WO2017033672A1 - Film optique stratifié, procédé de production de film optique stratifié, élément optique et dispositif d'affichage d'image - Google Patents

Film optique stratifié, procédé de production de film optique stratifié, élément optique et dispositif d'affichage d'image Download PDF

Info

Publication number
WO2017033672A1
WO2017033672A1 PCT/JP2016/072452 JP2016072452W WO2017033672A1 WO 2017033672 A1 WO2017033672 A1 WO 2017033672A1 JP 2016072452 W JP2016072452 W JP 2016072452W WO 2017033672 A1 WO2017033672 A1 WO 2017033672A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
void
cover layer
optical film
laminated optical
Prior art date
Application number
PCT/JP2016/072452
Other languages
English (en)
Japanese (ja)
Inventor
大輔 服部
恒三 中村
細川　和人
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2016149062A external-priority patent/JP6892744B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201680043414.XA priority Critical patent/CN107848251A/zh
Priority to KR1020177034375A priority patent/KR102418071B1/ko
Priority to US15/754,406 priority patent/US11536877B2/en
Priority to EP16839019.3A priority patent/EP3332959A4/fr
Publication of WO2017033672A1 publication Critical patent/WO2017033672A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a laminated optical film, a method for producing the laminated optical film, an optical member, and an image display device.
  • the gap between the two substrates becomes an air layer.
  • the air layer formed between the substrates functions as, for example, a low refractive layer that totally reflects light.
  • members such as a prism, a polarizing film, and a polarizing plate are arranged with a certain distance so that an air layer serving as a low refractive index layer is provided between the members. Yes.
  • each member in order to form an air layer in this way, each member must be arranged with a certain distance, and therefore, the members cannot be stacked in order, which takes time for manufacturing.
  • the overall thickness increases, which is contrary to the need for thin and light weight.
  • Non-Patent Document 1 the development of a laminated optical film that achieves both a high porosity (porosity) and excellent scratch resistance has not been reported.
  • an object of the present invention is to provide a laminated optical film, a method for producing a laminated optical film, an optical member, and an image display device that can achieve both a high porosity (porosity) and excellent scratch resistance.
  • the laminated optical film of the present invention comprises: A void layer is formed on the resin film, Further, a cover layer is directly formed on the gap layer, The void layer has a water contact angle of 90 ° or more and a porosity of 30% by volume or more.
  • the method for producing the laminated optical film of the present invention comprises: A method for producing the laminated optical film of the present invention, A void layer forming step of forming the void layer on the resin film, and The cover layer forming step of directly forming the cover layer on the gap layer is included.
  • the optical member of the present invention includes the laminated optical film of the present invention.
  • the image display device of the present invention includes the optical member of the present invention.
  • the laminated optical film of the present invention can achieve both high porosity (porosity) and excellent scratch resistance. Moreover, according to the method for producing a laminated optical film of the present invention, the laminated optical film of the present invention having both a high porosity (porosity) and excellent scratch resistance can be produced.
  • the laminated optical film of the present invention can be used for, for example, the optical member and the image display device of the present invention, but is not limited thereto and may be used for any application.
  • FIG. 1 is a process cross-sectional view schematically showing an example of a method for forming a void layer and a cover layer on a resin film in the present invention.
  • FIG. 2 schematically shows a part of steps in a method for producing a roll-shaped laminated optical film of the present invention (hereinafter sometimes referred to as “laminated optical film roll of the present invention”) and an example of an apparatus used therefor.
  • FIG. Drawing 3 is a figure showing typically a part of process in a manufacturing method of a lamination optical film roll of the present invention, and another example of an apparatus used therefor.
  • the porosity of the cover layer is 10% by volume or less.
  • the cover layer may be a layer formed by application of a water-based paint, for example.
  • the cover layer may be a layer having scratch resistance, for example.
  • the cover layer includes, for example, at least one of a water-soluble crosslinked body and a water-soluble polymer.
  • the cover layer is formed by, for example, directly applying a cover layer raw material liquid containing the cover layer raw material on the gap layer
  • the film may be transferred and formed after coating on the material.
  • at least one of heating and light irradiation may be performed.
  • the cover layer raw material liquid may be, for example, a liquid containing a compound that decomposes by heating or light irradiation to generate a base, for example, a liquid containing at least one of a monomer and an oligomer of a water-soluble alkoxysilane.
  • it may be a liquid containing a crosslinked product formed from at least one of a monomer and an oligomer of water-soluble alkoxysilane.
  • the void layer and the cover layer may include, for example, a water-soluble alkoxysilane monomer and / or oligomer, or a crosslinked product formed from a water-soluble alkoxysilane monomer and / or oligomer.
  • the void layer may be, for example, a layer formed of a porous body containing microporous particles and / or a layer formed of a fibrous substance such as nanofibers.
  • the refractive index of the void layer is, for example, 1.3 or less.
  • the cover layer forming step includes, for example, a cover layer raw material liquid coating step in which a cover layer raw material liquid containing the cover layer raw material is directly coated on the gap layer.
  • it includes a transfer step of transferring the cover layer prepared by coating the cover layer raw material liquid on another substrate onto the gap layer.
  • the cover layer raw material liquid after coating may be dried. The drying may be performed by heating, for example.
  • the cover layer is further formed by at least one of additional heating and light irradiation.
  • the cover layer raw material liquid may be, for example, a liquid containing a compound that decomposes by heating or light irradiation to generate a base.
  • the cover layer may be formed by further heating at 80 ° C. or lower for 1 hour or longer.
  • the cover layer raw material liquid is, for example, a liquid containing at least one of a water-soluble alkoxysilane monomer and oligomer.
  • the void layer is, for example, a porous body in which fine pore particles are chemically bonded.
  • the fine pore particles are Bond chemically.
  • the shape of the “particles” is not particularly limited, and may be, for example, spherical but may be other shapes.
  • the microporous particles may be, for example, sol-gel bead-like particles, nanoparticles (hollow nanosilica / nanoballoon particles), or the like.
  • the microporous particles are, for example, silicon compound microporous particles, and the porous body is a silicone porous body.
  • the fine pore particles of the silicon compound include, for example, a pulverized body of a gel-like silica compound.
  • the void layer there is a void layer made of a fibrous material such as nanofiber, and the fibrous material is entangled to form a layer including a void.
  • the method for producing such a void layer is not particularly limited.
  • the void layer is similar to the porous void layer in which the fine pore particles are chemically bonded to each other.
  • a void layer using hollow nanoparticles and nanoclay and a void layer formed using hollow nanoballoons and magnesium fluoride are also included.
  • these void layers may be void layers made of a single constituent material, or may be void layers made of a plurality of constituent materials.
  • the form of the gap layer may be a single form or a plurality of gap layers.
  • the porous structure of the porous body is, for example, an open cell structure having a continuous pore structure.
  • a containing liquid producing step for producing a containing liquid containing the fine pore particles for example, a coating step for coating the containing liquid on the resin film, and coating
  • the method further includes a drying step of drying the containing liquid, and in the void layer forming step, for example, the fine pore particles are chemically bonded to form the porous body.
  • the void layer forming step for example, the void layer is formed by chemically bonding the fine pore particles by the action of a catalyst.
  • the catalyst is, for example, a basic catalyst, and the containing liquid contains a base generator that generates the basic catalyst by, for example, light or heat.
  • the void layer is formed by chemically bonding the fine pore particles by light irradiation.
  • the void layer is formed by chemically bonding the fine pore particles by heating.
  • a void layer is formed on the resin film, and further, a cover layer is directly formed on the void layer, and the void layer has a water contact angle of 90 ° or more. And having a porosity of 30% by volume or more.
  • the laminated optical film of the present invention can achieve both high porosity (porosity) and excellent scratch resistance.
  • the reason (mechanism) is unknown, but is estimated from the following explanation, for example.
  • the scratch resistance of the void layer is improved by directly forming the cover layer on the void layer.
  • the void layer has a water contact angle of 90 ° or more and has a very high water repellency. For this reason, even if it forms a cover layer directly in the said void layer, it can suppress that the formation material of the said cover layer fills the void structure of the said void layer by the water-repellent effect of the said void layer.
  • the porosity of the said void layer is 30 volume% or more, and has a high porosity.
  • laminated optical film of the present invention that is not in the form of a roll and the laminated optical film of the present invention that is in the form of a roll (the aforementioned “laminated optical film roll of the present invention”) will be referred to simply as “laminated optical of the present invention.
  • laminated optical film of the present invention includes the laminated optical film roll of the present invention unless otherwise specified.
  • laminated optical film of this invention which is not roll-shaped can also be obtained, for example by cutting out a part of laminated optical film roll of this invention.
  • the laminated optical film of the present invention includes, for example, the gap layer, the cover layer, and the resin film, the gap layer is laminated on the resin film, and the cover layer is directly formed on the gap layer.
  • the laminated optical film is a low refractive material having the above characteristics.
  • the resin film is not particularly limited.
  • the resin include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP),
  • thermoplastic resins having excellent transparency such as triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), and polycarbonate (PC).
  • the void layer (hereinafter referred to as “the void layer of the present invention”) in the laminated optical film of the present invention may be laminated directly on the resin film or may be laminated via another layer, for example. Good.
  • the lower limit value of the water contact angle is 90 ° or more, for example, 95 ° or more, for example, 100 ° or more
  • the upper limit value of the water contact angle is, for example, 150 °.
  • it is 145 ° or less, for example, 140 ° or less
  • the range is, for example, 90 ° or more and 150 ° or less, for example, 95 ° or more and 145 ° or less, for example, 100 ° or more. 140 ° or less.
  • the contact angle is, for example, a value measured using a “fully automatic contact angle meter DM700” manufactured by Kyowa Interface Science Co., Ltd.
  • the void layer has a lower limit of porosity, for example, 30% by volume or more, 40% by volume or more, 45% by volume or more, 50% by volume or more, and an upper limit of the porosity, for example, 80% by volume or less. 70 volume% or less and 65 volume% or less, and the range thereof is, for example, 30 volume% or more and 80 volume% or less, for example, 40 volume% or more and 80 volume% or less, for example, 45 volume% or more and 70 volume% or less. For example, it is 50 volume% or more and 65 volume% or less.
  • the porosity can be measured by the following method based on the film density of the void layer.
  • the void layer of the present invention has, for example, a pore structure.
  • the pore size of the hole refers to the diameter of the major axis among the major axis diameter and minor axis diameter of the void (hole).
  • a preferable pore size is, for example, 2 nm to 500 nm.
  • the lower limit of the void size is, for example, 2 nm or more, 5 nm or more, 10 nm or more, 20 nm or more, and the upper limit thereof is, for example, 500 nm or less, 200 nm or less, 100 nm or less, and the range thereof is, for example, 2 nm to 500 nm, 5 nm to 500 nm, 10 nm to 200 nm, and 20 nm to 100 nm. Since a preferable void size is determined depending on the use of the void structure, for example, it is necessary to adjust the void size to a desired void size according to the purpose.
  • the void size can be evaluated by the following method, for example.
  • the void size can be quantified by a BET test method. Specifically, 0.1 g of the sample (the void layer of the present invention) was introduced into the capillary of a specific surface area measuring device (manufactured by Micromeritic: ASAP2020), and then dried under reduced pressure at room temperature for 24 hours. Degas the gas in the structure. The adsorption isotherm is drawn by adsorbing nitrogen gas to the sample, and the pore distribution is obtained. Thereby, the gap size can be evaluated.
  • the haze indicating transparency is not particularly limited, and the upper limit is, for example, less than 5% and less than 3%.
