substrate 10 is conveyed in one direction by a roller. The conveying speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, and 5 to 30 m / min.

First, the substrate 10 is conveyed while being output from the feed roller 101, and the coating step (1) is performed on the coating roller 102, that is, the gel-containing liquid 20 '' of the present invention is coated on the substrate, and then continued The transition to the drying step (2) is performed in the oven area 110. In the coating apparatus of FIG. 2, a pre-drying step is performed after the coating step (1) and before the drying step (2). The pre-drying step may be performed at room temperature without heating. In the drying step (2), a heating mechanism 111 is used. As described above, the heating mechanism 111 may be a heater, a heating roller, a far-infrared heater, or the like. In addition, for example, the drying step (2) can be divided into a plurality of steps, so that the drying temperature becomes higher with the subsequent drying step.

After the drying step (2), a chemical treatment step (3) is performed in the chemical treatment zone 120. In the chemical treatment step (3), for example, when the dried coating film 20 'contains a photoactive catalyst, the light is irradiated with a lamp (lighting mechanism) 121 disposed above and below the substrate 10. Alternatively, for example, when the dried coating film 20 ′ contains a thermally active catalyst, a hot air heater (heating mechanism) is used instead of the lamp (lighting device) 121, and the hot air heater 121 disposed above and below the base material 10 heats the base material 10. . By this cross-linking treatment, the aforementioned pulverized materials in the coating film 20 'can be chemically bonded to each other, and the low refractive index layer 20 can be hardened. strengthen. In addition, although illustration is omitted, the aforementioned steps (4) to (8) of FIG. 1 may be performed by using a roll to roll method to manufacture the aforementioned adhesive sheet containing a low refractive index layer. Thereafter, the produced adhesive sheet containing the low-refractive index layer is taken up by a take-up roll 105.

FIG. 3 schematically shows an example of a coating device of a microgravure method (microgravure coating method) and the aforementioned porous structure forming method using the same. Although this figure is a cross-sectional view, hatching has been omitted for readability.

As shown in the figure, the steps of the method using the apparatus are performed in the same manner as in FIG. 2 while the substrate 10 is conveyed in one direction by a roller. The conveying speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, and 5 to 30 m / min.

First, the coating step (1) is performed while conveying the substrate 10 from the sending-out roller 201 for conveyance, and the substrate 10 is coated with the gel-pulverized liquid 20 '' of the present invention. The coating of the liquid 20 "containing the pulverized gel was performed using a liquid storage area 202, a doctor knife 203, and a microgravure 204 as shown in the figure. Specifically, the liquid 20 '' containing the pulverized gel stored in the liquid storage area 202 is attached to the surface of the microgravure 204, and then controlled to a predetermined thickness by a doctor blade 203 and simultaneously coated on the substrate with the microgravure 204材 10 surface. In addition, the micro gravure 204 is exemplified and is not limited to this, and any other coating mechanism may be used.

Next, a drying step (2) is performed. Specifically, as shown in the figure, the substrate 10 coated with the gel-containing pulverized liquid 20 ″ is transferred to the oven zone 210 and dried by heating by a heating mechanism 211 in the oven zone 210. The heating mechanism 211 may be the same as, for example, FIG. 2. In addition, for example, the drying step (2) can be divided into a plurality of steps by dividing the oven area 210 into a plurality of blocks, so that the drying temperature becomes higher and higher with the subsequent drying step. After the drying step (2), a chemical treatment step (3) is performed in the chemical treatment zone 220. In the chemical processing step (3), for example, when the dried coating film 20 'contains a photoactive catalyst, the light is irradiated with a lamp (lighting mechanism) 221 disposed above and below the substrate 10. Or, for example, when the dried coating film 20 'contains a thermally active catalyst, a hot air heater (heating mechanism) is used instead of the lamp (lighting device) 221, and the hot air heater (heating mechanism) disposed below the substrate 10 is used. 221 The substrate 10 is heated. By this cross-linking treatment, chemical bonding between the aforementioned pulverized materials in the coating film 20 ′ is initiated, and the low refractive index layer 20 is formed.

In addition, although illustration is omitted, the aforementioned steps (4) to (8) of FIG. 1 may be performed by using a roll to roll method to manufacture the aforementioned adhesive sheet containing a low refractive index layer. Thereafter, the prepared adhesive sheet containing the low-refractive index layer is wound up by a take-up roll 251.

[4. Void layer] Hereinafter, a case where the low-refractive index layer of the present invention is a void layer (the void layer of the present invention) will be exemplified. However, these are examples and do not limit the present invention. In addition, the following description of matters (such as haze, refractive index, layer thickness, abrasion resistance, Rz coefficient, etc.) other than matters related to the void itself (such as porosity, pore size, etc.) may be described without special notice. The low refractive index layer used in the present invention is a case other than the void layer.

The void layer system of the present invention may be, for example, a void ratio of 35% by volume or more and a peak pore diameter of 50 nm or less. However, this is an example, and the void layer of the present invention is not limited to this.

The porosity may be, for example, 35 vol% or more, 38 vol% or more, or 40 vol% or more, and may be 90 vol% or less, 80 vol% or less, or 75 vol% or less. The void layer of the present invention may be a high void layer having a void ratio of 60% by volume or more.

The porosity can be measured by, for example, the following measurement method.

(Measurement method of porosity) If the layer to be measured for porosity contains voids in a single layer, the ratio (volume ratio) of the layer constituent substance to the air can be calculated by a conventional method (for example, measuring the weight and volume to calculate the density). Therefore, the porosity (volume%) can be calculated from this. In addition, since the refractive index has a correlation with the porosity, the porosity can also be calculated from the refractive index 的 of the layer, for example. Specifically, for example, the refractive index 测 measured by an ellipsometer can be used to calculate the porosity according to Lorentz-Lorenz's formula.

The void layer of the present invention can be produced, for example, as described above, through chemical bonding of a pulverized gel (fine-pored particles). At this time, for convenience, the voids of the void layer can be classified into the following three types (1) to (3). (1) The voids in the raw gel itself (inside the particles) (2) The voids in the gel pulverized substance unit (3) The voids between the pulverized substances due to the accumulation of the pulverized gel

The void in the above (2) refers to the case where each particle group generated by pulverizing the gel is regarded as a single block (block) regardless of the size and size of the pulverized gel (fine-pored particles). The voids that can be formed in the body are different from those formed during the crushing of (1) above. The voids in the above (3) are voids caused by the size, size, and the like of the pulverized gel (fine-pored particles) during the pulverization (for example, medium-free pulverization, etc.). The void layer of the present invention has an appropriate porosity and peak pore diameter, for example, by having the voids (1) to (3).

