WO2017033672A1 - Laminated optical film, method for producing laminated optical film, optical member, and image display device - Google Patents

Laminated optical film, method for producing laminated optical film, optical member, and image display device Download PDF

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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
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WIPO (PCT)
Prior art keywords
layer
void
cover layer
optical film
laminated optical
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PCT/JP2016/072452
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French (fr)
Japanese (ja)
Inventor
大輔 服部
恒三 中村
細川 和人
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日東電工株式会社
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Priority claimed from JP2016149062A external-priority patent/JP6892744B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020177034375A priority Critical patent/KR102418071B1/en
Priority to US15/754,406 priority patent/US11536877B2/en
Priority to EP16839019.3A priority patent/EP3332959A4/en
Priority to CN201680043414.XA priority patent/CN107848251A/en
Publication of WO2017033672A1 publication Critical patent/WO2017033672A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/18Layered 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
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective 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.

Abstract

The purpose of the invention is to provide a laminated optical film capable of achieving both high voidage (porosity) and excellent scratch resistance. In this laminated optical film, a void layer is formed on a resin film, and a cover layer is directly formed on the void layer. The void layer has a water contact angle of 90° or greater and a voidage of 30 vol% or higher.

Description

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LAMINATED OPTICAL FILM, METHOD FOR PRODUCING LAMINATED OPTICAL FILM, OPTICAL MEMBER, AND IMAGE DISPLAY DEVICE
 本発明は、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に関する。 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.
 2つの基板を一定の間隔をあけて配置すると、両基板の間の空隙が空気層となる。このように、前記基板間に形成された空気層は、例えば、光を全反射する低屈折層として機能する。このため、例えば、光学フィルムであれば、プリズム、偏光フィルムおよび偏光板等の部材を、一定の距離を持って配置することにより、前記部材間に、低屈折率層となる空気層を設けている。しかし、このように、空気層を形成するには、各部材を一定の距離を持って配置しなければならないため、部材を、順に積層していくことができず、製造に手間がかかる。また、空気層を維持するためにスペーサー(枠)等を介して光学部材を組合わせると、全体の厚みが大きくなり、薄型軽量化のニーズに反することにもなる。 ¡When two substrates are arranged at a certain interval, the gap between the two substrates becomes an air layer. Thus, the air layer formed between the substrates functions as, for example, a low refractive layer that totally reflects light. For this reason, for example, in the case of an optical film, 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. However, 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. Further, when optical members are combined through spacers (frames) or the like to maintain the air layer, the overall thickness increases, which is contrary to the need for thin and light weight.
 このような問題を解消するために、部材間の空隙により形成される空気層に代わり、低屈折性を示す空隙層の適用が試みられている。(例えば、非特許文献1参照)。 In order to solve such a problem, an attempt is made to apply a void layer exhibiting low refractive index instead of an air layer formed by voids between members. (For example, refer nonpatent literature 1).
 前記部材開発において、低屈折性を示すために、空隙率を高く設計する必要がある。しかしながら、前記空隙率を高くすると、前記部材のかさ密度が低下するために強度が著しく低下し、耐擦傷性が低くなる問題がある。非特許文献1においても、得られた空隙層の膜強度が劣り、耐擦傷性が低い問題がある。このように、高い空隙率(空孔率)および優れた耐擦傷性を両立した積層光学フィルムの開発は、報告されていない。 In the above-mentioned member development, it is necessary to design the porosity to be high in order to show low refraction. However, when the porosity is increased, the bulk density of the member is lowered, so that the strength is remarkably lowered and the scratch resistance is lowered. Also in Non-Patent Document 1, there is a problem that the obtained void layer has poor film strength and low scratch resistance. Thus, the development of a laminated optical film that achieves both a high porosity (porosity) and excellent scratch resistance has not been reported.
 そこで、本発明は、高い空隙率(空孔率)および優れた耐擦傷性を両立可能な積層光学フィルム、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の提供を目的とする。 Therefore, 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.
 前記目的を達成するために、本発明の積層光学フィルムは、
 樹脂フィルム上に空隙層が形成され、
 さらに、前記空隙層上にカバー層が直接形成され、
 前記空隙層は、水の接触角が90°以上であり、かつ、空隙率が30体積%以上である。
In order to achieve the above object, 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.