  • the lower limit is, for example, 0.1% or more and 0.2% or more, and the range is, for example, 0.1% or more and less than 5%, or 0.2% or more and less than 3%.
  • the haze can be measured by, for example, the following method.
  • the void layer (the void layer of the present invention) is cut into a size of 50 mm ⁇ 50 mm, and set in a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd .: HM-150) to measure haze.
  • the refractive index is generally the ratio of the transmission speed of the wavefront of light in a vacuum to the propagation speed in the medium is called the refractive index of the medium.
  • the upper limit of the refractive index of the void layer of the present invention is, for example, 1.3 or less, 1.25 or less, 1.2 or less, 1.15 or less, and the lower limit thereof is, for example, 1.05 or more, 1 0.06 or more and 1.07 or more, and the range is, for example, 1.05 or more and 1.3 or less, 1.06 or more and 1.25 or less, and 1.07 or more and 1.2 or less.
  • the refractive index means a refractive index measured at a wavelength of 550 nm unless otherwise specified.
  • the measuring method of a refractive index is not specifically limited, For example, it can measure with the following method.
  • a void layer (the void layer of the present invention) on the acrylic film, it is cut into a size of 50 mm ⁇ 50 mm, and this is bonded to the surface of a glass plate (thickness: 3 mm) with a cover layer.
  • the back surface central part (diameter of about 20 mm) of the glass plate is painted with black magic to prepare a sample that does not reflect on the back surface of the glass plate.
  • the sample is set in an ellipsometer (manufactured by JA Woollam Japan: VASE), the refractive index is measured under the conditions of a wavelength of 500 nm and an incident angle of 50 to 80 degrees, and the average value is taken as the refractive index.
  • the thickness of the void layer of the present invention is not particularly limited, and the lower limit thereof is, for example, 0.01 ⁇ m or more, 0.05 ⁇ m or more, 0.1 ⁇ m or more, 0.3 ⁇ m or more, and the upper limit thereof is, for example, 1000 ⁇ m or less. 100 ⁇ m or less, 80 ⁇ m or less, 50 ⁇ m or less, 10 ⁇ m or less, and the range is, for example, 0.01 to 100 ⁇ m.
  • the void layer includes, for example, a portion in which one type or a plurality of types of structural units forming a fine void structure are directly or indirectly chemically bonded. Also good. Further, for example, in the void layer, there may be a portion that is not chemically bonded even if the structural units are in contact with each other.
  • the structural units are “indirectly bonded” means that the structural units are bonded to each other through a small amount of a binder component equal to or less than the structural unit amount. The structural units are “directly bonded” means that the structural units are directly bonded without using a binder component or the like.
  • the bond between the structural units may be, for example, a bond through catalytic action.
  • the bond between the structural units may include, for example, a hydrogen bond or a covalent bond.
  • the structural unit forming the void layer may have a structure having at least one of a particle shape, a fiber shape, and a flat plate shape, for example.
  • the particulate and flat structural units may be made of an inorganic substance, for example.
  • the constituent element of the particulate structural unit may include at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr, for example.
  • the structure (structural unit) that forms the particles may be a real particle or a hollow particle, and specifically includes silicone particles, silicone particles having fine pores, silica hollow nanoparticles, silica hollow nanoballoons, and the like.
  • the fibrous structural unit is, for example, a nanofiber having a diameter of nanometer, and specifically includes cellulose nanofiber and alumina nanofiber.
  • Examples of the plate-like structural unit include nanoclay, specifically, nano-sized bentonite (for example, Kunipia F [trade name]) and the like.
  • the fibrous structural unit is not particularly limited, but for example, from the group consisting of carbon nanofiber, cellulose nanofiber, alumina nanofiber, chitin nanofiber, chitosan nanofiber, polymer nanofiber, glass nanofiber, and silica nanofiber. It may be at least one fibrous material selected.
  • the structural unit may be, for example, a fine pore particle.
  • the void layer is a porous body in which fine pore particles are chemically bonded. In the void layer forming step, for example, the fine pore particles are directly or indirectly chemically bonded. You may let them.
  • the particles may be bonded to each other through a binder having a fine pore particle amount or less.
  • the shape of the “particles” is not particularly limited, and may be, for example, spherical but may be other shapes.
  • the fine pore particles may be, for example, sol-gel beaded particles, nanoparticles (hollow nanosilica / nanoballoon particles), nanofibers, or the like, as described above.
  • the microporous particles are, for example, silicon compound microporous particles, and the porous body is a silicone porous body.
  • the fine pore particles of the silicon compound include, for example, a pulverized body of a gel-like silica compound.
  • the void layer there is a void layer made of a fibrous material such as nanofiber, and the fibrous material is entangled to form a layer including a void.
  • the method for producing such a void layer is not particularly limited.
  • the void layer is similar to the porous void layer in which the fine pore particles are chemically bonded to each other.
  • a void layer using hollow nanoparticles or nanoclay and a void layer formed using hollow nanoballoons or magnesium fluoride are also included.
  • these void layers may be void layers made of a single constituent material, or may be void layers made of a plurality of constituent materials.
  • the form of the gap layer may be a single form or a plurality of gap layers.
  • the void layer of the present invention is a layer formed of, for example, a porous body containing fine pore particles.
  • the fine pore particles include a pulverized product of a gel compound.
  • the pulverized materials are chemically bonded to each other.
  • the form of chemical bonding (chemical bonding) between the pulverized products is not particularly limited, and specific examples of the chemical bonding include, for example, cross-linking. The method of chemically bonding the pulverized products will be described in detail in the production method of the present invention.
  • the gel form of the gel compound is not particularly limited. “Gel” generally refers to a solidified state in which a solute has a structure in which it loses independent motility due to interaction and aggregates.
  • a wet gel includes a dispersion medium and a solute has a uniform structure in the dispersion medium.
  • a xerogel is a network structure in which the solvent is removed and the solute has voids.
  • the gel compound may be, for example, a wet gel or a xerogel.
  • Examples of the gel compound include a gelled product obtained by gelling a monomer compound.
  • the gel compound may be, for example, a gel silicon compound.
  • examples of the gel silicon compound include gelled products in which the monomer silicon compounds are bonded to each other, and specific examples include gelled products in which the monomer silicon compounds are bonded to each other through hydrogen bonding or intermolecular force bonding.
  • Examples of the bond include a bond by dehydration condensation. The gelation method will be described later in the production method of the present invention.
  • the volume average particle diameter showing the particle size variation of the fine pore particles is not particularly limited, and the lower limit thereof is, for example, 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.4 ⁇ m or more,
  • the upper limit is, for example, 2 ⁇ m or less, 1.5 ⁇ m or less, 1 ⁇ m or less, and the range is, for example, 0.1 ⁇ m to 2 ⁇ m, 0.2 ⁇ m to 1.5 ⁇ m, or 0.4 ⁇ m to 1 ⁇ m.
  • the volume average particle diameter is measured by, for example, a particle size distribution evaluation apparatus such as a dynamic light scattering method and a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM). Can do.
  • a particle size distribution evaluation apparatus such as a dynamic light scattering method and a laser diffraction method
  • an electron microscope such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM).
  • the particle size distribution showing the particle size variation of the fine pore particles is not particularly limited.
  • particles having a particle size of 0.4 ⁇ m to 1 ⁇ m are 50 to 99.9% by weight, 80 to 99.8% by weight, 90%.
  • particles having a particle size of 1 ⁇ m to 2 ⁇ m are 0.1 to 50% by weight, 0.2 to 20% by weight, or 0.3 to 10% by weight.
  • the particle size distribution can be measured by, for example, a particle size distribution evaluation apparatus or an electron microscope.
  • the type of the gel compound is not particularly limited.
  • the gel compound include a gel silicon compound.
  • the gel compound is a gel silicon compound will be described as an example, but the present invention is not limited thereto.
  • the cross-linking is, for example, a siloxane bond.
  • the siloxane bond include T2 bond, T3 bond, and T4 bond shown below.
  • T2 bond T3 bond
  • T4 bond shown below.
  • the void layer of the present invention may have any one kind of bond, may have any two kinds of bonds, or may have all three kinds of bonds.
  • the siloxane bonds the greater the ratio of T2 and T3, the more flexible and the expected properties of the gel can be expected, but the film strength becomes weaker.
  • the T4 ratio in the siloxane bond is large, the film strength is easily developed, but the void size becomes small and the flexibility becomes brittle. For this reason, for example, it is preferable to change the ratio of T2, T3, and T4 according to the application.
  • the void layer of the present invention for example, it is preferable that contained silicon atoms have siloxane bonds.
  • the ratio of unbonded silicon atoms (that is, residual silanol) in the total silicon atoms contained in the void layer is, for example, less than 50%, 30% or less, or 15% or less.
  • the monomer silicon compound is not particularly limited.
  • the silicon compound of the monomer include a compound represented by the following formula (1).
  • the gelled silicon compound is a gelled product in which monomeric silicon compounds are bonded to each other by hydrogen bonding or intermolecular force bonding as described above, the monomers of formula (1) are bonded to each other through, for example, each hydroxyl group. it can.
  • X is 2, 3 or 4
  • R 1 is a linear or branched alkyl group.
  • the carbon number of R 1 is, for example, 1-6, 1-4, 1-2.
  • Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • Examples of the branched alkyl group include an isopropyl group and an isobutyl group.
  • X is, for example, 3 or 4.
  • the silicon compound represented by the formula (1) include a compound represented by the following formula (1 ′) in which X is 3.
  • R 1 is the same as in the above formula (1), and is, for example, a methyl group.
  • the silicon compound is tris (hydroxy) methylsilane.
  • X is 3, the silicon compound is, for example, a trifunctional silane having three functional groups.
  • silicon compound represented by the formula (1) examples include a compound in which X is 4.
  • the silicon compound is, for example, a tetrafunctional silane having four functional groups.
  • the silicon compound of the monomer may be, for example, a hydrolyzate of a silicon compound precursor.
  • the silicon compound precursor is not particularly limited as long as it can generate the silicon compound by hydrolysis, and specific examples thereof include a compound represented by the following formula (2).
  • R 1 and R 2 are each a linear or branched alkyl group, R 1 and R 2 may be the same or different, R 1 s may be the same as or different from each other when X is 2. R 2 may be the same as or different from each other.
  • X and R 1 are, for example, the same as X and R 1 in the formula (1).
  • R 2 is, for example, can be exemplified for R 1 is incorporated in the formula (1).
  • the silicon compound precursor represented by the formula (2) include compounds represented by the following formula (2 ′) in which X is 3.
  • R 1 and R 2 are the same as those in the formula (2), respectively.
  • the silicon compound precursor is trimethoxy (methyl) silane (hereinafter also referred to as “MTMS”).
  • the silicon compound of the monomer is preferably the trifunctional silane from the viewpoint of excellent low refractive index, for example.
  • the silicon compound as the monomer is preferably the tetrafunctional silane from the viewpoint of excellent strength (for example, scratch resistance).
  • the silicon compound of the said monomer used as the raw material of the said gel-like silicon compound only 1 type may be used and 2 or more types may be used together, for example.
  • the silicon compound of the monomer for example, only the trifunctional silane may be included, only the tetrafunctional silane may be included, or both the trifunctional silane and the tetrafunctional silane may be included.
  • other silicon compounds may be included.
  • the ratio is not particularly limited and can be set as appropriate.
  • the void layer may contain, for example, a catalyst for chemically bonding one type or a plurality of types of structural units forming the fine void structure.
  • the content of the catalyst is not particularly limited, but is, 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 structural unit.
  • the void layer may further contain, for example, a crosslinking aid for indirectly bonding one type or a plurality of types of structural units forming the fine void structure.
  • the content of the crosslinking aid 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 with respect to the weight of the structural unit. .
  • the cover layer is not particularly limited.
  • the “cover layer” is, for example, a layer (covering layer) that covers the void layer, and is, for example, a layer having scratch resistance (overcoat layer).
  • the cover layer is formed directly on the gap layer.
  • directly forming may be formed, for example, by coating the cover layer on the gap layer, as described later.