The peak pore diameter may be, for example, 5 nm or more, 10 nm or more, or 20 nm or more, and may be 50 nm or less, 40 nm or less, or 30 nm or less. In the void layer, if the peak pore diameter is too large in a state where the void ratio is high, light is scattered and becomes opaque. In addition, in the present invention, the lower limit of the peak pore diameter of the void layer is not particularly limited. However, if the peak pore diameter is too small, it is difficult to increase the porosity, so the peak pore diameter should not be too small. In the present invention, the peak pore diameter can be measured, for example, by the following method.

(Measurement method of peak pore diameter) Using a pore distribution / specific surface area measuring device (a brand name of BELLSORP MINI / MicrotracBEL), the peak pore diameter was calculated from the calculation results of the BJH chart and BET chart of nitrogen adsorption, and the isothermal adsorption line. Aperture.

The thickness of the void layer of the present invention is not particularly limited, and may be, for example, 100 nm or more, 200 nm or more, or 300 nm or more, and may be 10,000 nm or less, 5000 nm or less, or 2000 nm or less.

In the void layer or the low-refractive-index layer of the present invention, the surface roughness Rz coefficient should preferably be as low as possible from the relationship of surface strength and the like. The aforementioned surface roughness Rz coefficient may be, for example, 100 nm or less, 95 nm or less, or 90 nm or less. If the surface roughness Rz coefficient is 100 nm or more, the strength of the surface of the void layer or the low-refractive index layer of the present invention can be easily suppressed or prevented from being easily damaged when dropped. The lower limit 値 of the surface roughness Rz coefficient is not particularly limited, and is, for example, 50 nm or more.

In the present invention, the aforementioned surface roughness Rz coefficient refers to a ten-point average roughness defined by JIS B 0601: 1970 / JIS B 0601: 1994. The definition of the aforementioned surface roughness Rz coefficient (ten-point average roughness) is specifically taken from the roughness curve in the direction of its average line to intercept only the reference length, and the measured portion is measured from the average line in the direction of the vertical magnification. The sum of the average 値 of the absolute value of the elevation (Yp) of the highest peak to the fifth peak and the average 値 of the absolute value of the elevation (Yv) of the lowest valley to the 5th lowest, the coefficient is the value. The aforementioned surface roughness Rz coefficient can be measured, for example, by a method using an atomic force microscope (AFM). Specifically, the surface of a certain range was measured using the aforementioned interatomic force microscope, and the ten-point surface roughness (Rz) of the area was calculated. For example, SPI3800 (trade name) manufactured by Seiko Instruments Inc. may be used as the interatomic force microscope to measure a surface image in a range of 5 μm × 5 μm in DFM mode, and calculate a ten-point surface roughness (Rz) using a body mounted on the device.

In addition, the void layer of the present invention, for example, indicates that the abrasion resistance measured using BEMCOT (registered trademark) of the film strength can be 60 to 100%, and the number of fold resistance obtained by the MIT test indicating flexibility can be measured. It is 100 times or more, but it is not limited to this.

For example, the void layer of the present invention uses the pulverized material of the porous body gel, so that the three-dimensional structure of the porous body gel is destroyed, and a new three-dimensional structure different from the porous body gel is formed. In this way, the void layer of the present invention will be a layer formed by a new pore structure (new void structure) and a new pore structure that cannot be obtained from the layer formed by the aforementioned porous body gel, thereby forming a high void ratio Nano-scale void layer. In addition, in the void layer of the present invention, for example, when the void layer is a porous polysiloxane, for example, while adjusting the number of siloxane bond functional groups of a silicon compound gel, the pulverized materials are chemically treated with each other. Combined. In addition, after the formation of a new three-dimensional structure as a precursor of the aforementioned void layer, chemical bonding (for example, cross-linking) is performed in the bonding step. Therefore, for example, when the aforementioned void layer is a functional porous body, It has a void structure, but still maintains sufficient strength and flexibility. Therefore, according to the present invention, it is possible to easily and simply apply the void layer to various objects.

The void layer of the present invention is, for example, a pulverized product containing a porous body gel as described above, and the pulverized products are chemically bonded to each other. In the void layer of the present invention, the chemical bonding (chemical bond) form of the pulverized materials is not particularly limited, and specific examples of the chemical bond include cross-linking bonding and the like. The method of chemically bonding the pulverized materials to each other is, for example, as described in detail in the method for producing the void layer.

The cross-linking bonding system is, for example, a siloxane bond. Examples of the siloxane bond include a T2 bond, a T3 bond, and a T4 bond as shown below. When the polysiloxane porous body of the present invention has a siloxane bond, for example, it may have any kind of bond, any two kinds of bonds, or all three kinds of bonds. Among the aforementioned siloxane bonds, the higher the ratio of T2 and T3, the more flexible it is, and the inherent properties of the gel can be expected, but the film strength becomes weak. On the other hand, if the T4 ratio in the siloxane bond is higher, the strength of the film is more likely to be exhibited, but the void size becomes smaller and the flexibility becomes weaker. Therefore, it is desirable to change the T2, T3, and T4 ratios according to, for example, use.

[Chemical Formula 5]

When the void layer of the present invention has the aforementioned siloxane bond, the ratio of T2, T3, and T4 is, for example, when T2 is represented by "1", T2: T3: T4 = 1: [1 to 100]: [0 to 50] , 1: [1 to 80]: [1 to 40], 1: [5 to 60]: [1 to 30].

The void layer of the present invention is preferably, for example, when the silicon atoms contained therein are siloxane bonded. As a specific example, the proportion of unbound silicon atoms (that is, residual silanol) in all silicon atoms contained in the aforementioned polysilica porous body is, for example, less than 50%, 30% or less, and 15% or less.

The void layer of the present invention has a pore structure, and the pore void size refers to the aforementioned major axis diameter of the major axis diameter and the minor axis diameter of the gap (hole). The pore size is, for example, 5 nm to 50 nm. The lower limit of the gap size is, for example, 5 nm or more, 10 nm or more, and 20 nm or more. The upper limit is, for example, 50 nm or less, 40 nm or less, and 30 nm or less. The range is, for example, 5 nm to 50 nm, 10 nm to 40 nm. Since the ideal gap size is determined according to the use of the gap structure, the gap size must be adjusted to a desired gap size according to, for example, the purpose. The void size can be evaluated, for example, by the following method.