 本発明の積層光学フィルムの製造方法は、
 前記本発明の積層光学フィルムの製造方法であって、
 前記樹脂フィルム上に前記空隙層を形成する空隙層形成工程、および、
 前記空隙層上に前記カバー層を直接形成する前記カバー層形成工程を含む。
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.
 本発明の光学部材は、前記本発明の積層光学フィルムを含む。 The optical member of the present invention includes the laminated optical film of the present invention.
 本発明の画像表示装置は、前記本発明の光学部材を含む。 The image display device of the present invention includes the optical member of the present invention.
 本発明の積層光学フィルムは、高い空隙率(空孔率)および優れた耐擦傷性を両立可能である。また、本発明の積層光学フィルムの製造方法によれば、高い空隙率(空孔率)および優れた耐擦傷性を両立した本発明の積層光学フィルムを製造することができる。本発明の積層光学フィルムは、例えば、本発明の光学部材および画像表示装置に用いることができるが、これに限定されず、どのような用途に用いても良い。 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.
図1は、本発明において、樹脂フィルム上に空隙層およびカバー層を形成する方法の一例を模式的に示す工程断面図である。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. 図2は、ロール状である本発明の積層光学フィルム(以下「本発明の積層光学フィルムロール」ということがある。)の製造方法における工程の一部と、それに用いる装置の一例とを模式的に示す図である。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. 図3は、本発明の積層光学フィルムロールの製造方法における工程の一部と、それに用いる装置の別の一例とを模式的に示す図である。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.
 本発明の積層光学フィルムは、例えば、前記カバー層の空隙率が10体積%以下である。 In the laminated optical film of the present invention, for example, the porosity of the cover layer is 10% by volume or less.
 本発明の積層光学フィルムまたは本発明の積層光学フィルムの製造方法において、前記カバー層は、例えば、水性塗料の塗工により形成された層であってもよい。また、前記カバー層は、例えば、耐擦傷性を有する層であってもよい。 In the laminated optical film of the present invention or the method for producing the laminated optical film of the present invention, 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.
 本発明の積層光学フィルムにおいて、前記カバー層は、例えば、水溶性架橋体および水溶性ポリマーの少なくとも一方を含む。 In the laminated optical film of the present invention, the cover layer includes, for example, at least one of a water-soluble crosslinked body and a water-soluble polymer.
 本発明の積層光学フィルムまたは本発明の積層光学フィルムの製造方法において、前記カバー層は、例えば、前記カバー層の原料を含むカバー層原料液を前記空隙層上に直接塗工成膜もしくは他基材上に塗工成膜したあと転写し形成してもよい。さらに前記カバー層を前記空隙層上に積層させた後、加熱および光照射の少なくとも一方を行ってもよい。前記カバー層原料液は、例えば、加熱または光照射により分解し塩基を発生する化合物を含む液であってもよいし、例えば、水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方を含む液であっても良いし、水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方から形成された架橋体を含む液であってもよい。 In the laminated optical film of the present invention or the method for producing the laminated optical film of the present invention, 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. Furthermore, after laminating the cover layer on the gap layer, 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. Alternatively, it may be a liquid containing a crosslinked product formed from at least one of a monomer and an oligomer of water-soluble alkoxysilane.
 本発明の積層光学フィルムにおいて、前記空隙層およびカバー層は、例えば、水溶性アルコキシシランのモノマーおよび/もしくはオリゴマー、または水溶性アルコキシシランのモノマーおよび/もしくはオリゴマーから形成された架橋体を含んでもよい。 In the laminated optical film of the present invention, 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. .
 本発明の積層光学フィルムにおいて、前記空隙層は、例えば、微細孔粒子を含む多孔体により形成された層および/もしくはナノファイバー等の繊維状物質により形成された層であっても良い。 In the laminated optical film of the present invention, 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.
 本発明の積層光学フィルムにおいて、前記空隙層の屈折率が、例えば、1.3以下である。 In the laminated optical film of the present invention, the refractive index of the void layer is, for example, 1.3 or less.