  • the gap layer and the cover layer Are prepared separately, and the cover layer is transferred onto the gap layer.
  • the cover layer may be, for example, a cover layer composition liquid using a hydrocarbon solvent such as hexane or water as a solvent from the viewpoint of suppressing the influence on the solvent resistance since the solvent resistance of the void layer is low.
  • the void layer is, for example, a cover layer composition liquid using water as a solvent.
  • a composition in the said composition liquid what was illustrated by the composition (formation material) of the said space
  • the cover layer is, for example, a layer formed by applying a water-based paint.
  • a water-based paint is, for example, an aqueous solvent coating solution, and the aqueous solvent coating solution may be in the form of a solution or a dispersion.
  • the specific forming material of the water-based paint is not particularly limited, and may be, for example, those exemplified as the forming material for the void layer.
  • the cover layer preferably includes at least one of a water-soluble crosslinked body and a water-soluble polymer. Due to the high water repellency of the void layer, if the water-based paint that is the raw material of the cover layer is composed only of monomers and oligomers and has a low viscosity, the cover layer may not be formed on the void layer due to repelling during coating. is there. On the other hand, by including a water-soluble crosslinked product or a water-soluble polymer, the water-based paint can be made highly viscous to prevent repelling.
  • the water-soluble crosslinked body and the water-soluble polymer are not particularly limited, and for example, the water-soluble crosslinked body and the water-soluble polymer exemplified as the material for forming the void layer may be used.
  • the water-soluble crosslinked body include a crosslinked body formed from at least one of a monomer and an oligomer of a water-soluble alkoxysilane that is an inorganic-organic hybrid (hereinafter sometimes referred to as “water-soluble silane crosslinked body”). It is done.
  • the water-soluble silane crosslinked product is not particularly limited, and examples thereof include a silica compound crosslinked by the siloxane bond. Examples of the silica compound having the T2 bond, the T3 bond, and the T4 bond include Can be mentioned.
  • Examples of the water-soluble polymer include acrylic-based, vinyl alcohol-based, silicone-based, polyester-based, polyurethane-based, and polyether-based polymers, such as silicone-based polymers.
  • Examples of the silicone-based polymers include: Examples include polymers of alkoxysilanes represented by the formula (2).
  • polyvinyl alcohol-based or polyurethane-based, self-crosslinking acrylic emulsion and the like are preferable from the viewpoint of the stability of the aqueous polymer solution and the increase in viscosity.
  • the cover layer By including at least one of the water-soluble crosslinked body and the water-soluble polymer in the cover layer, for example, a hydrogen bond is formed between the constituent materials of the gap layer, and the adhesion between the gap layer and the cover layer Can be improved. Furthermore, by including a silane monomer and / or a silane oligomer in the cover layer, it is possible to improve the adhesion by making the cover layer and the void layer compatible.
  • At least one of these water-soluble crosslinked products and water-soluble polymers may be used alone or in combination (for example, mixing, lamination, etc.).
  • the cover layer is, for example, a layer formed by applying a cover layer raw material liquid containing the cover layer raw material on the gap layer and drying it, and then performing at least one of heating and light irradiation.
  • the cover layer raw material liquid is, for example, a liquid containing a compound that decomposes by heating or light irradiation to generate a base (hereinafter simply referred to as “base generating compound”), or a water-soluble alkoxysilane that is an inorganic-organic hybrid. It is a liquid containing at least one of a monomer and an oligomer, and may be a liquid containing both the base generating compound and at least one of the monomer and oligomer of the water-soluble alkoxysilane.
  • the base generating compound is not particularly limited, and may be those exemplified as the material for forming the void layer. Specifically, for example, a substance that generates a basic catalyst by heat (thermal base generator) And a substance that generates a basic catalyst by photoirradiation (photobase generator) and the like, for example, a photobase generator.
  • thermal base generator examples include urea.
  • Examples of the photobase generator include 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E) -1- [3- (2- Hydroxyphenyl) -2-propenoyl] piperidine ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, trade name WPBG-027), 1- (anthraquinone-2-yl) ethyl imidazolecarboxy Rate (1- (anthraquinon-2-yl) ethyl imidazolecarboxylate, trade name WPBG-140), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate (trade name WPBG-165), 1,2-diisopropyl- 3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (trade name WPBG-266), 1 , 2-dicy
  • the monomer of the water-soluble alkoxysilane is not particularly limited, and may be those exemplified as the material for forming the void layer. Specifically, for example, a silicon compound represented by the formula (2), etc.
  • Examples of the water-soluble alkoxysilane oligomer include an oligomer of a silicon compound represented by the formula (2).
  • the base generating compound in the cover layer for example, by a catalytic reaction using the photobase generator, the compounds in the cover layer (for example, monomers and oligomers of the water-soluble alkoxysilane) Then, chemical bonding (for example, cross-linking reaction) of the void layer with the microporous particles proceeds, and adhesion between the cover layer and the void layer is further improved.
  • the compounds in the cover layer for example, monomers and oligomers of the water-soluble alkoxysilane
  • chemical bonding for example, cross-linking reaction
  • the cover layer is formed by performing the strength improving step (void layer strength improving step) on the formed gap layer, and then forming the cover. You may perform a strength improvement process (cover layer strength improvement process) about a layer.
  • the gap layer strength improving step and the cover layer strength improving step may be performed separately.
  • the cover layer is formed, and the cover layer strength improving step is performed.
  • gap layer strength improvement process may be performed. That is, both the steps may be performed separately, or both steps may be performed simultaneously.
  • the compound in the cover layer and the microporous particles of the void layer can be gelled simultaneously,
  • the adhesion between the cover layer and the gap layer is improved, and the scratch resistance of the cover layer is also improved.
  • the thickness of the cover layer is not particularly limited, and is, for example, 50 nm to 10000 nm, 100 nm to 5000 nm, 150 nm to 4000 nm, or 200 nm to 3000 nm.
  • the porosity of the cover layer is not particularly limited, and is, for example, 10% by volume or less, preferably 9% by volume or less, or 8% by volume or less from the viewpoint of improving scratch resistance.
  • the porosity can be measured by a method based on the film density of the void layer described above.
  • the laminated optical film of the present invention is, for example, a roll body.
  • the laminated optical film of the present invention may further include a resin film as described above, for example, and the gap layer may be formed on the long resin film.
  • another long film may be laminated on the laminated optical film of the present invention, and another long resin film (for example, the laminated optical film of the present invention including the resin film and the gap layer). , Interleaving paper, release film, surface protective film, etc.), and then wound around a roll body.
  • the manufacturing method of the laminated optical film of the present invention is not particularly limited, for example, it can be manufactured by the manufacturing method of the present invention shown below.
  • the method for producing a laminated optical film of the present invention includes a void layer forming step of forming the void layer on the resin film, and a cover layer forming step of directly forming the cover layer on the void layer. It is characterized by including.
  • multilayer optical film of the said invention can be used for the manufacturing method of this invention.
  • the void layer is, for example, a porous body in which fine pore particles are chemically bonded.
  • the fine pore particles are Are chemically bonded.
  • the method for producing a laminated optical film of the present invention includes, for example, as described above, a containing liquid preparation step for producing a containing liquid containing the fine pore particles, a coating step for coating the containing liquid on the resin film, and Further, the method may further include a drying step of drying the coated liquid, and in the gap layer forming step, for example, the porous body may be formed by chemically bonding the microporous particles.
  • the void layer may be formed by chemically bonding the fine pore particles by the action of a catalyst.
  • the catalyst is, for example, a basic catalyst
  • the containing liquid contains a base generator that generates the basic catalyst by light or heat.
  • the void layer forming step may include a chemical treatment step in which the fine pore particles are chemically bonded to each other by light irradiation or heating to form the void layer, and the void layer is strengthened by heating or the like. You may perform the intensity
  • the void layer there is a void layer made of a fibrous material such as nanofiber, and the fibrous material is entangled to form a layer including a void.
  • the manufacturing method is the same as that of the fine pore particles.
  • a void layer using hollow nanoparticles and nanoclay, and a void layer formed using hollow nanoballoons and magnesium fluoride are also included.
  • microporous particle-containing liquid is not particularly limited, and is, for example, a suspension containing the microporous particles.
  • the fine pore particles are a pulverized product of a gel-like compound and the void layer is a porous body (preferably a silicone porous material) containing the crushed product of a gel-like compound will be described.
  • the present invention can also be carried out in the same manner when the fine pore particles are other than the pulverized product of the gel compound.
  • a void layer exhibiting an excellent low refractive index is formed.
  • the reason is estimated as follows, for example, but the present invention is not limited to this estimation.
  • the microporous particles used in the production method of the present invention are, for example, those obtained by pulverizing the gel silicon compound, so that the three-dimensional structure of the gel silicon compound before pulverization is dispersed in a three-dimensional basic structure. It is in the state. And in the manufacturing method of this invention, the precursor of the porous structure based on the said three-dimensional basic structure is formed by apply
  • the said void layer finally obtained can show the low refractive index which functions to the same extent as an air layer, for example.
  • the new three-dimensional structure is fixed in order to chemically bond the microporous particles.
  • the said void layer finally obtained is a structure which has a space
  • the void layer obtained by the production method of the present invention is useful, for example, as a substitute for the air layer, in terms of the function of low refraction, and in strength and flexibility.
  • the air layer for example, it is necessary to form an air layer between the members by stacking the members with a gap provided therebetween via a spacer or the like.
  • the void layer obtained by the production method of the present invention can exhibit low refraction properties that function to the same extent as the air layer, for example, only by being disposed at a target site. Therefore, as described above, for example, an optical member can be imparted with low refractive index that functions to the same extent as the air layer more easily and simply than the formation of the air layer.
  • the void layer formed by the production method of the present invention may have, for example, a pore structure (porous structure) as described above, for example, even if the pore structure is a continuous foam structure.
  • the open cell structure means, for example, that the porous structure of the silicone is three-dimensionally connected with the pore structure, and the internal voids of the pore structure can be said to be continuous.
  • the porous body has an open cell structure, it is possible to increase the porosity occupied in the bulk body, but when using closed cell particles such as hollow silica, the open cell structure is formed. Can not.
  • the void layer of the present invention is applied, for example, when silica sol particles (a crushed product of a gel-like silicon compound that forms a sol) are used, because the particles have a three-dimensional dendritic structure.
  • the dendritic particles settle and deposit, so that an open cell structure can be easily formed.
  • the void layer of the present invention more preferably forms a monolith structure in which the open cell structure has a plurality of pore distributions.
  • the monolith structure refers to, for example, a structure in which nano-sized fine voids exist and a hierarchical structure that exists as an open cell structure in which the nano voids are aggregated.
  • the monolith structure for example, it is possible to achieve both film strength and high porosity by providing a high porosity with coarse open-cell voids while providing film strength with fine voids.
  • the monolith structure can be formed by controlling the particle size distribution of the pulverized silica sol particles to a desired size.
  • the void layer is formed by chemically bonding the microporous particles by a catalytic reaction using a photobase generator.
  • chemical bonding for example, cross-linking