(Sectional SEM observation of void layer) In the present invention, the shape of the void layer can be observed and analyzed with a SEM (scanning electron microscope). Specifically, for example, the void layer is subjected to FIB processing (acceleration voltage: 30 kV) under cooling, and the obtained cross-sectional sample is FIB-SEM (manufactured by FEI: brand name Helios NanoLab 600, acceleration voltage: 1 kV) to observe a magnification of 100,000. Obtain cross-section electronic images.

(Evaluation of void size) In the present invention, the aforementioned void size can be legally quantified by a BET test. Specifically, a pore distribution / specific surface area measuring device (BELLSORP MINI / MicrotracBEL trade name) was charged with a 0.1 g sample (the void layer of the present invention) in a capillary tube, and then dried under reduced pressure at room temperature for 24 hours. Degas the gas in the void structure. Then, by adsorbing nitrogen on the sample, a BET chart, a BJH chart, and an adsorption isotherm were drawn to obtain a pore distribution. Thereby, the void size can be evaluated.

The void layer of the present invention, for example, has a scratch resistance of 60 to 100% as measured by BEMCOT (registered trademark), which indicates film strength. Since the present invention has such a film strength, for example, it has excellent scratch resistance in various processes. The present invention has, for example, scratch resistance in a production process when winding and processing a product film after the formation of the void layer film. On the other hand, instead of reducing the porosity, the void layer of the present invention can use a catalyst reaction in a heating step described later to increase the particle size of the pulverized material of the silicon compound gel and the pulverized material to each other. The binding power of the neck. With this, the void layer of the present invention can, for example, impart a certain level of strength to the originally weak void structure.

The lower limit of the abrasion resistance is, for example, 60% or more, 80% or more, and 90% or more. The upper limit is, for example, 100% or less, 99% or less, and 98% or less, and the ranges are, for example, 60 to 100%, 80 to 99%. , 90 ~ 98%.

The abrasion resistance can be measured, for example, by the following method.

(Evaluation of abrasion resistance) (1) A void layer (low refractive index layer of the present invention) which has been coated and formed on an acrylic film is sampled into a circular sample having a diameter of about 15 mm. (2) Next, the sample was identified by fluorescent X-rays (Shimadzu Corporation: ZSX Primus II), and the Si coating amount (Si ₀ ) was measured. Then, the gap layer on the acrylic film was cut to a size of 50 mm × 100 mm in the vicinity of the sampling place and fixed to a glass plate (thickness 3 mm), and then a sliding test was performed with Bemcot (registered trademark). . The sliding condition was 100 g in weight, 10 times back and forth. (3) In the same manner as in the above (1), a sample was taken from the gap layer on which sliding was performed, and fluorescence X measurement was performed to measure the residual amount of Si (Si ₁ ) after the abrasion test. The abrasion resistance is defined by the Si residual rate (%) before and after the Bemcot (registered trademark) sliding test, and is shown by the following formula. Scratch resistance (%) = [Residual Si amount (Si ₁ ) / Si coating amount (Si ₀ )] × 100 (%)

The void layer of the present invention has, for example, flexibility that is 100 times or more by the MIT test. Since the present invention has such flexibility, it has excellent operability, for example, during winding or use in a manufacturing process.

The lower limit of the number of times of folding resistance is, for example, 100 times or more, 500 times, or 1,000 times or more, and the upper limit is not particularly limited. For example, the upper limit is 10,000 times or less, and the range is, for example, 100 to 10,000 times, 500 to 10,000 times, or 1,000 to 10,000 times. .

The aforementioned flexibility means, for example, the ease with which a substance deforms. The number of times of folding resistance obtained by the MIT test can be measured by the following method, for example.

(Evaluation of Bending Resistance Test) The above-mentioned void layer (the void layer of the present invention) was cut into a straight strip of 20 mm × 80 mm, and then loaded into a MIT bending tester (manufactured by Tester Sangyo: BE-202), and 1.0 N was applied. The burden. The clamping portion that clamped the void layer was R2.0 mm, and the number of times of folding resistance was 10,000 times at most. The number of times when the void layer was broken was taken as the number of times of folding resistance.

In the void layer of the present invention, the film density indicating the porosity is not particularly limited, and its lower limit is, for example, 1 g / cm ³ or more, 5 g / cm ³ or more, 10 g / cm ³ or more, and 15 g / cm ³ or more, and its upper limit is, for example, 50 g / cm ³ or less, 40 g / cm ³ or less, 30 g / cm ³ or less, 2.1 g / cm ³ or less, and the range is, for example, 5 to 50 g / cm ³ , 10 to 40 g / cm ³ , 15 to 30 g / cm ³ , 1 ~ 2.1g / cm ³ .

The film density can be measured, for example, by the following method.

(Film density evaluation) After forming a void layer (the void layer of the present invention) on an acrylic film, the X-ray reflectance in the total reflection region was measured using an X-ray diffraction device (manufactured by RIGAKU: RINT-2000). After fitting between Intensity and 2θ, the porosity (P%) was calculated from the critical angle of the total reflection of the void layer and the substrate. The film density can be expressed by the following formula. Membrane density (%) = 100 (%)-porosity (P%)

The void layer of the present invention may have a pore structure (porous structure) as described above, and the pore structure may be, for example, a continuous continuous cell structure. The open foamed structure indicates, for example, a state in which the pore structures are connected in a three-dimensional manner in the void layer, and the internal voids of the pore structure are connected together. In the case where the porous body has a continuous cell structure, the porosity occupied by the entire body can be increased, but when a single cell particle such as hollow silica is used, a continuous cell structure cannot be formed. In contrast, the void layer of the present invention has a three-dimensional tree structure because the sol particles (the pulverized product of the porous body gel forming the sol) have a three-dimensional tree structure. Therefore, the tree particles can be used in the coating film (containing the porous body). The coating film of the sol of the gel pulverized substance is deposited and accumulated, and a continuous foam structure is easily formed. In addition, the void layer of the present invention preferably forms a monolith structure having a "continuous cell structure with a plurality of fine pore distributions". The aforementioned monolithic structure refers to, for example, a structure in which nano-level fine voids exist, and a hierarchical structure in which the same nano-voids are aggregated to form a continuous cell structure. In the case of forming the aforementioned monolithic structure, for example, the strength of the film can be imparted with fine voids and the high void fraction can be imparted with coarse continuous voids to achieve both film strength and high void fraction. To form such a monolithic structure, for example, it is important to first control the pore distribution of the void structure generated by the aforementioned porous body gel at a stage before being crushed into the aforementioned pulverized material. In addition, for example, when the porous body gel is pulverized, the particle size distribution of the pulverized material can be controlled to a desired size to form the monolithic structure.