 本発明の積層光学フィルムの製造方法において、前記カバー層形成工程は、例えば、前記空隙層上に前記カバー層の原料を含むカバー層原料液を直接塗工製膜するカバー層原料液塗工工程もしくは別基材上で前記カバー層原料液を塗工成膜し作製したカバー層を前記空隙層上に転写する転写工程を含む。前記カバー層原料液を、前記空隙層上に直接または別基材上で塗工製膜する工程において、例えば、塗工後の前記カバー層原料液を乾燥させても良い。前記乾燥は、例えば、加熱により行っても良い。そして、前記カバー層原料液塗工工程または前記転写工程の後に、例えば、さらに、追加加熱および光照射の少なくとも一方により前記カバー層を形成する。前記カバー層原料液は、例えば、さらに、加熱または光照射により分解し塩基を発生する化合物を含む液であっても良い。前記カバー層原料液乾燥工程後に、例えば、さらに、80℃以下で1hr以上加熱して前記カバー層を形成しても良い。 In the method for producing a laminated optical film of the present invention, 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. Alternatively, 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. In the step of coating the cover layer raw material liquid on the gap layer directly or on another substrate, for example, the cover layer raw material liquid after coating may be dried. The drying may be performed by heating, for example. Then, after the cover layer raw material liquid coating step or the transfer step, 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. After the cover layer raw material liquid drying step, for example, the cover layer may be formed by further heating at 80 ° C. or lower for 1 hour or longer.
 本発明の積層光学フィルムの製造方法において、前記カバー層原料液は、例えば、水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方を含む液である。 In the method for producing a laminated optical film of the present invention, the cover layer raw material liquid is, for example, a liquid containing at least one of a water-soluble alkoxysilane monomer and oligomer.
 本発明の積層光学フィルムの製造方法において、前記空隙層は、例えば、微細孔粒子同士が化学的に結合している多孔体であり、前記空隙層形成工程において、例えば、前記微細孔粒子同士を化学的に結合させる。なお、本発明において、「粒子」(例えば、前記微細孔粒子等)の形状は、特に限定されず、例えば、球状でも良いが、他の形状でも良い。また、本発明において、前記微細孔粒子は、例えば、ゾルゲル数珠状粒子、ナノ粒子(中空ナノシリカ・ナノバルーン粒子)等であっても良い。本発明の積層光学フィルムの製造方法において、前記微細孔粒子が、例えば、ケイ素化合物の微細孔粒子であり、前記多孔体が、シリコーン多孔体である。前記ケイ素化合物の微細孔粒子が、例えば、ゲル状シリカ化合物の粉砕体を含む。また、前記空隙層の別形態として、ナノファイバー等の繊維状物質からなり、前記繊維状物質が絡まり合い空隙を含む形で層を成している空隙層がある。このような空隙層の製造方法は、特に限定されないが、例えば、前記微細孔粒子同士が化学的に結合している多孔体の空隙層と同様である。さらに他にも、中空ナノ粒子やナノクレイを用いた空隙層、中空ナノバルーンやフッ化マグネシウムを用いて形成した空隙層も含まれる。また、それらの空隙層は単一の構成物質からなる空隙層であってもよいし、また複数の構成物質からなる空隙層であってもよい。空隙層の形態も単一の前記形態であってもよいし、複数の前記形態からなる空隙層であってもよい。以下においては、主に、前記微細孔粒子同士が化学的に結合している多孔体の空隙層について説明する。 In the method for producing a laminated optical film of the present invention, the void layer is, for example, a porous body in which fine pore particles are chemically bonded. In the void layer forming step, for example, the fine pore particles are Bond chemically. In the present invention, the shape of the “particles” (for example, the fine pore particles) is not particularly limited, and may be, for example, spherical but may be other shapes. In the present invention, the microporous particles may be, for example, sol-gel bead-like particles, nanoparticles (hollow nanosilica / nanoballoon particles), or the like. In the method for producing a laminated optical film of the present invention, 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. Further, as another form of 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. For example, the void layer is similar to the porous void layer in which the fine pore particles are chemically bonded to each other. In addition, a void layer using hollow nanoparticles and nanoclay, and a void layer formed using hollow nanoballoons and magnesium fluoride are also included. In addition, 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. In the following, the porous void layer in which the fine pore particles are chemically bonded to each other will be mainly described.
 本発明の積層光学フィルムの製造方法において、前記多孔体の多孔質構造が、例えば、孔構造が連続した連泡構造体である。 In the method for producing a laminated optical film of the present invention, the porous structure of the porous body is, for example, an open cell structure having a continuous pore structure.