  • the base catalyst generated from the photobase generator remains in the precursor, chemical bonding (for example, cross-linking) between the microporous particles by heating or the like in the cover layer forming step. Reaction) further proceeds. This is considered to improve the strength of the void layer.
  • the fine pore particles are fine pore particles of a silicon compound (for example, a crushed product of a gel-like silica compound), and residual silanol groups (OH groups) are present in the void layer, the residual silanol It is thought that the groups are chemically bonded by a crosslinking reaction.
  • a silicon compound for example, a crushed product of a gel-like silica compound
  • residual silanol groups OH groups
  • the cover layer forming step includes, for example, a cover layer raw material liquid coating step in which a cover layer raw material liquid containing the cover layer raw material is directly coated on the gap layer, and A chemical treatment including a cover layer raw material liquid drying step for drying a liquid containing the coated cover layer raw material, and further forming a cover layer by at least one of heating and light irradiation after the cover layer raw material liquid drying step; After the step, the cover layer raw material liquid drying step, a strength improving step of forming the cover layer by heating at 80 ° C. or lower for 1 hour or longer may be included.
  • the cover layer raw material liquid (hereinafter may be simply referred to as “raw material liquid”) is not particularly limited, but is, for example, a compound that decomposes by heating or light irradiation to generate a base (hereinafter simply referred to as “base generating compound”). Or a liquid containing at least one of a water-soluble alkoxysilane monomer and oligomer, and the cover layer raw material liquid is at least one of the base-generating compound and the water-soluble alkoxysilane monomer and oligomer. One of both may be included.
  • Examples of the base generating compound include the base generating compounds exemplified in the cover layer of the laminated optical film of the present invention, and examples of the water-soluble alkoxysilane monomer and oligomer include the cover layer of the laminated optical film of the present invention. And monomers and oligomers of the water-soluble alkoxysilane exemplified above.
  • the production method of the present invention can be referred to the explanation of the laminated optical film of the present invention unless otherwise specified.
  • the description of the void layer of the present invention can be used for the fine pore particles, the monomer compound and the precursor of the monomer compound.
  • gap layer forming step [2.3.1 Details of gap layer forming step]
  • a void layer made of a porous body of silica particles will be described, but the method for forming the void layer is not limited to this.
  • the method for producing a laminated optical film of the present invention includes, for example, a contained liquid preparation step for producing a containing liquid containing the fine pore particles as described above.
  • a pulverized product of a gel-like silica compound is included.
  • the pulverized product is obtained, for example, by pulverizing a gel silicon compound (gel silicon compound).
  • the gelation of the silicon compound can be performed, for example, by hydrogen bonding or intermolecular force bonding of the silicon compounds.
  • Examples of the silicon compound include a silicon compound represented by the formula (1) described in the void layer of the present invention.
  • the monomers of the formula (1) can be hydrogen bonded or intermolecularly bonded via, for example, each hydroxyl group.
  • the silicon compound may be a hydrolyzate of the silicon compound precursor.
  • the silicon compound precursor represented by the formula (2) described in the void layer of the present invention It may be produced by hydrolysis.
  • the method for hydrolysis of the silicon compound precursor is not particularly limited, and can be performed, for example, by a chemical reaction in the presence of a catalyst.
  • the catalyst include acids such as oxalic acid and acetic acid.
  • an aqueous solution of oxalic acid is slowly dropped and mixed in a mixed solution (for example, suspension) of the silicon compound and dimethyl sulfoxide in a room temperature environment, and then stirred for about 30 minutes. Can be done.
  • a mixed solution for example, suspension
  • hydrolyzing the silicon compound precursor for example, by completely hydrolyzing the alkoxy group of the silicon compound precursor, further heating and immobilization after gelation / aging / void structure formation, It can be expressed efficiently.
  • the gelation of the silicon compound can be performed, for example, by a dehydration condensation reaction between the monomers.
  • the dehydration condensation reaction is preferably performed, for example, in the presence of a catalyst.
  • the catalyst include acid catalysts such as hydrochloric acid, oxalic acid, and sulfuric acid, and ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide, and the like.
  • a dehydration condensation catalyst such as a base catalyst.
  • the dehydration condensation catalyst is particularly preferably a base catalyst.
  • the amount of the catalyst added to the silicon compound is not particularly limited, and the catalyst is, for example, 0.1 to 10 mol, 0.05 to 7 mol, relative to 1 mol of the silicon compound, 0.1 to 5 moles.
  • the gelation of the silicon compound is preferably performed in a solvent, for example.
  • the ratio of the monomer compound in the solvent is not particularly limited.
  • the solvent include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), ⁇ -butyllactone (GBL), acetonitrile (MeCN), ethylene Examples thereof include glycol ethyl ether (EGEE).
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • DMAc N, N-dimethylacetamide
  • DMF dimethylformamide
  • GBL ⁇ -butyllactone
  • MeCN acetonitrile
  • EGEE glycol ethyl ether
  • one type of solvent may be used, or two or more types may be used in combination.
  • the solvent used for the gelation is also referred to as “gelling solvent”.
  • the gelation conditions are not particularly limited.
  • the treatment temperature for the solvent containing the monomer compound is, for example, 20-30 ° C., 22-28 ° C., 24-26 ° C., and the treatment time is, for example, 1-60 minutes, 5-40 minutes, 10-30. Minutes.
  • the process conditions in particular are not restrict
  • the gel-like silica compound obtained by the gelation is preferably subjected to an aging treatment after the gelation reaction.
  • the aging treatment for example, by further growing primary particles of a gel having a three-dimensional structure obtained by gelation, it is possible to increase the size of the particles themselves.
  • the contact state of the contacting neck portion can be increased from point contact to surface contact.
  • the gel subjected to the aging treatment as described above for example, increases the strength of the gel itself, and as a result, can improve the strength of the three-dimensional basic structure after pulverization.
  • the pore size of the void structure in which the three-dimensional basic structure is deposited can be prevented from shrinking due to solvent volatilization during the drying process.
  • the aging treatment can be performed, for example, by incubating the gel silica compound at a predetermined temperature for a predetermined time.
  • the predetermined temperature is not particularly limited, and the lower limit thereof is, for example, 30 ° C or higher, 35 ° C or higher, 40 ° C or higher, and the upper limit thereof is, for example, 80 ° C or lower, 75 ° C or lower, 70 ° C or lower.
  • the range is, for example, 30 to 80 ° C., 35 to 75 ° C., 40 to 70 ° C.
  • the predetermined time is not particularly limited, and the lower limit thereof is, for example, 5 hours or more, 10 hours or more, 15 hours or more, and the upper limit thereof is, for example, 50 hours or less, 40 hours or less, 30 hours or less.
  • the range is, for example, 5 to 50 hours, 10 to 40 hours, 15 to 30 hours.
  • the optimum conditions for aging are mainly the conditions under which, for example, the increase in the silica primary particle size and the increase in the contact area of the neck portion can be obtained. Furthermore, it is preferable to consider the boiling point of the solvent being used.
  • the aging temperature is too high, the solvent will be volatilized excessively, and the concentration of the coating liquid (gel solution) will increase, resulting in a three-dimensional void structure. There is a possibility that a problem such as closing of the pores of the liquid crystal will occur.
  • the aging temperature is too low, not only the effect of the aging described above can be obtained sufficiently, but also the temperature variation over time of the mass production process increases, and there is a possibility that a product with poor quality can be produced. There is.
  • the same solvent as the gelation treatment can be used, and specifically, the reaction product after the gelation treatment (that is, the solvent containing the gel silica compound) is applied as it is. It is preferable.
  • the number of moles of residual silanol groups contained in the gel (the gel-like silica compound, for example, the gel-like silicon compound) after the aging treatment after gelation is, for example, the added raw material (for example, the silicon compound precursor) )
  • the lower limit is, for example, 50% or more, 40% or more, 30% or more
  • the upper limit is, for example, 1% or less.
  • the range is, for example, 1 to 50%, 3 to 40%, or 5 to 30%.
  • the lower the number of moles of residual silanol groups the better. If the number of moles of silanol groups is too high, for example, there is a possibility that the void structure cannot be maintained before the precursor of the porous silicone material is crosslinked. On the other hand, if the number of moles of silanol groups is too low, for example, in the step of preparing the fine pore particle-containing liquid (for example, suspension) and / or the subsequent step, the pulverized product of the gel compound cannot be crosslinked, There is a possibility that sufficient film strength cannot be imparted.
  • a silanol group for example, when a silicon compound as a monomer is modified with various reactive functional groups, the same phenomenon can be applied to each functional group.
  • the gel silica compound obtained is pulverized.
  • the gel-like silica compound in the gelation solvent may be pulverized as it is, or after the gelation solvent is replaced with another solvent, the other solvent You may grind
  • the other solvent is also referred to as a “grinding solvent”.
  • the solvent for grinding is not particularly limited, and for example, an organic solvent can be used.
  • the organic solvent include solvents having a boiling point of 130 ° C. or lower, a boiling point of 100 ° C. or lower, and a boiling point of 85 ° C. or lower. Specific examples include isopropyl alcohol (IPA), ethanol, methanol, butanol, propylene glycol monomethyl ether (PGME), methyl cellosolve, acetone, dimethylformamide (DMF) and the like.
  • the pulverizing solvent may be, for example, one type or a combination of two or more types.
  • the combination of the gelling solvent and the grinding solvent is not particularly limited, and examples thereof include a combination of DMSO and IPA, DMSO and ethanol, DMSO and methanol, and a combination of DMSO and butanol.
  • a more uniform coating film can be formed, for example, in coating film formation described below.
  • the method for pulverizing the gel-like silica compound is not particularly limited, and may be performed by, for example, an ultrasonic homogenizer, a high-speed rotation homogenizer, a pulverizer using other cavitation phenomenon, or a pulverizer that obliquely collides liquids with each other at high pressure. it can.
  • a device for performing media grinding such as a ball mill physically destroys the void structure of the gel at the time of grinding
  • a cavitation type grinding device preferable for the present invention such as a homogenizer is, for example, a gel-less system.
  • the relatively weakly bonded silica particle bonding surface already contained in the three-dimensional structure is peeled off with a high shear force.
  • the obtained sol three-dimensional structure can hold, for example, a void structure having a certain range of particle size distribution, and can re-create the void structure by deposition during coating and drying.
  • the conditions for the pulverization are not particularly limited.
  • the gel can be pulverized without volatilizing the solvent by instantaneously applying a high-speed flow.
  • the work amount is excessive, for example, the sol particles become finer than the desired particle size distribution, and the void size deposited after coating and drying becomes fine, which may not satisfy the desired porosity. .
  • a liquid for example, a suspension
  • the fine pore particles for example, a pulverized product of a gel-like silica compound
  • a catalyst containing the fine pore particles and the catalyst is produced by adding a catalyst that chemically bonds the fine pore particles to each other. can do.
  • the addition amount of the catalyst is not particularly limited, but is, 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 fine pore particles.
  • the catalyst may be, for example, a catalyst that promotes cross-linking between the microporous particles.
  • the fine pore particles As a chemical reaction for chemically bonding the fine pore particles, it is preferable to use a dehydration condensation reaction of residual silanol groups contained in silica sol molecules. By promoting the reaction between the hydroxyl groups of the silanol group with the catalyst, it is possible to form a continuous film that cures the void structure in a short time.
  • the catalyst include a photoactive catalyst and a thermally active catalyst. According to the photoactive catalyst, for example, in the void layer forming step, the fine pore particles can be chemically bonded (for example, crosslinked) without being heated. According to this, for example, in the gap layer forming step, since the shrinkage of the entire gap layer hardly occurs, a higher porosity can be maintained.
  • a substance that generates a catalyst may be used.
  • a substance that generates a catalyst by light may be used, or in addition to or instead of the thermally active catalyst