In the void layer of the present invention, there is no particular limitation on the elongation at break caused by fracture, which indicates flexibility, and the lower limit thereof is, for example, 0.1% or more, 0.5% or more, and 1% or more, and the upper limit thereof is, for example, 3% or less. The range of the elongation at which the fracture occurs is, for example, 0.1 to 3%, 0.5 to 3%, or 1 to 3%.

The elongation at which the fracture and crack occurs can be measured, for example, by the following method.

(Evaluation of elongation at break and crack occurrence) After forming a void layer (the void layer of the present invention) on an acrylic film, a 5 mm × 140 mm straight strip was sampled. Next, the sample was clamped to a tensile tester (manufactured by Shimadzu Corporation: AG-Xplus) so that the distance between the clamps was 100 mm, and then a tensile test was performed at a tensile speed of 0.1 mm / s. The foregoing sample in the test was carefully observed, and the test was terminated when a part of the sample appeared cracking, and the elongation (%) at the time of cracking was taken as the elongation at which cracking occurred.

In the void layer of the present invention, the haze indicating transparency is not particularly limited, and its lower limit is, for example, 0.1% or more, 0.2% or more, and 0.3% or more, and its upper limit is, for example, 10% or less, 5% or less, and 3% or less. The range is, for example, 0.1 to 10%, 0.2 to 5%, and 0.3 to 3%.

The haze can be measured, for example, by the following method.

(Evaluation of Haze) The void layer (the void layer of the present invention) was cut into a size of 50 mm × 50 mm and set on a haze meter (manufactured by Murakami Color Technology Research Institute: HM-150), and the haze was measured. The haze value was calculated by the following formula. Haze (%) = [diffusive transmittance (%) / full light transmittance (%)] × 100 (%)

The aforementioned refractive index is generally referred to as the refractive index of the medium by the ratio of the transmission speed of the light wave surface in the vacuum to the propagation speed in the medium. The refractive index of the void layer (for example, a polysilicon porous body) of the present invention is not particularly limited, and its upper limit is, for example, 1.3 or less, less than 1.3, 1.25 or less, 1.2 or less, and 1.15 or less, and its lower limit is, for example, 1.05 or more, 1.06 or more, 1.07 or more, for example, ranges from 1.05 or more and 1.3 or less, 1.05 or more and less than 1.3, 1.05 or more and 1.25 or less, 1.06 or more and less than 1.2, 1.07 or more and 1.15 or less.

In the present invention, unless otherwise specified, the aforementioned refractive index refers to a refractive index measured at a wavelength of 550 nm. The method for measuring the refractive index is not particularly limited, and it can be measured, for example, by the following method.

(Evaluation of refractive index) After forming a void layer (the void layer of the present invention) on an acrylic film, it was cut into a size of 50 mm × 50 mm and bonded to the surface of a glass plate (thickness: 3 mm) with an adhesive layer. The central part (about 20 mm in diameter) of the back surface of the glass plate was black-coated with a black singular pen to prepare a sample that was not reflected on the back surface of the glass plate. The aforementioned sample was mounted on an elliptical polarimeter (J‧ A‧ Woollam Japan: VASE), and the refractive index was measured at a wavelength of 500 nm and an incident angle of 50 to 80 degrees, and the average chirp was taken as the refractive index.

The thickness of the void layer of the present invention is not particularly limited, and its lower limit is, for example, 0.05 μm or more and 0.1 μm or more, and its upper limit is, for example, 1000 μm or less and 100 μm or less, and its range is, for example, 0.05 to 1000 μm or 0.1 to 100 μm.

The form of the void layer of the present invention is not particularly limited, and may be, for example, a film shape or a block shape.

The method for producing the void layer of the present invention is not particularly limited, and it can be produced, for example, by using the aforementioned method for producing the void layer.

Examples Next, examples of the present invention will be described. However, the present invention is not limited to the following examples.

In addition, in the following reference examples, examples, and comparative examples, the parts (relative amount) of each substance are parts by mass (parts by weight) unless otherwise specified.

[Reference Example 1] First, gelation of a silicon compound (step (1) below) and aging step (step (2) below) were performed to produce a gel having a porous structure (polysiloxane porous body) . Then, the following (3) morphology control step, (4) solvent replacement step, (5) concentration measurement (concentration management) and concentration adjustment step, and (6) pulverization step are further performed to obtain a coating for forming a low refractive index layer. Liquid (liquid containing pulverized gel). In addition, as described below, for example, the reference (3) form control step is performed as a step different from the following step (1). However, the present invention is not limited to this, and for example, the following (3) form control step may be performed in the following step (1).

(1) Gelation of silicon compound Dissolve 9.5 kg of the silicon compound precursor MTMS in 22 kg of DMSO. 5 kg of an 0.01 mol / L oxalic acid aqueous solution was added to the aforementioned mixed solution, and MTMS was hydrolyzed by stirring at room temperature for 120 minutes to generate ginsyl (hydroxy) methylsilane.

After adding 3.8 kg of 28% ammonia water and 2 kg of pure water to 55 kg of DMSO, the hydrolyzed mixture was added, and the mixture was stirred at room temperature for 60 minutes. The liquid after stirring for 60 minutes was poured into a stainless steel container having a length of 30 cm × width 30 cm × height 5 cm and allowed to stand at room temperature, thereby performing gelation of ginsyl (hydroxy) methylsilane to obtain a gel-like silicon compound.

(2) Maturation step The gelatinous silicon compound obtained by the aforementioned gelation treatment was incubated at 40 ° C for 20 hours and subjected to a maturation treatment to obtain the aforementioned cuboid shaped gel. The amount of DMSO (high boiling point solvent above 130 ° C) used in the raw material of the gel accounts for about 83% by weight of the entire raw material, so the high boiling point solvent above 130 ° C obviously contains more than 50% by weight. In addition, the amount of MTMS (monomer as a constituent unit of the gel) in the raw material of the gel accounts for about 8% by weight of the entire raw material. Therefore, the hydrolysis of the monomer (MTMS) as the constituent unit of the gel is 130 ° C below the boiling point The content of the solvent (in this case, methanol) is clearly below 20% by weight.