 本発明の積層光学フィルムの製造方法において、例えば、前記微細孔粒子を含む含有液を作製する含有液作製工程、前記樹脂フィルム上に前記含有液を塗工する塗工工程、および、塗工した前記含有液を乾燥させる乾燥工程をさらに含み、前記空隙層形成工程において、例えば、前記微細孔粒子同士を化学的に結合させて前記多孔体を形成する。前記空隙層形成工程において、例えば、前記微細孔粒子同士を触媒の作用により化学的に結合させて前記空隙層を形成する。前記触媒が、例えば、塩基性触媒であり、前記含有液が、例えば、光または熱により前記塩基性触媒を発生する塩基発生剤を含む。前記空隙層形成工程において、例えば、光照射により、前記微細孔粒子同士を化学的に結合させて前記空隙層を形成する。前記空隙層形成工程において、例えば、加熱により、前記微細孔粒子同士を化学的に結合させて前記空隙層を形成する。 In the method for producing a laminated optical film of the present invention, for example, a containing liquid producing step for producing a containing liquid containing the fine pore particles, 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. In 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. In the void layer forming step, for example, the void layer is formed by chemically bonding the fine pore particles by light irradiation. In the void layer forming step, for example, the void layer is formed by chemically bonding the fine pore particles by heating.
 以下、本発明について、例を挙げてさらに具体的に説明する。ただし、本発明は、以下の説明により限定および制限されない。 Hereinafter, the present invention will be described more specifically with examples. However, the present invention is not limited or restricted by the following description.
 本発明の積層光学フィルムは、前述のとおり、樹脂フィルム上に空隙層が形成され、さらに、前記空隙層上にカバー層が直接形成され、前記空隙層は、水の接触角が90°以上であり、かつ、空隙率が30体積%以上であることを特徴とする。 As described above, in the laminated optical film of the present invention, 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.
 本発明の積層光学フィルムは、前述のとおり、高い空隙率(空孔率)と、優れた耐擦傷性を両立可能である。この理由(メカニズム)は不明であるが、例えば、以下の説明により推測される。まず、前記空隙層上に前記カバー層を直接形成することにより、前記空隙層の耐擦傷性が向上する。そして、前記空隙層は、水の接触角が90°以上であり、撥水性が非常に高い。このため、前記空隙層に直接カバー層を形成しても、前記空隙層の撥水効果により、前記カバー層の形成材料が、前記空隙層の空隙構造を埋めることを抑制できる。また、前記空隙層の空隙率が30体積%以上であり、高い空隙率を有している。これにより、本発明の積層光学フィルムは、高空隙率と優れた耐擦傷性の両立が可能であると推測される。ただし、この理由(メカニズム)は、推測される理由(メカニズム)の一例であり、本発明を限定しない。 As described above, 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. First, 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. Moreover, the porosity of the said void layer is 30 volume% or more, and has a high porosity. Thereby, it is speculated that the laminated optical film of the present invention can achieve both high porosity and excellent scratch resistance. However, this reason (mechanism) is an example of a presumed reason (mechanism), and does not limit the present invention.
 なお、以下において、ロール状でない本発明の積層光学フィルムと、ロール状である本発明の積層光学フィルム(前記「本発明の積層光学フィルムロール」)とをまとめて、単に「本発明の積層光学フィルム」という場合がある。すなわち、以下において「本発明の積層光学フィルム」という場合は、特に断らない限り、本発明の積層光学フィルムロールをも含むものとする。なお、ロール状でない本発明の積層光学フィルムは、例えば、本発明の積層光学フィルムロールの一部を切り出して得ることも可能である。 In the following, the 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. Sometimes referred to as “film”. That is, in the following, the term “laminated optical film of the present invention” includes the laminated optical film roll of the present invention unless otherwise specified. In addition, the 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.
[1. 積層光学フィルム]
 本発明の積層光学フィルムは、例えば、前記空隙層および前記カバー層と前記樹脂フィルムとを含み、前記樹脂フィルム上に前記空隙層が積層され、さらに、前記空隙層上にカバー層が直接形成される。前記積層光学フィルムは、前記特性を有することを特徴とする低屈折材ということもできる。
[1. Laminated optical film]
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 It can also be said that the laminated optical film is a low refractive material having the above characteristics.