  • a substance that generates water may be used.
  • the photocatalyst generator is not particularly limited, and examples thereof include a photobase generator (a substance that generates a basic catalyst by light irradiation), a photoacid generator (a substance that generates an acidic catalyst by light irradiation), and the like.
  • a photobase generator is preferred.
  • Examples of the photobase generator include 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E) -1- [3- (2- Hydroxyphenyl) -2-propenoyl] piperidine ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, trade name WPBG-027), 1- (anthraquinone-2-yl) ethyl imidazolecarboxy Rate (1- (anthraquinon-2-yl) ethyl imidazolecarboxylate, trade name WPBG-140), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate (trade name WPBG-165), 1,2-diisopropyl- 3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (trade name WPBG-266), 1 , 2-dicy
  • the trade names including “WPBG” are trade names of Wako Pure Chemical Industries, Ltd.
  • Examples of the photoacid generator include triallylsulfonyl compounds.
  • the catalyst for chemically bonding the fine pore particles is not limited to the photoactive catalyst and the photocatalyst generator, and may be a thermal catalyst or a thermal catalyst generator such as urea.
  • Examples of the catalyst that chemically bonds the fine pore particles include a base catalyst such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide, and an acid catalyst such as hydrochloric acid, acetic acid, and oxalic acid. Of these, base catalysts are preferred.
  • the catalyst or catalyst generator that chemically bonds the fine pore particles is added to, for example, a sol particle liquid (eg, suspension) containing the pulverized product (fine pore particles) immediately before coating.
  • a sol particle liquid eg, suspension
  • fine pore particles the pulverized product
  • it can be used as a mixed solution in which the catalyst or the catalyst generator is mixed with a solvent.
  • the mixed liquid is, for example, a coating liquid dissolved by directly adding to the sol particle liquid, a solution in which the catalyst or catalyst generator is dissolved in a solvent, or a dispersion in which the catalyst or catalyst generator is dispersed in a solvent.
  • the solvent is not particularly limited, and examples thereof include water, buffer solutions, and various organic solvents.
  • the microporous particles are a pulverized product of a gel-like silicon compound obtained from a silicon compound containing at least a trifunctional or lower saturated bond functional group
  • a crosslinking aid for indirectly bonding the fine pore particles may be added during the production process.
  • the cross-linking aid enters between the particles, and the particles and the cross-linking aid interact or bond with each other, so that it is possible to bond particles that are slightly apart from each other and efficiently increase the strength. It becomes possible.
  • the crosslinking aid a polycrosslinked silane monomer is preferable.
  • the multi-crosslinked silane monomer has, for example, an alkoxysilyl group having 2 or more and 3 or less, the chain length between alkoxysilyl groups may be 1 to 10 carbon atoms, and an element other than carbon May also be included.
  • crosslinking aid examples 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 (tri Methoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) -N-butyl-N-propyl-ethane-1
  • a containing liquid (for example, a suspension) containing the fine pore particles is applied onto a resin film (hereinafter sometimes referred to as “base material”) (coating step).
  • base material for example, various coating methods described later can be used, and the present invention is not limited thereto.
  • a coating film containing the fine pore particles and the catalyst can be formed by directly coating a liquid containing the fine pore particles (for example, a pulverized product of a gel-like silica compound) on the resin film.
  • the coating film can also be referred to as a coating layer, for example.
  • the coating film (coating layer) may be referred to as an “uncrosslinked film”.
  • the pulverized material in which the three-dimensional structure is destroyed settles and deposits, whereby a new three-dimensional structure is constructed.
  • the liquid containing the fine pore particles may not contain a catalyst that chemically bonds the fine pore particles.
  • the void layer forming step may be performed after or while spraying a catalyst that chemically bonds the fine pore particles to the coating film (uncrosslinked film).
  • the liquid containing the fine pore particles contains a catalyst that chemically bonds the fine pore particles, and the fine pore particles are produced by the action of the catalyst contained in the coating film (uncrosslinked film).
  • the porous body (void layer) may be formed by chemically bonding them together.
  • the solvent (hereinafter also referred to as “coating solvent”) is not particularly limited, and for example, an organic solvent can be used.
  • the organic solvent include solvents having a boiling point of 130 ° C. or lower. Specific examples include, for example, IPA, ethanol, methanol, butanol and the like, and the same solvents as the grinding solvent can be used.
  • the present invention includes a step of pulverizing the gel silica compound, in the step of forming the coating film (uncrosslinked film), for example, the pulverizing solvent containing the pulverized product of the gel silica compound, It may be used as it is.
  • the sol-like pulverized material dispersed in the solvent (hereinafter also referred to as “sol particle liquid”) is preferably applied onto the substrate.
  • the sol particle liquid of the present invention can continuously form a void layer having a film strength of a certain level or more by performing the chemical crosslinking after coating and drying on a substrate, for example.
  • the “sol” in the present invention refers to a state in which the silica sol particles having a nano three-dimensional structure retaining a part of the void structure are dispersed in a solvent and exhibit fluidity by pulverizing the three-dimensional structure of the gel. Say.
  • the concentration of the pulverized product in the solvent is not particularly limited, and for example, 0.3 to 50% (v / v), 0.5 to 30% (v / v), 1.0 to 10% (v / v) v).
  • concentration of the pulverized product is too high, for example, the fluidity of the sol particle solution is remarkably lowered, and there is a possibility that aggregates and coating streaks are generated during coating.
  • concentration of the pulverized product is too low, for example, not only does it take a considerable amount of time to dry the solvent of the sol particle liquid, but also the residual solvent immediately after drying increases, so the porosity decreases. There is a possibility that.
  • the physical properties of the sol are not particularly limited.
  • the shear viscosity of the sol is, for example, a viscosity of 100 cPa ⁇ s or less, a viscosity of 10 cPa ⁇ s or less, and a viscosity of 1 cPa ⁇ s or less at a shear rate of 10001 / s. If the shear viscosity is too high, for example, coating streaks may occur, and problems such as a decrease in the transfer rate of gravure coating may be observed. Conversely, when the shear viscosity is too low, for example, the wet coating (coating) thickness at the time of coating cannot be increased, and a desired thickness may not be obtained after drying.
  • the amount of the pulverized material applied to the substrate is not particularly limited, and can be appropriately set according to, for example, the desired thickness of the silicone porous body.
  • the amount of the pulverized material applied to the base material is, for example, 0.01 to 60000 ⁇ g per 1 m 2 of the base material. 0.1 to 5000 ⁇ g and 1 to 50 ⁇ g.
  • the preferable coating amount of the sol particle liquid is, for example, related to the concentration of the liquid, the coating method, etc., and thus it is difficult to define it uniquely. Is preferred.
  • the coating amount (coating amount) is too large, for example, the possibility of drying in a drying furnace before the solvent volatilizes increases. As a result, the nano-ground sol particles settle and deposit in the solvent, and the solvent is dried before the void structure is formed, so that void formation may be inhibited and the porosity may be greatly reduced.
  • the coating amount is too thin, there is a possibility that the risk of occurrence of coating repellency due to unevenness of the substrate, variation in hydrophilicity / hydrophobicity, or the like may increase.
  • the manufacturing method of this invention has a drying process which dries the coating film (non-crosslinked film
  • the drying process in the drying step for example, not only the solvent (solvent contained in the sol particle liquid) in the coating film (uncrosslinked film) is removed, but also the sol particles are precipitated and dried during the drying process.
  • the purpose is to deposit and form a void structure.
  • the drying treatment temperature is, for example, 50 to 250 ° C., 60 to 150 ° C., 70 to 130 ° C.
  • the drying treatment time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, 0 .3-3 minutes.
  • the drying process temperature and time are preferably lower and shorter in relation to, for example, continuous productivity and high porosity. If the conditions are too strict, for example, when the substrate is a resin film, the substrate is extended in a drying furnace by being close to the glass transition temperature of the substrate, and formed immediately after coating. Defects such as cracks may occur in the void structure. On the other hand, if the conditions are too loose, for example, since the residual solvent is included at the time of leaving the drying furnace, there is a possibility that defects in appearance such as scratches will occur when rubbing with the roll in the next process. is there.
  • the drying treatment may be, for example, natural drying, heat drying, or vacuum drying.
  • the drying method is not particularly limited, and for example, a general heating means can be used.
  • the heating means include a hot air fan, a heating roll, and a far infrared heater.
  • heat drying when it is premised on industrial continuous production, it is preferable to use heat drying.
  • a solvent having a low surface tension is preferable for the purpose of suppressing the generation of shrinkage stress accompanying the solvent volatilization during drying and the cracking phenomenon of the void layer (the silicone porous body).
  • the solvent examples include, but are not limited to, lower alcohols typified by isopropyl alcohol (IPA), hexane, perfluorohexane, and the like. Further, a small amount of a perfluoro-based surfactant or a silicon-based surfactant may be added to the IPA or the like to reduce the surface tension.
  • IPA isopropyl alcohol
  • hexane hexane
  • perfluorohexane perfluorohexane
  • silicon-based surfactant may be added to the IPA or the like to reduce the surface tension.
  • the fine pore particles are chemically bonded by the action of the catalyst to form the porous body (void layer) (void layer forming step).
  • the three-dimensional structure of the pulverized product in the coating film (uncrosslinked film) is fixed.
  • high temperature treatment at 200 ° C. or higher induces dehydration condensation of silanol groups and formation of siloxane bonds.
  • various additives that catalyze the above dehydration condensation reaction for example, a relatively low drying temperature of about 100 ° C. and several without causing damage to the base material (resin film), and several
  • the void structure can be continuously formed and fixed in a short processing time of less than a minute.
  • the method of chemically bonding is not particularly limited, and can be appropriately determined according to, for example, the type of the gel silicon compound.
  • the chemical bonding can be performed by, for example, chemical cross-linking between the pulverized products, and, for example, inorganic particles such as titanium oxide are added to the pulverized product. In this case, it is conceivable to chemically cross-link the inorganic particles and the pulverized product.
  • a biocatalyst such as an enzyme is supported, a site other than the catalytic active site and the pulverized product may be chemically crosslinked.
  • the present invention can be applied to, for example, not only a void layer (silicone porous body) formed by the sol particles but also an organic-inorganic hybrid void layer, a host guest void layer, and the like, but is not limited thereto.
  • the drying step may also serve as the gap layer forming step.
  • the void layer forming step of chemically bonding the fine pore particles by the action of the catalyst may be performed.
  • the catalyst is a photoactive catalyst, and the porous body (void layer) may be formed by chemically bonding the fine pore particles by light irradiation in the gap layer forming step. good.
  • the catalyst may be a thermally active catalyst, and the porous body (void layer) may be formed by chemically bonding the fine pore particles by heating in the gap layer forming step.
  • the chemical reaction may be performed by, for example, irradiating or heating the coating film containing the catalyst or the catalyst generator previously added to the sol particle liquid (for example, suspension), or on the coating film, It can be carried out by light irradiation or heating after spraying the catalyst, or by light irradiation or heating while spraying the catalyst or catalyst generator.
  • Integrated light intensity in the light irradiation is not particularly limited, @ in 360nm terms, for example, 200 ⁇ 800mJ / cm 2, 250 ⁇ 600mJ / cm 2 or 300 ⁇ 400mJ / cm 2,.
  • an integrated light amount of 200 mJ / cm 2 or more is good. Further, from the viewpoint of preventing the base material under the void layer from being damaged and generating thermal wrinkles, an integrated light amount of 800 mJ / cm 2 or less is good.
  • the conditions for the heat treatment are not particularly limited, and the heating temperature is, for example, 50 to 250 ° C., 60 to 150 ° C., 70 to 130 ° C., and the heating time is, for example, 0.1 to 30 minutes, 0.2 to 10 minutes and 0.3 to 3 minutes.