(3) Morphology control step Pour water as a replacement solvent on the gel synthesized in the aforementioned 30 cm x 30 cm x 5 cm stainless steel container through the steps (1) and (2). Next, the gel was slowly inserted from above into the cutting jig, a cutting blade, into the stainless steel container, and the gel was cut into a rectangular parallelepiped having a size of 1.5 cm × 2 cm × 5 cm.

(4) Solvent replacement step Next, the solvent replacement step is performed in the following manner (4-1) to (4-3).

(4-1) After the aforementioned "(3) morphology control step", the gel-like silicon compound was immersed in 8 times the weight of the gel-like silicon compound in water, and slowly stirred for 1 h with only water convection. After 1h, change the water with the same amount of water and stir for 3h. After that, the water was changed again, and then slowly stirred at 60 ° C while heating for 3 hours.

(4-2) After (4-1), water was replaced with 4 times the weight of isopropyl alcohol of the aforementioned gelatinous silicon compound, and the same was stirred at 60 ° C for 6 hours and heated.

(4-3) After (4-2), replace isopropanol with isobutanol of the same weight, and heat it at 60 ° C for 6 hours to replace the solvent contained in the gel-like silicon compound with isobutanol. . In the above manner, a gel for producing a void layer of the present invention was produced.

(5) Concentration measurement (concentration management) and concentration adjustment step After the solvent replacement step of the above (4), the block-shaped gel is taken out, and the solvent attached to the periphery of the gel is removed. Then, the solid content concentration in a single gel block was measured by a weight drying method. At this time, in order to obtain the reproducibility of the measurement cymbal, measurement was performed on six randomly taken blocks, and the deviation between the average 値 and the number 値 was calculated. At this time, the average 値 of the solid content concentration (gel concentration) in the gel was 5.20% by weight, and the deviation of the aforementioned gel concentration 中 in the six gels was within ± 0.1%. Based on the measured value, an isobutanol solvent was added to adjust the gel solid content concentration (gel concentration) to approximately 3.0% by weight.

(6) Gel pulverization step The pulverization of the gel (gel-like silicon compound) after the concentration measurement (concentration management) and the concentration adjustment step in (5) is performed in two steps. The first pulverization step is continuous emulsification dispersion ( Made by Pacific Machinery Co., Ltd., Milder MDN304 type), the second pulverization stage is high-pressure non-media pulverization (made by Sugino Machine: Star Burst HJP-25005 type). This pulverization process is to add 46.6 kg of gel made of the gel-like silicon compound containing the solvent replaced by the aforementioned solvent, add 26.6 kg of isobutanol, and measure the pulverization. The first pulverization stage is cyclic pulverization for 20 minutes. The crushing pressure in the crushing stage is 100 MPa. In this way, an isobutanol dispersion liquid (a liquid containing a gel-pulverized product) in which nano-sized particles (the gel-pulverized product) were dispersed was obtained. Furthermore, 224 g of a 1.5% by weight methyl isobutyl ketone solution of WPBG-266 (trade name, manufactured by Wako) was added to 3 kg of the gel-pulverized liquid, and 67.2 g of bis (trimethoxysilyl) was further added. After a 5 wt% solution of methyl isobutyl ketone in ethane (manufactured by TCI), 31.8 g of N, N-dimethylformamide was added and mixed to obtain a coating solution.

The solid content concentration (gel concentration) of the solution (high-viscosity gel pulverization solution) was measured after the first pulverization step (coarse pulverization step) and before the second pulverization step (nano pulverization step). It was 3.01% by weight. After the first pulverization step (coarse pulverization step) and before the second pulverization step (nano pulverization step), the volume average particle diameter of the gel pulverized material is 3 to 5 μm, and the shear viscosity of the liquid is 4,000 mPa ・ s. The high-viscosity gel pulverized liquid at this time does not have solid-liquid separation due to its high viscosity, and can be used as a homogeneous liquid. Therefore, the measurement 后 after the first pulverization step (coarse pulverization step) described above is directly used. Furthermore, after the second pulverization step (nano pulverization step), the volume average particle diameter of the pulverized material of the gel is 250 to 350 nm, and the shear viscosity of the liquid is 5 m to 10 mPa.s. Further after the second pulverization step (nano pulverization step), the solid content concentration (gel concentration) of the liquid (liquid containing gel pulverized material) was measured again. As a result, it was 3.01% by weight, which was the same as the first pulverization step. No change after (coarse pulverization step).

In addition, in this reference example, the average particle diameter of the pulverized material (sol particles) of the gel after the first pulverization stage and after the second pulverization stage is based on a dynamic light scattering Nanotrac particle size analyzer (Nikkiso equipment Company system, trade name UPA-EX150). In this embodiment, the shear viscosity of the liquid after the first pulverization stage and after the second pulverization stage are identified with a vibration viscosity measuring machine (manufactured by Sekonic Corporation, trade name FEM-1000V). The same applies to the following examples and comparative examples.

In addition, after the first pulverization step (coarse pulverization step), the solid content (gel) of the gel-containing pulverized material was measured (calculated) in the functional group (silanol group) constituting the unit monomer. The ratio of the functional group (residual silanol group) which is not beneficial to the cross-linked structure in the gel, as a result, 11 mol% of the measured fluorene was obtained. In addition, the ratio of functional groups (residual silanol groups) that are not conducive to the cross-linking structure in the gel is determined by the following method: After drying the gel, the solid-state NMR (Si-NMR) is measured, and the calculation from the NMR peak ratio is not beneficial The ratio of residual silanol groups in the crosslinked structure.

In the above manner, a coating liquid (a liquid containing a pulverized gel) for forming a void layer of the present reference example (Reference Example 1) was produced. The peak pore diameter of the pulverized gel (fine-pored particles) in the coating liquid (a pulverized gel-containing liquid) for forming a void layer was measured by the method described above, and it was 12 nm.

[Reference Example 2: Formation of Adhesive Layer] An adhesive layer of this reference example (Reference Example 2) was formed through the following procedures (1) to (3).