[樹脂フィルム]
 本発明の積層光学フィルムにおいて、前記樹脂フィルムは、特に制限されず、前記樹脂の種類は、例えば、ポリエチレンテレフタレート(PET)、アクリル、セルロースアセテートプロピオネート(CAP)、シクロオレフィンポリマー(COP)、トリアセチルセルロース(TAC)、ポリエチレンナフタレート(PEN)、ポリエチレン(PE)、ポリプロピレン(PP)、ポリカーボネート(PC)等の、透明性に優れた熱可塑性樹脂等が挙げられる。
[Resin film]
In the laminated optical film of the present invention, the resin film is not particularly limited. Examples of the resin include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP), Examples thereof include thermoplastic resins having excellent transparency such as triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), and polycarbonate (PC).
 本発明の積層光学フィルムにおける前記空隙層(以下「本発明の空隙層」という。)は、例えば、前記樹脂フィルム上に、直接積層されてもよいし、他の層を介して積層されてもよい。 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.
[空隙層]
 本発明の空隙層は、水の接触角の下限値が90°以上であり、例えば、95°以上であり、例えば、100°以上であり、前記水の接触角の上限値が例えば、150°以下であり、例えば、145°以下であり、例えば、140°以下であり、その範囲が例えば、90°以上150°以下であり、例えば、95°以上145°以下であり、例えば、100°以上140°以下である。前記接触角は、例えば、協和界面科学(株)製「全自動接触角計DM700」を用いて測定した値である。
[Void layer]
In the void layer of the present invention, the lower limit value of the water contact angle is 90 ° or more, for example, 95 ° or more, for example, 100 ° or more, and the upper limit value of the water contact angle is, for example, 150 °. For example, it is 145 ° or less, for example, 140 ° or less, and 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.
 前記空隙層は、空隙率の下限値が、例えば、30体積%以上、40体積%以上、45体積%以上、50体積%以上であり、前記空隙率の上限値が、例えば、80体積%以下、70体積%以下、65体積%以下であり、その範囲が、例えば、30体積%以上80体積%以下であり、例えば、40体積%以上80体積%以下であり、例えば、45体積%以上70体積%以下であり、例えば、50体積%以上65体積%以下である。前記空隙率は、前記空隙層の膜密度に基づいて、以下の方法により測定できる。 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.
(膜密度、空孔率の評価)
 基材(アクリルフィルム)上に空隙層(本発明の空隙層)を形成した後、この積層体における前記空隙層について、X線回折装置(RIGAKU社製:RINT-2000)を用いて全反射領域のX線反射率を測定する。そして、Intensityと2θのフィッティグを行った後に、前記積層体(空隙層・基材)の全反射臨界角から膜密度(g/cm)を算出し、さらに、空孔率(P%)を、以下の式より算出する。
 
    空孔率(P%)=45.48×膜密度(g/cm)+100(%)
 
(Evaluation of film density and porosity)
After forming a void layer (the void layer of the present invention) on a base material (acrylic film), the total reflection region of the void layer in this laminate using an X-ray diffractometer (RIGAKU, RINT-2000) was used. The X-ray reflectivity of is measured. And after performing Intensity and 2θ fitting, the film density (g / cm 3 ) is calculated from the total reflection critical angle of the laminate (void layer / base material), and the porosity (P%) is further calculated. Calculated from the following equation.

Porosity (P%) = 45.48 × membrane density (g / cm 3 ) +100 (%)
 本発明の空隙層は、例えば、孔構造を有している。前記孔の空隙サイズは、空隙(孔)の長軸の直径および短軸の直径のうち、前記長軸の直径を指すものとする。好ましい空孔サイズは、例えば、2nm~500nmである。前記空隙サイズは、その下限が、例えば、2nm以上、5nm以上、10nm以上、20nm以上であり、その上限が、例えば、500nm以下、200nm以下、100nm以下であり、その範囲が、例えば、2nm~500nm、5nm~500nm、10nm~200nm、20nm~100nmである。空隙サイズは、空隙構造を用いる用途に応じて、好ましい空隙サイズが決まるため、例えば、目的に応じて、所望の空隙サイズに調整する必要がある。空隙サイズは、例えば、以下の方法により評価できる。 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.