  • the step of drying the sol particle liquid (for example, suspension) applied as described above may also serve as the step of performing a chemical reaction in the presence of the catalyst. That is, in the step of drying the coated sol particle liquid (for example, suspension), the pulverized material (microporous particles) may be chemically bonded to each other by a chemical reaction in the presence of the catalyst. . In this case, the pulverized product (fine pore particles) may be further bonded to each other by further heating the coating film after the drying step. Further, it is assumed that the chemical reaction in the presence of the catalyst may occur in the step of preparing the microporous particle-containing liquid (for example, suspension) and the step of applying the microporous particle-containing liquid. Is done.
  • a solvent having a low surface tension is preferable for the purpose of suppressing the generation of shrinkage stress accompanying the solvent volatilization during drying and the cracking phenomenon of the void layer.
  • examples thereof include, but are not limited to, lower alcohols typified by isopropyl alcohol (IPA), hexane, perfluorohexane, and the like.
  • strength improvement process (aging process) which processes a void layer of this invention, for example, heat-aging, etc., and improves an intensity
  • the void layer of the present invention may be heated.
  • the temperature in the strength improving step (aging step) is, for example, 30 to 80 ° C., 35 to 70 ° C., 40 to 60 ° C., or 50 to 60 ° C.
  • the time for performing the aging step is, for example, 1 to 50 hr, 3 to 40 hr, 5 to 30 hr, or 7 to 25 hr.
  • the adhesive peel strength can be improved while suppressing the shrinkage of the void layer, and both high porosity and strength can be achieved.
  • cover layer forming step the cover layer is directly formed on the gap layer (cover layer forming step).
  • the cover layer may be formed on the gap layer by bonding the cover layer onto the gap layer.
  • the cover layer forming step is not particularly limited, and includes, for example, the cover layer raw material liquid coating step, the cover layer raw material liquid drying step, and the cover layer strength improving step (aging step).
  • cover layer raw material liquid containing the cover layer raw material is directly coated on the gap layer (cover layer raw material liquid coating step).
  • the cover layer raw material liquid coating step may use the same coating method as the coating step in the gap layer forming step.
  • the solvent exemplified in the coating solvent in the void layer forming step may be used as the coating solvent.
  • the liquid containing the coated raw material of the cover layer is dried (cover layer raw material liquid drying step).
  • the temperature and time of the drying treatment may be the temperature and time exemplified in the drying step in the gap layer forming step.
  • the cover layer is formed by at least one of heating and light irradiation after the cover layer raw material drying step.
  • the compound in the cover layer and the micropores of the void layer may be chemically bonded by light irradiation
  • the catalyst is a thermally active catalyst
  • the cover layer forming step the compound in the cover layer and the fine pore particles may be chemically bonded by heating.
  • the light irradiation amount in the light irradiation, the temperature of the heat treatment, and the heating time are not particularly limited, and may be the same as those exemplified in the gap layer forming step.
  • the strength of the formed cover layer may be improved by heating at 80 ° C. or lower for 1 hour or longer (strength improving step (aging step)).
  • the upper limit of the heating temperature is, for example, 80 ° C. or less, for example, 70 ° C. or less, for example, 60 ° C. or less
  • the lower limit of the heating temperature is, for example, 30 ° C. or more, for example, 35 ° C. or more.
  • it is 40 degreeC or more
  • the range is 30 degreeC or more and 80 degrees C or less, for example, 35 degreeC or more and 70 degrees C or less, for example, 40 degreeC or more and 60 degrees C or less.
  • the lower limit of the heating time is 1 hr (hour) or more, for example, 3 hr (hour) or more, for example, 4 hr (hour) or more
  • the upper limit is, for example, 50 hr or less, for example, 40 hr or less.
  • it is 30 hr or less
  • the range thereof is, for example, 1 hr or more and 50 hr or less, for example, 3 hr or more and 40 hr or less, for example, 4 hr or more and 30 hr or less.
  • the method for producing a laminated optical film of the present invention can be performed.
  • the laminated optical film produced by the production method of the present invention can be made into, for example, a roll-shaped porous body, and has advantages such as good production efficiency and easy handling.
  • the laminated optical film (void layer) of the present invention thus obtained may be further laminated with another film (layer) to form a laminated structure including the porous structure.
  • each component may be laminated via, for example, a pressure-sensitive adhesive or an adhesive.
  • the lamination may be performed by continuous processing using a long film (so-called Roll to Roll, etc.). May be laminated with batch processing.
  • FIG. 2 although forming the said silicone porous body and showing the process of bonding and winding up a protective film, when laminating
  • the illustrated film forming method is merely an example, and the present invention is not limited thereto.
  • the substrate may be the resin film described above in the explanation of the laminated optical film of the present invention.
  • the void layer of the present invention is obtained by forming the void layer on the substrate.
  • the said void layer is laminated
  • FIG. 1 schematically shows an example of a process in the manufacturing method of the present invention in which the gap layer and the cover layer are laminated in the above order on the base material (resin film).
  • the formation method of the said void layer is the coating process (1) which coats the sol particle liquid 20 '' of the said microporous particle
  • the sol particle liquid 20 ′′ is dried to form a dried coating film 20 ′ (2).
  • the coating film 20 ′ is subjected to chemical treatment (for example, cross-linking treatment) to form the void layer 20
  • chemical treatment for example, cross-linking treatment
  • a chemical treatment process for example, a crosslinking process (3), a strength improving process (4) for improving the strength of the void layer 20 to improve the strength, and a cover layer raw material liquid on the void layer 21
  • Cover layer coating process (cover layer raw material liquid coating process) (5) for directly coating 22 ′′, the coated cover layer raw material liquid 22 ′′ is dried, and the coating film 22 ′ after drying is formed.
  • Forming chemical process e.g., cross-linking step
  • a laminated optical film in which the gap layer 21 and the cover layer 23 are laminated in the above order on the resin film 10 can be manufactured.
  • the method for producing a laminated optical film of the present invention may or may not include steps other than the steps (1) to (8) as appropriate.
  • the step (4) may be combined with the cover layer step (8). That is, in the cover layer strength improving step (8), the strength of the void layer may be improved at the same time.
  • the coating method of the sol particle liquid 20 ′′ is not particularly limited, and a general coating method can be adopted.
  • the coating method (1) include a slot die method, a reverse gravure coating method, a micro gravure method (micro gravure coating method), a dip method (dip coating method), a spin coating method, a brush coating method, a roll coating method, Examples include a flexographic printing method, a wire bar coating method, a spray coating method, an extrusion coating method, a curtain coating method, and a reverse coating method.
  • the extrusion coating method, the curtain coating method, the roll coating method, the micro gravure coating method and the like are preferable from the viewpoints of productivity, coating film smoothness, and the like.
  • the coating amount of the sol particle liquid 20 ′′ is not particularly limited, and can be appropriately set so that, for example, the thickness of the void layer 20 is appropriate.
  • the thickness of the gap layer 21 is not particularly limited, and is as described above, for example.
  • the sol particle liquid 20 ′′ is dried (that is, the dispersion medium contained in the sol particle liquid 20 ′′ is removed), and the coating film after drying (a precursor of the void layer) 20 ′.
  • the conditions for the drying treatment are not particularly limited and are as described above.
  • the coating film 20 ′ containing the catalyst for example, photoactive catalyst, photocatalyst generator, thermal active catalyst or thermal catalyst generator
  • the void layer 20 is formed by heating and chemically bonding (for example, crosslinking) the fine pore particles in the coating film 20 ′.
  • the light irradiation or heating conditions in the chemical treatment step (3) are not particularly limited and are as described above.
  • the strength of the void layer 20 is improved.
  • the treatment temperature and treatment time in the strength improving step (4) are not particularly limited and are as described above.
  • this process (4) may be performed simultaneously with process (8) mentioned later, and a cover layer coating process (5) may be performed immediately after passing through a process process by process (3). At this time, winding may be performed once before the step (5), or the coating step (5) may be continuously performed without winding.
  • the coating method of the cover layer raw material liquid 22 ′′ is not particularly limited, and the method exemplified in the coating process (1) may be used. Further, the coating amount of the cover layer raw material liquid 22 ′′ is not particularly limited, and can be set as appropriate so that the thickness of the cover layer 22 is appropriate. The thickness of the cover layer 22 is not particularly limited and is as described above.
  • the conditions for the drying treatment for drying the cover layer raw material liquid 22 '' are not particularly limited, and may be the same drying treatment conditions as in the drying step (2).
  • the fine pore particles of the void layer 21 and the compound in the cover layer raw material liquid 22 ′′ are chemically bonded (for example, crosslinked) by light irradiation or heating,
  • the cover layer 22 is formed.
  • the light irradiation or heating conditions in the chemical treatment step (7) are not particularly limited, and may be the same as those in the chemical treatment step (3).
  • the strength of the cover layer 22 is improved.
  • the treatment temperature and treatment time in the strength improving step (8) are not particularly limited, but are as described above, for example.
  • FIG. 2 schematically shows an example of a slot die coating apparatus and a method for forming the void layer using the same.
  • FIG. 2 is a cross-sectional view, hatching is omitted for easy viewing.
  • each step in the method using this apparatus is performed while the substrate 10 is conveyed in one direction by a roller.
  • the conveyance speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, or 5 to 30 m / min.
  • a coating process (1) for coating the base material 10 with the sol particle liquid 20 ′′ is performed on the coating roll 102 while the base material 10 is fed out and conveyed from the feed roller 101, and then the oven zone.
  • the process proceeds to the drying step (2).
  • a preliminary drying process is performed after a coating process (1) and prior to a drying process (2).
  • the preliminary drying step can be performed at room temperature without heating.
  • the heating means 111 is used.
  • the heating means 111 as described above, a hot air fan, a heating roll, a far infrared heater, or the like can be used as appropriate.
  • the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the chemical treatment step (3) is performed in the chemical treatment zone 120.
  • the chemical treatment step (3) for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 121 disposed above and below the base material 10.
  • lamps (light irradiation means) 121 disposed above and below the base material 10.
  • a hot air fan 121 disposed above and below the substrate 10 using a hot air fan (heating means) instead of the lamp (light irradiation device) 121.
  • the fine pore particles in the coating film 20 ′ are chemically bonded to each other, and the void layer 20 is cured and strengthened.
  • the chemical treatment step (3) is performed after the drying step (2).
  • the chemical bonding between the microporous particles is caused at any stage of the production method of the present invention.
  • the drying step (2) may also serve as the chemical treatment step (3).
  • the chemical treatment step (3) may be further performed to further strengthen the chemical bonding between the microporous particles.
  • Bonding may occur in the step prior to the drying step (2) (for example, a preliminary drying step, a coating step (1), a step of preparing a coating liquid (for example, a suspension), etc.) Bonding may occur.
  • the strength improvement step (4) is performed in the strength improvement zone 130.
  • the air gap layer 20 may be heated using a hot air fan (heating means) 131 disposed on the base material 10.
  • heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
  • the coating step (5) is performed in the cover layer coating zone 140.
  • the cover layer raw material liquid is directly applied (coated) on the gap layer 20 by the cover layer coating means 141.
  • bonding such as a tape having a cover layer may be used instead of applying (coating) the cover layer raw material liquid.
  • the drying step (6) is performed using the heating means 151 in the oven zone 150.
  • a preliminary drying step may be performed at room temperature or the like, or the drying step (6) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the heating unit 151 the illustrated heating unit 111 may be used in the drying step (2).
  • the chemical treatment step (7) is performed using the light irradiation means or the heating means 161 in the chemical treatment zone 160.
  • the chemical treatment step (7) for example, the compound in the cover layer and the fine pore particles in the void layer are cross-linked by chemical bonding.
  • the strength improving step (8) is performed by the heating means 171 in the strength improving zone 170.