(1) Prepolymer composition was prepared from a monomer mixture consisting of 68 parts of 2-ethylhexyl acrylate, 14.5 parts of N-ethylene-2-pyrrolidone, and 17.5 parts of 2-hydroxyethyl acrylate In the mixture, 0.035 parts of a photopolymerization initiator (trade name "IRGACURE 184", BASF Corporation) and 0.035 parts of a photopolymerization initiator (trade name "IRGACURE 651", BASF Corporation) were blended, and then an external line was irradiated to the viscosity (BH viscometer No. (5 rotor, 10 rpm, measurement temperature 30 ° C.) until about 20 Pa · s, to obtain a prepolymer composition in which a part of the monomer components has been polymerized.

(2) Preparation of acrylic adhesive composition To the prepolymer composition prepared in (1) above, 0.150 parts of hexanediol diacrylate (HDDA) and a silane coupling agent ("KBM-403" Shin-Etsu Chemical Co., Ltd.) were added. Industry Co., Ltd.) 0.3 parts and mixed to obtain an acrylic adhesive composition.

(3) Formation of Adhesive Layer The acrylic adhesive composition (acrylic adhesive solution) prepared in the above (2) was applied on the adhesive layer (adhesive layer) after drying to a thickness of 25 μm. A coating layer was formed on one side of a polyethylene terephthalate (PET) film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., thickness: 50 μm) treated with silicone. A polyethylene terephthalate (PET) film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., thickness: 38 μm) was provided on the coating layer to cover the coating layer to block oxygen. To form a laminated body. Next, a black light (manufactured by Toshiba) was irradiated with ultraviolet light having an illuminance of 5 mW / cm ² for 300 seconds from the upper surface (MRF38 side) of the laminated body. Then, a drying process was performed in a 90 ° C. dryer for 2 minutes to volatilize the remaining monomers to form an adhesive layer (adhesive layer). The storage elastic modulus G ′ of the adhesive layer (adhesive layer) at 23 ° C. was 1.1 × 10 ⁵ .

[Reference Example 3: Formation of Adhesive Layer] An adhesive layer of this reference example (Reference Example 3) was formed through the following procedures (1) to (3).

(1) Preparation of acrylic polymer solution: 90.7 parts of butyl acrylate, 6 parts of N-propenyl morpholine, 3 parts of acrylic acid, 0.3 parts of 2-hydroxybutyl acrylate, and polymerization initiator 2,2'- 0.1 part by weight of azobisisobutyronitrile was placed together with 100 g of ethyl acetate into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. Next, the contents of the four-necked flask were slowly stirred while introducing nitrogen to replace the nitrogen. Then, the liquid temperature in the 4-necked flask was maintained at about 55 ° C., and a polymerization reaction was performed for 8 hours to prepare an acrylic polymer solution.

(2) Preparation of acrylic adhesive composition The acrylic adhesive composition (acrylic adhesive solution) was prepared by mixing isocyanate with 100 parts of the solid content of the acrylic polymer solution obtained in the above (1). Crosslinking agent (trade name "CORONATE L" manufactured by Japan Polyurethane Industry Corporation, toluene diisocyanate adduct of trimethylolpropane), benzyl peroxide (trade name "Nyper BMT" manufactured by Japan Oil Corporation) ) 0.3 parts, and 0.2 parts of γ-glycidoxypropylmethoxysilane (trade name "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.).

(3) Formation of Adhesive Layer The acrylic adhesive composition obtained in the above (2) was coated on polyethylene terephthalate treated with polysiloxane so that the thickness of the adhesive layer after drying was 5 μm. One side of a diester (PET) film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., thickness: 38 μm) was dried at 150 ° C. for 3 minutes to form an adhesive layer (adhesive layer). The storage elastic modulus G ′ of the adhesive layer (adhesive layer) at 23 ° C. was 1.3 × 10 ⁵ .

[Reference Example 4: Formation of Adhesive Layer] An adhesive layer of this reference example (Reference Example 4) was formed through the following procedures (1) to (3).

(1) Preparation of acrylic polymer solution: 97 parts of butyl acrylate, 3 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate, and 0.1 part of 2,2'-azobisisobutyronitrile and 100 g of Ethyl acetate was put together in a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. Next, the contents of the four-necked flask were slowly stirred while introducing nitrogen to replace the nitrogen. Then, the liquid temperature in the 4-necked flask was maintained at about 55 ° C., and a polymerization reaction was performed for 8 hours to prepare an acrylic polymer solution.

(2) Preparation of acrylic adhesive composition The acrylic adhesive composition (acrylic adhesive solution) was prepared by mixing isocyanate with 100 parts of the solid content of the acrylic polymer solution obtained in the above (1). Crosslinking agent (trade name "CORONATE L" manufactured by Japan Polyurethane Industry Co., Ltd., toluene diisocyanate adduct of trimethylolpropane), benzylhydrazine peroxide ("Nyper BMT" ") 0.2 parts, and 0.2 parts of γ-glycidoxypropylmethoxysilane (trade name" KBM-403 "manufactured by Shin-Etsu Chemical Co., Ltd.).

(3) Formation of Adhesive Layer The solution of the acrylic adhesive composition obtained in the above (2) was applied to poly (phenylene terephthalate) treated with polysiloxane so that the thickness of the adhesive layer after drying was 20 μm. One side of ethylene formate (PET) film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., thickness: 38 μm) was dried at 150 ° C. for 3 minutes to form an adhesive layer (adhesive layer). The storage elastic modulus G ′ of the adhesive layer (adhesive layer) at 23 ° C. was 1.1 × 10 ⁵ .

[Reference Example 5: Formation of Adhesive Layer] An adhesive layer of this reference example (Reference Example 5) was formed through the following procedures (1) to (3).

(1) Preparation of acrylic polymer solution: 77 parts of butyl acrylate, 20 parts of phenoxyethyl acrylate, 2 parts of N-ethylene-2-pyrrolidone, 0.5 parts of acrylic acid, and 4-hydroxybutyl acrylate 0.5 Parts and 0.1 parts of polymerization initiator 2,2'-azobisisobutyronitrile and 100 parts of ethyl acetate were put into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube and a cooler. Next, the contents of the four-necked flask were slowly stirred while introducing nitrogen to replace the nitrogen. Then, the liquid temperature in the 4-necked flask was maintained at about 55 ° C., and a polymerization reaction was performed for 8 hours to prepare an acrylic polymer solution.