(空隙サイズの評価)
 本発明において、前記空隙サイズは、BET試験法により定量化できる。具体的には、比表面積測定装置(マイクロメリティック社製:ASAP2020)のキャピラリに、サンプル(本発明の空隙層)を0.1g投入した後、室温で24時間、減圧乾燥を行って、空隙構造内の気体を脱気する。そして、前記サンプルに窒素ガスを吸着させることで吸着等温線を描き、細孔分布を求める。これによって、空隙サイズが評価できる。
(Evaluation of gap size)
In the present invention, 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.
 本発明の空隙層において、透明性を示すヘイズは、特に制限されず、その上限は、例えば、5%未満であり、3%未満である。また、その下限は、例えば、0.1%以上、0.2%以上であり、その範囲が、例えば、0.1%以上5%未満、0.2%以上3%未満、である。 In the void layer of the present invention, 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%.
 前記ヘイズは、例えば、以下のような方法により測定できる。 The haze can be measured by, for example, the following method.
(ヘイズの評価)
 空隙層(本発明の空隙層)を50mm×50mmのサイズにカットし、ヘイズメーター(村上色彩技術研究所社製:HM-150)にセットしてヘイズを測定する。ヘイズ値については、以下の式より算出を行う。
 
    ヘイズ(%)=[拡散透過率(%)/全光線透過率(%)]×100(%)
 
(Evaluation of haze)
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 haze value is calculated from the following formula.

Haze (%) = [diffuse transmittance (%) / total light transmittance (%)] × 100 (%)
 前記屈折率は、一般に、真空中の光の波面の伝達速度と、媒質内の伝播速度との比を、その媒質の屈折率という。本発明の空隙層の屈折率は、その上限が、例えば、1.3以下、1.25以下、1.2以下、1.15以下であり、その下限が、例えば、1.05以上、1.06以上、1.07以上であり、その範囲が、例えば、1.05以上~1.3以下、1.06以上~1.25以下、1.07以上~1.2以下である。 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.
 本発明において、前記屈折率は、特に断らない限り、波長550nmにおいて測定した屈折率をいう。また、屈折率の測定方法は、特に限定されず、例えば、下記の方法により測定できる。 In the present invention, the refractive index means a refractive index measured at a wavelength of 550 nm unless otherwise specified. Moreover, the measuring method of a refractive index is not specifically limited, For example, it can measure with the following method.
(屈折率の評価)
 アクリルフィルムに空隙層(本発明の空隙層)を形成した後に、50mm×50mmのサイズにカットし、これをカバー層でガラス板(厚み:3mm)の表面に貼合する。前記ガラス板の裏面中央部(直径20mm程度)を黒マジックで塗りつぶして、前記ガラス板の裏面で反射しないサンプルを調製する。エリプソメーター(J.A.Woollam Japan社製:VASE)に前記サンプルをセットし、500nmの波長、入射角50~80度の条件で、屈折率を測定し、その平均値を屈折率とする。
(Evaluation of refractive index)
After forming 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.
 本発明の空隙層の厚みは、特に制限されず、その下限が、例えば、0.01μm以上、0.05μm以上、0.1μm以上、0.3μm以上であり、その上限が、例えば、1000μm以下、100μm以下、80μm以下、50μm以下、10μm以下であり、その範囲が、例えば、0.01~100μmである。 The thickness of the void layer of the present invention is not particularly limited, and the lower limit thereof is, for example, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.3 μm or more, and the upper limit thereof is, for example, 1000 μm or less. 100 μm or less, 80 μm or less, 50 μm or less, 10 μm or less, and the range is, for example, 0.01 to 100 μm.