  • the heating temperature and the treatment time in the strength improving step (8) are as described above.
  • the strength improving step (aging step) (8) is performed, the strength of the cover layer is improved by the heating means 171 and the gap layer is also heated by the heating means 171 so that the strength improvement step of the gap layer is performed.
  • (Aging process) (4) may be performed.
  • the compound in the cover layer and the microporous particles of the void layer can be gelled at the same time, the adhesion between the cover layer and the void layer is improved, and the resistance of the cover layer is improved. Abrasion is also improved.
  • a laminated body is wound up with the winding roll 105.
  • the laminate may be further covered with a protective sheet fed from the roll 106, or may be covered with another layer formed of a long film instead of the protective sheet.
  • FIG. 3 schematically shows an example of a micro gravure method (micro gravure coat method) coating apparatus and a method for forming the void layer using the same.
  • the hatch is abbreviate
  • each step in the method using this apparatus is performed while the substrate 10 is conveyed in one direction by a roller, as in FIG.
  • the conveyance speed is not particularly limited, and is, for example, 1 to 100 m / min, 3 to 50 m / min, or 5 to 30 m / min.
  • a coating step (1) for coating the base material 10 with the sol particle liquid 20 ′′ is performed while the base material 10 is fed out and conveyed from the feed roller 201.
  • the coating of the sol 20 particle liquid ′′ is performed using a liquid reservoir 202, a doctor (doctor knife) 203, and a micro gravure 204 as shown in the figure.
  • the sol particle liquid 20 ′′ stored in the liquid reservoir 202 is attached to the surface of the microgravure 204, and further, the substrate 10 is controlled by the microgravure 204 while being controlled to a predetermined thickness by the doctor 203. Apply to the surface.
  • the microgravure 204 is merely an example, and the present invention is not limited to this, and any other coating means may be used.
  • a drying step (2) is performed. Specifically, as shown in the drawing, the base material 10 coated with the sol particle liquid 20 ′′ is conveyed into the oven zone 210 and heated by the heating means 211 in the oven zone 210 to be heated to the sol particle liquid 20 ′. 'Dry.
  • the heating means 211 may be the same as that shown in FIG. Further, for example, by dividing the oven zone 210 into a plurality of sections, the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the chemical treatment step (3) is performed in the chemical treatment zone 220.
  • the chemical treatment step (3) for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 221 disposed above and below the substrate 10.
  • lamps (light irradiation means) 221 disposed above and below the substrate 10.
  • a hot air fan (heating means) disposed above and below the substrate 10 using a hot air fan (heating means) instead of the lamp (light irradiation device) 221.
  • the substrate 10 is heated by the heating means 221.
  • the strength improvement step (4) is performed in the strength improvement zone 230.
  • the air gap layer 20 may be heated using hot air blowers (heating means) 231 disposed above and below the base material 10.
  • heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
  • the coating step (5) is performed in the cover layer coating zone 240.
  • the cover layer raw material liquid is directly applied (coated) on the gap layer 20 by the cover layer coating means 241. Further, as described above, instead of applying (coating) the cover layer raw material liquid, bonding (sticking) such as a tape having a cover layer may be used.
  • the drying step (6) is performed using the heating means 251 in the oven zone 250.
  • a preliminary drying step may be performed at room temperature or the like, or the drying step (6) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.
  • the heating means 251 the heating means 211 exemplified in the drying step (2) may be used.
  • the chemical treatment step (7) is performed using the light irradiation means or the heating means 261 in the chemical treatment zone 260.
  • the chemical treatment step (7) for example, the compound in the cover layer and the fine pore particles in the void layer are cross-linked by chemical bonding.
  • the strength improvement step (8) is performed in the strength improvement zone 270.
  • the heating temperature and the treatment time in the strength improving step (8) are as described above.
  • the optical member of the present invention includes the laminated optical film of the present invention as described above.
  • the optical member of the present invention is characterized by including the laminated optical film of the present invention, and other configurations are not limited at all.
  • the optical member of the present invention may further include other layers in addition to the laminated optical film of the present invention, for example.
  • the optical member of the present invention includes, for example, the laminated optical film of the present invention as a low reflection layer.
  • the optical member of the present invention may further include other layers in addition to the laminated optical film of the present invention, for example.
  • the optical member of the present invention has a roll shape, for example.
  • the image display device of the present invention includes the optical member of the present invention.
  • the image display device of the present invention is characterized by including the optical member of the present invention, and other configurations are not limited at all.
  • the image display device of the present invention may further include other configurations in addition to the optical member of the present invention, for example.
  • the laminated optical film of the present invention was produced as follows.
  • the number of parts of the substance used for manufacture is a weight part (mass part).
  • the concentration (%) is% by weight unless otherwise specified.
  • the gel-like compound is crushed into granules of several mm to several cm in size, IPA is added 4 times the amount of gel, lightly stirred, and then allowed to stand at room temperature for 6 hours to decant the solvent and catalyst in the gel. did. The same decantation treatment was repeated three times to complete the solvent replacement.
  • the gel compound was subjected to high-pressure medialess pulverization (homogenizer (trade name: UH-50, manufactured by SMT)) to prepare a sol solution.
  • homogenizer trade name: UH-50, manufactured by SMT
  • a sol solution When the volume average particle size indicating the particle size variation of the sol solution at this time was confirmed with a dynamic light scattering type nanotrack particle size analyzer (trade name UPA-EX150, manufactured by Nikkiso Co., Ltd.), 0.50 to 0.00. 70.
  • an IPA (isopropyl alcohol) solution of 1.5% by weight of a photobase generating catalyst (Wako Pure Chemical Industries, Ltd .: trade name WPBG266) is prepared, and 0.031 part with respect to 0.75 part of the sol particle liquid.
  • Addition 0.015 parts of 5% bis (trimethoxysilyl) ethane was added to prepare a coating solution.
  • the coating solution was applied to the surface of a polyethylene terephthalate substrate (resin film) to form a coating film.
  • the coated film was treated at a temperature of 100 ° C. for 1 minute and dried to form a 1 ⁇ m thick silicone porous film. Thereafter, the porous film was irradiated with UV (350 mJ / cm 2 (@ 360 nm)), and further heated at 60 ° C. for 20 hours to obtain a void layer.
  • Reference Example 4 Formation of void layer
  • the gel compound of Reference Example 1 was changed to a dispersion of acicular silica gel IPA-ST-UP (trade name of Nissan Chemical Industries, Ltd.), and the refractive index was 1.19. A low refractive index void layer was obtained.
  • Example 1 On the void layer obtained in Reference Example 1, 40 parts of polyvinyl alcohol (trade name JC40: degree of polymerization 4000) (9% aqueous solution), 60 parts of methyltrimethoxysilane, 15 parts of urea, 4 parts of BYK333 (trade name) The blended cover layer composition aqueous solution (cover layer raw material liquid) was applied and dried by heating at 100 ° C. for 4 minutes. Furthermore, 60 degreeC20hr aging was performed and the laminated optical film was obtained. This laminated optical film was a laminated optical film in which the gap layer was formed on the polyethylene terephthalate substrate (resin film), and a cover layer having a thickness of 1 ⁇ m was directly formed on the gap layer. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 2 A laminated optical film was obtained in the same manner as in Example 1 except that VC-10 (trade name) having a polymerization degree of 1000 was used instead of JC40 as the polyvinyl alcohol of the cover layer raw material liquid. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 3 A laminated optical film was obtained in the same manner as in Example 1 except that the composition of polyvinyl alcohol and methyltrimethoxysilane in the cover layer raw material liquid was changed to 30 parts polyvinyl alcohol and 70 parts methyltrimethoxysilane. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 4 A laminated optical film was obtained in the same manner as in Example 1 except that the composition of polyvinyl alcohol and methyltrimethoxysilane in the cover layer raw material liquid was changed to 70 parts polyvinyl alcohol and 30 parts methyltrimethoxysilane. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 5 A laminated optical film was obtained in the same manner as in Example 1 except that the cover layer raw material urea was changed to 7 parts of ⁇ -picoline. The evaluation results of this laminated optical film are shown in Table 1.
  • the composition of the raw material liquid for the cover layer is 95 parts of polyester polyol urethane polymer (17.5% aqueous solution) (trade name x-7096, manufactured by Nikka Chemical Co., Ltd.), 5 parts of methyltrimethoxysilane, 3 parts of urea, BYK3500 (trade name) )
  • a laminated optical film was obtained in the same manner as in Example 1 except for changing to 4 parts. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 7 A laminated optical film was obtained in the same manner as in Example 1 except that the cover layer raw material liquid was changed to a cationic self-crosslinking nanoemulsion (trade name UW-550CS: Taisei Fine Chemical). The evaluation results of this laminated optical film are shown in Table 1.
  • Example 8 A laminated optical film was obtained in the same manner as in Example 1 except that the cover layer raw material urea was changed to 7 parts of ⁇ -picoline. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 9 A laminated optical film was obtained in the same manner as in Example 1 except that the gap layer obtained in Reference Example 2 was used instead of the gap layer obtained in Reference Example 1. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 10 A laminated optical film was obtained in the same manner as in Example 1 except that the gap layer obtained in Reference Example 3 was used instead of the gap layer obtained in Reference Example 1. The evaluation results of this laminated optical film are shown in Table 1.
  • Example 11 A laminated optical film was obtained in the same manner as in Example 1 except that the gap layer obtained in Reference Example 4 was used instead of the gap layer obtained in Reference Example 1. The evaluation results of this laminated optical film are shown in Table 1.
  • This laminated optical film was a laminated optical film in which the gap layer was formed on the polyethylene terephthalate substrate (resin film), and a cover layer having a thickness of 1 ⁇ m was directly formed on the gap layer.
  • the evaluation results of this laminated optical film are shown in Table 1.
  • “scratch resistance” is the scratch resistance of the cover layer.
  • “Refractive index” and “porosity” are the refractive index and porosity of the void layer, respectively.
  • the “contact angle” is the contact angle of water in the void layer. The porosity of the void layer and the contact angle of water were measured by the methods described above.
  • the refractive index of the void layer and the scratch resistance of the cover layer were measured by the following evaluation method (measurement method).
  • a laminated optical film capable of achieving both a high porosity (porosity) and excellent scratch resistance could be obtained.
  • the porosity of the cover layer was measured by the same measurement method as that of the void layer, and all were 10% by volume or less.
  • the laminated optical film of the present invention can achieve both high porosity (porosity) and excellent scratch resistance. Moreover, according to the method for producing a laminated optical film of the present invention, the laminated optical film of the present invention having both a high porosity (porosity) and excellent scratch resistance can be produced.
  • the laminated optical film of the present invention can be used for, for example, the optical member and the image display device of the present invention, but is not limited thereto and may be used for any application.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'objectif de l'invention consiste à fournir un film optique stratifié pouvant obtenir à la fois un taux de vide (porosité) élevé et une excellente résistance aux rayures. Dans ce film optique stratifié, une couche de vide est formée sur un film de résine, et une couche de protection est formée directement sur la couche de vide. La couche de vide a un angle de contact avec l'eau de 90° ou plus et un taux de vide de 30 % en volume ou plus.
PCT/JP2016/072452 2015-08-24 2016-07-29 Film optique stratifié, procédé de production de film optique stratifié, élément optique et dispositif d'affichage d'image WO2017033672A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201680043414.XA CN107848251A (zh) 2015-08-24 2016-07-29 层叠光学膜、层叠光学膜的制造方法、光学构件及图像显示装置
KR1020177034375A KR102418071B1 (ko) 2015-08-24 2016-07-29 적층 광학 필름, 적층 광학 필름의 제조 방법, 광학 부재, 및 화상 표시 장치
US15/754,406 US11536877B2 (en) 2015-08-24 2016-07-29 Laminated optical film, method of producing laminated optical film, optical element, and image display
EP16839019.3A EP3332959A4 (fr) 2015-08-24 2016-07-29 Film optique stratifié, procédé de production de film optique stratifié, élément optique et dispositif d'affichage d'image