(2) Preparation of acrylic adhesive composition A solution of the acrylic adhesive composition was prepared by mixing an isocyanate crosslinking agent (Mitsui with respect to 100 parts of the solid content of the acrylic polymer solution obtained in the above (1)). Chemical Co., Ltd. trade name "Takenate D160N", trimethylolpropane hexamethylene isocyanate) 0.1 part, benzyl peroxide (0.3N part of Nippon Oil Company, trade name "Nyper BMT"), γ-epoxy 0.2 parts of propoxypropylmethoxysilane (trade name "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.).

(3) Formation of Adhesive Layer The solution of the acrylic adhesive composition obtained in the above (2) was applied to a polyethylene terephthalate film (separator film: Mitsubishi) treated with a silicone release agent. One side of Chemical Polyester Film Co., Ltd. (trade name "MRF38") was dried at 150 ° C for 3 minutes to form an adhesive layer (adhesive layer) having a thickness of 20 µm on the surface of the separator film. The storage elastic modulus G ′ of the adhesive layer (adhesive layer) at 23 ° C. was 1.1 × 10 ⁵ .

[Example 1] A coating liquid for forming a low refractive index layer prepared in Reference Example 1 was applied to a thickness of 100 μm and was composed of an alicyclic structure resin film (Japanese ZEON Corporation, trade name "ZEONOR: ZF14 film"). The substrate (substrate film) was dried, and a low refractive index layer (refractive index: 1.18) with a film thickness of about 800 nm was formed. Then, the adhesive (the first adhesive layer) obtained in Reference Example 2 with a separator (75 μm) and a thickness of 25 μm was laminated on a low refractive index layer, and the accumulated light amount from the alicyclic structure resin film side was 300 mJ / cm ² of UV irradiation. Then, the alicyclic structure resin film (base film) is peeled from the aggregate of the adhesive (adhesive layer) and the low refractive index layer. Then, the adhesive agent (the second adhesive layer) obtained in Reference Example 3 with a thickness of 5 μm and another separator was attached to the surface on which the substrate film was peeled off, to obtain a low refractive index with a total thickness (overall thickness) of about 31 μm. The adhesive layer is bonded to the sheet. In addition, the total thickness (overall thickness) refers to the total thickness of the laminated body [excluding separated parts] of the first adhesive layer, the low-refractive index layer, and the second adhesive layer. The same applies to the following examples and comparative examples. . In the adhesive sheet with a low refractive index layer, the thickness of the adhesive (adhesive layer) (total thickness of the first adhesive layer and the second adhesive layer) is accounted for the total thickness (overall thickness) The ratio is about 97%. The optical characteristics of the low-refractive-index-containing adhesive sheet are shown in Table 1. In addition, the results of the luminance characteristics when the light guide plate and the reflection plate used for the LED side-light type backlight of the liquid crystal TV are integrated using the aforementioned adhesive sheet with a low refractive index layer are also shown in Table 1.

[Example 2] Let both the adhesives described in Example 1 be those obtained in Reference Example 3, and perform the same operation as in Example 1 to obtain a low refractive index layer with a total thickness (overall thickness) of about 11 μm. The sticky sheet. In the adhesive sheet with a low refractive index layer, the thickness of the adhesive (adhesive layer) (total thickness of the first adhesive layer and the second adhesive layer) is accounted for the total thickness (overall thickness) The ratio is about 91%. The optical characteristics of the low-refractive-index-containing adhesive sheet are shown in Table 1. In addition, the results of the luminance characteristics when the light guide plate and the reflection plate used for the LED side-light type backlight of the liquid crystal TV are integrated using the aforementioned adhesive sheet with a low refractive index layer are also shown in Table 1.

[Example 3] Let the first adhesive layer in the adhesive described in Example 1 be the adhesive (adhesive layer) obtained in Reference Example 4, and let the second adhesive layer be the adhesive (adhesive layer) obtained in Reference Example 5. Layer), and the same operation as in Example 1 was performed to obtain a low refractive index layer-containing adhesive sheet having a total thickness (overall thickness) of about 41 μm. The ratio of the thickness of the adhesive (adhesive layer) (total thickness of the first adhesive layer and the second adhesive layer) to the total thickness (overall thickness) of the adhesive sheet with a low refractive index layer The ratio is about 98%. The optical characteristics of the low-refractive-index-containing adhesive sheet are shown in Table 1. In addition, the results of the luminance characteristics when the light guide plate and the reflection plate used for the LED side-light type backlight of the liquid crystal TV are integrated using the aforementioned adhesive sheet with a low refractive index layer are also shown in Table 1.

[Comparative Example 1] The same operation as in Example 1 was performed except that the low-refractive index layer described in Example 1 was changed to a low-refractive index layer having a refractive index of 1.28 to obtain an adhesive sheet containing a low-refractive index layer. The optical characteristics of the low-refractive-index-containing adhesive sheet are shown in Table 1. In addition, the results of the luminance characteristics when the light guide plate and the reflection plate used for the LED side-light type backlight of the liquid crystal TV are integrated using the aforementioned adhesive sheet with a low refractive index layer are also shown in Table 1.

[Comparative Example 2] The light guide plate and the reflection plate were integrated only with an adhesive having a thickness of 25 μm that did not include a low refractive index layer. The measurement results of the optical characteristics are shown in Table 1.

[Comparative Example 3] The light guide plate and the reflecting plate were not integrated, and only an air layer (a low-refractive index layer and an adhesive layer was not used) was laminated together to measure optical characteristics. The results are shown in Table 1.

The luminance characteristics (brightness uniformity) in Table 1 were measured in the following manner.

(Measurement method of luminance characteristics) Between the light guide plate and the reflection plate of a TV having an LED side-light backlight, an adhesive sheet including a low refractive index layer described in the embodiment is introduced to integrate the light guide plate and the reflection plate. The TV was made completely white, and the luminance of each coordinate was measured from the incident side of the LED of the light guide plate to the terminal side using a spectroradiometer SR-UL2 (TOPCON TECHNOHOUSE company trade name).

The surface of the low-refractive-index layer (void layer) in the adhesive sheet containing the low-refractive index layer in Examples 1 to 3 and Comparative Example 1 was measured by the aforementioned measuring method using SPI3800 (trade name) manufactured by Seiko Instruments Inc. Coarseness Rz coefficient (ten-point average thickness). The measurement results are shown in Table 1.