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2015165291 2015-08-24
JP2015-165291 2015-08-24
JP2015-176210 2015-09-07
JP2015176210 2015-09-07
JP2016149062A JP6892744B2 (ja) 2015-08-24 2016-07-28 積層光学フィルム、積層光学フィルムの製造方法、光学部材、および画像表示装置
JP2016-149062 2016-07-28

Publications (1)

Publication Number Publication Date
WO2017033672A1 true WO2017033672A1 (fr) 2017-03-02

Family

ID=58100057

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/072452 WO2017033672A1 (fr) 2015-08-24 2016-07-29 Film optique stratifié, procédé de production de film optique stratifié, élément optique et dispositif d'affichage d'image

Country Status (1)

Country Link
WO (1) WO2017033672A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023189556A1 (fr) * 2022-03-31 2023-10-05 日東電工株式会社 Stratifié optique, procédé de production de stratifié optique, élément optique et procédé de production d'élément optique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000284102A (ja) * 1999-03-30 2000-10-13 Fuji Photo Film Co Ltd 反射防止膜および画像表示装置
JP2002311204A (ja) * 2001-04-10 2002-10-23 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板および画像表示装置
JP2004354699A (ja) * 2003-05-29 2004-12-16 Konica Minolta Opto Inc 反射防止フィルム及び偏光板
JP2014046518A (ja) * 2012-08-30 2014-03-17 Asahi Kasei Chemicals Corp 積層体、偏光板、光学材料、表示装置及びタッチパネル

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000284102A (ja) * 1999-03-30 2000-10-13 Fuji Photo Film Co Ltd 反射防止膜および画像表示装置
JP2002311204A (ja) * 2001-04-10 2002-10-23 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板および画像表示装置
JP2004354699A (ja) * 2003-05-29 2004-12-16 Konica Minolta Opto Inc 反射防止フィルム及び偏光板
JP2014046518A (ja) * 2012-08-30 2014-03-17 Asahi Kasei Chemicals Corp 積層体、偏光板、光学材料、表示装置及びタッチパネル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023189556A1 (fr) * 2022-03-31 2023-10-05 日東電工株式会社 Stratifié optique, procédé de production de stratifié optique, élément optique et procédé de production d'élément optique

Similar Documents

Publication Publication Date Title
JP7309787B2 (ja) 低屈折率層、積層フィルム、低屈折率層の製造方法、積層フィルムの製造方法、光学部材および画像表示装置
JP6604781B2 (ja) 積層フィルムロールおよびその製造方法
JP6612563B2 (ja) シリコーン多孔体およびその製造方法
JP6599699B2 (ja) 触媒作用を介して結合した空隙構造フィルムおよびその製造方法
JP6563750B2 (ja) 塗料およびその製造方法
JP6713871B2 (ja) 光学積層体、光学積層体の製造方法、光学部材、画像表示装置、光学部材の製造方法および画像表示装置の製造方法
JP6713872B2 (ja) 積層フィルム、積層フィルムの製造方法、光学部材、画像表示装置、光学部材の製造方法および画像表示装置の製造方法
WO2017022690A1 (fr) Stratifié optique, procédé de fabrication de stratifié optique, élément optique, et dispositif d'affichage d'image
WO2016104762A1 (fr) Objet de silicone poreux et son procédé de production
TWI691732B (zh) 積層薄膜卷材及其製造方法
JP2021073491A (ja) 積層光学フィルム、積層光学フィルムの製造方法、光学部材、および画像表示装置
WO2017043496A1 (fr) Couche à faible indice de réfraction, film stratifié, procédé de fabrication d'une couche à faible indice de réfraction, procédé de fabrication d'un film stratifié, élément optique, et dispositif d'affichage d'image
WO2017057331A1 (fr) Procédé de production d'un liquide contenant un gel poreux, liquide contenant un gel poreux, procédé de production d'une couche de porosité élevée, procédé de production d'un corps poreux de porosité élevée et procédé de production d'un rouleau de film stratifié
JP2017064954A (ja) 積層フィルムの製造方法および画像表示装置の製造方法
JP2017057116A (ja) ゾル液およびその製造方法、積層フィルムの製造方法、積層フイルム、光学部材、並びに画像表示装置
WO2017033672A1 (fr) Film optique stratifié, procédé de production de film optique stratifié, élément optique et dispositif d'affichage d'image
WO2016104765A1 (fr) Matériau de revêtement d'argent et procédé de fabrication associé
JP2017066209A (ja) 塗工液、塗工液の製造方法、積層フィルムの製造方法および画像表示装置の製造方法
WO2017051831A1 (fr) Gel de production de film à faible indice de réfraction, procédé de production d'un gel de production de film à faible indice de réfraction, matériau de revêtement pour la production d'un film à faible indice de réfraction, procédé de production d'un matériau de revêtement pour la production d'un film à faible indice de réfraction, procédé de production de film stratifié et procédé de production de dispositif d'affichage d'image
TWI744241B (zh) 積層薄膜、積層薄膜之製造方法、光學構件、影像顯示裝置、光學構件之製造方法及影像顯示裝置之製造方法
WO2017131220A1 (fr) Procédé de production de liquide contenant un gel pulvérisé
WO2016104763A1 (fr) Film structuré à vides lié par action catalytique et procédé pour le fabriquer
WO2017131219A1 (fr) Liquide contenant un gel pulvérisé, et procédé de production de liquide contenant un gel pulvérisé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16839019

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20177034375

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15754406

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016839019

Country of ref document: EP