[Table 1]

As shown in Table 1, in the case where the light guide plate and the reflective plate are integrated using the adhesive sheet with a low refractive index layer of Examples 1 and 2, light from the LED propagates from the incident side of the light guide plate to the terminal side. Brightness characteristics are good (uniform brightness). When the light guide plate and the reflecting plate are integrated, the reflecting plate is not warped and the workability is good. In contrast, in Comparative Example 1 in which the refractive index of the low refractive index layer exceeds 1.25, and Comparative Example 2 in which the low refractive index layer is not provided, when the light guide plate and the reflective plate are integrated, light propagates to the terminal side of the light guide plate There will be light leakage before, and the light does not reach the terminal side, so the brightness is not uniform. Further, in Comparative Example 3, in which an air layer was used instead of the adhesive sheet containing a low refractive index layer, the reflection plate was warped when the light guide plate and the reflection plate were integrated, and the work was difficult. Furthermore, the uneven brightness defect caused by the warpage of the reflecting plate also occurs.

In addition, the low-refractive-index layers used in Examples 1 to 3 had an extremely low refractive index of only 1.18 (that is, a high porosity), and the surface roughness Rz coefficient was still as small as 87 nm. This number of 87 nm is almost inferior to that of the low refractive index layer of Comparative Example 1. In the case of such a low refractive index layer having a small surface roughness Rz coefficient, as described above, the strength of the surface of the low refractive index layer is easily suppressed or prevented from being easily damaged when dropped. Therefore, it is also easy to suppress or prevent the degradation of the optical characteristics caused by the surface damage of the low refractive index layer.

Industrial Applicability As described above, according to the present invention, it is possible to provide a thin, low-refractive-index adhesive sheet containing a low-refractive index layer, a method for manufacturing an adhesive sheet including a low-refractive index layer, and an optical device. The application of the present invention is not particularly limited. For example, it can be widely used in optical components such as liquid crystal displays, organic EL displays, micro LED displays, and organic EL lighting.

This application claims priority based on Japanese Patent Application Japanese Patent Application No. 2017-016188 filed on January 31, 2017 and Japanese Patent Application Japanese Patent Application No. 2017-194713 filed on October 4, 2017. Its full disclosure is incorporated into this case.

10‧‧‧ Substrate

20‧‧‧ Low refractive index layer

20'‧‧‧ coated film (precursor layer)

20``‧‧‧Liquid containing smashed gel

30‧‧‧ Adhesive layer (adhesive)

40‧‧‧ Separator

101‧‧‧feed out roller

102‧‧‧Coating roller

105‧‧‧ take-up roll

106‧‧‧Roller

110‧‧‧Oven area

111‧‧‧hot air heater (heating mechanism)

120‧‧‧Chemical treatment zone

121‧‧‧ lamp (lighting mechanism) or hot air heater (heating mechanism)

201‧‧‧feed out roller

202‧‧‧Liquid storage area

203‧‧‧ doctor knife

204‧‧‧Micro-gravure

210‧‧‧ Oven area

211‧‧‧Heating mechanism

220‧‧‧Chemical treatment zone

221‧‧‧ lamp (lighting mechanism) or hot air heater (heating mechanism)

251‧‧‧ take-up roller

FIG. 1 is a cross-sectional view of a manufacturing process, which schematically illustrates an example of a method for manufacturing a low refractive index layer and a method for manufacturing an adhesive sheet including a low refractive index layer according to the present invention. FIG. 2 is a view schematically showing a part of the steps of the method for manufacturing the low-refractive index layer and the method for manufacturing the adhesive sheet including the low-refractive index layer of the present invention, and an example of an apparatus used therefor. FIG. 3 is a view schematically showing a part of the steps of the method for manufacturing the low-refractive index layer and the method for manufacturing the adhesive sheet containing the low-refractive index layer and another example of the device used in the present invention. FIG. 4 is a cross-sectional SEM image of an adhesive sheet containing a low refractive index layer according to an embodiment.

Claims (11)

An adhesive sheet with a low refractive index layer is characterized in that it has a first adhesive layer, a low refractive index layer, and a second adhesive layer laminated in this order, and the refractive index of the aforementioned low refractive index layer is 1.25 or less. For example, the adhesive sheet with a low refractive index layer according to claim 1, wherein the total thickness of the first adhesive layer and the second adhesive layer is larger than that of the first adhesive layer, the low refractive index layer, and the foregoing. The total thickness of the second adhesive layer is 85% or more. For example, the low-refractive index layer-containing adhesive sheet according to claim 1 or 2, wherein the aforementioned low-refractive index layer is a void layer. For example, the low-refractive-index-containing adhesive sheet according to claim 1 or 2 is located on at least one of the first adhesive layer and the second adhesive layer on the opposite side of the low-refractive index layer. Separator is attached on the surface. A method for manufacturing an adhesive sheet with a low refractive index layer is to manufacture the adhesive sheet with a low refractive index layer according to any one of claims 1 to 4. The aforementioned manufacturing method includes the following steps: A layer forming step of forming the aforementioned low refractive index layer on the transfer resin film substrate; and a transferring step of transferring the aforementioned low refractive index layer onto the adhesive layer. The manufacturing method according to claim 5, wherein the adhesive sheet with a low refractive index layer is the adhesive sheet containing a low refractive index layer as described in claim 4, and the manufacturing method further has a step of attaching a separate piece: at The adhesive layer is provided with a separator on a side opposite to the low refractive index layer. The manufacturing method according to claim 6, further comprising a step of peeling the resin film substrate for transfer: after the step of attaching the separator, peeling the resin film substrate for transfer. The method according to claim 7, wherein the peeling force between the separator and the adhesive layer is greater than the peeling force between the transfer resin film substrate and the low refractive index layer. According to the manufacturing method of any one of claims 5 to 8, the resin film base material for transfer is made of an alicyclic structure resin. A method for manufacturing an adhesive sheet with a low refractive index layer is to produce the adhesive sheet with a low refractive index layer according to any one of claims 1 to 4. The aforementioned manufacturing method includes the following steps: a coating step Directly coating a coating liquid that is a raw material of the low refractive index layer on the adhesive layer; and a drying step of drying the coating liquid. An optical component, characterized in that it comprises: a low refractive index layer-containing adhesive sheet according to any one of claims 1 to 4, a first optical function layer and a second optical function layer, and the aforementioned first optical function layer The second adhesive layer is attached to the low-refractive index layer on the side opposite to the low-refractive index layer, and the second optical function layer is attached to the low-refractive index layer On the opposite side.