 本発明の積層光学フィルムにおいて、前記空隙層は、例えば、微細な空隙構造を形成する一種類または複数種類の構成単位同士が直接的または間接的に化学的に結合している部分を含んでいても良い。また、例えば、前記空隙層において、構成単位同士が接触していても化学的に結合していない部分が存在していても良い。また、本発明において、構成単位同士が「間接的に結合している」とは、構成単位量以下の少量のバインダー成分を仲介して構成単位同士が結合していることを指す。構成単位同士が「直接的に結合している」とは、構成単位同士が、バインダー成分等を介さずに直接結合していることを指す。前記構成単位同士の結合は、例えば、触媒作用を介した結合でも良い。前記構成単位同士の結合は、例えば、水素結合もしくは共有結合を含んでいても良い。本発明において、前記空隙層を形成する前記構成単位は、例えば、粒子状、繊維状、平板状の少なくとも一つの形状を有する構造からなっていても良い。前記粒子状および平板状の構成単位は、例えば、無機物からなっていても良い。また、前記粒子状構成単位の構成元素は、例えば、Si、Mg、Al、Ti、ZnおよびZrからなる群から選択される少なくとも一つの元素を含んでいても良い。粒子状を形成する構造体(構成単位)は、実粒子でも中空粒子でもよく、具体的にはシリコーン粒子や微細孔を有するシリコーン粒子、シリカ中空ナノ粒子やシリカ中空ナノバルーン等が挙げられる。繊維状の構成単位は、例えば、直径がナノサイズのナノファイバーであり、具体的にはセルロースナノファイバーやアルミナナノファイバー等が挙げられる。平板状の構成単位は、例えば、ナノクレイが挙げられ、具体的にはナノサイズのベントナイト(例えばクニピアF[商品名])等が挙げられる。前記繊維状の構成単位は、特に限定されないが、例えば、カーボンナノファイバー、セルロースナノファイバー、アルミナナノファイバー、キチンナノファイバー、キトサンナノファイバー、ポリマーナノファイバー、ガラスナノファイバー、およびシリカナノファイバーからなる群から選択される少なくとも一つの繊維状物質であっても良い。また、前記構成単位は、例えば、微細孔粒子であっても良い。例えば、前記空隙層は、微細孔粒子同士が化学的に結合している多孔体であり、前記空隙層形成工程において、例えば、前記微細孔粒子同士を直接的もしくは間接的に化学的な結合をさせても良い。この時の間接的とは、前述のとおり、例えば、少量のバインダー成分のことを指し、微細孔粒子量以下のバインダーを介して粒子同士が結合していてもよい。なお、本発明において、「粒子」(例えば、前記微細孔粒子等)の形状は、特に限定されず、例えば、球状でも良いが、他の形状でも良い。また、本発明において、前記微細孔粒子は、例えば、前述のとおり、ゾルゲル数珠状粒子、ナノ粒子(中空ナノシリカ・ナノバルーン粒子)、ナノ繊維等であっても良い。本発明の積層フィルムの製造方法において、前記微細孔粒子が、例えば、ケイ素化合物の微細孔粒子であり、前記多孔体が、シリコーン多孔体である。前記ケイ素化合物の微細孔粒子が、例えば、ゲル状シリカ化合物の粉砕体を含む。また、前記空隙層の別形態として、ナノファイバー等の繊維状物質からなり、前記繊維状物質が絡まり合い空隙を含む形で層を成している空隙層がある。このような空隙層の製造方法は、特に限定されないが、例えば、前記微細孔粒子同士が化学的に結合している多孔体の空隙層と同様である。さらに他にも、前述のとおり、中空ナノ粒子やナノクレイを用いた空隙層、中空ナノバルーンやフッ化マグネシウムを用いて形成した空隙層も含まれる。また、それらの空隙層は単一の構成物質からなる空隙層であってもよいし、また複数の構成物質からなる空隙層であってもよい。空隙層の形態も単一の前記形態であってもよいし、複数の前記形態からなる空隙層であってもよい。 In the laminated optical film of the present invention, 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. Further, in the present invention, 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. In the present invention, 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. In addition, 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. For example, 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. Indirect at this time refers to, for example, a small amount of a binder component as described above, and the particles may be bonded to each other through a binder having a fine pore particle amount or less. In the present invention, the shape of the “particles” (for example, the fine pore particles) is not particularly limited, and may be, for example, spherical but may be other shapes. In the present invention, the fine pore particles may be, for example, sol-gel beaded particles, nanoparticles (hollow nanosilica / nanoballoon particles), nanofibers, or the like, as described above. In the method for producing a laminated film of the present invention, 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. Further, as another form of 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. For example, the void layer is similar to the porous void layer in which the fine pore particles are chemically bonded to each other. Furthermore, as described above, a void layer using hollow nanoparticles or nanoclay, and a void layer formed using hollow nanoballoons or magnesium fluoride are also included. In addition, 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.
 本発明の空隙層は、例えば、微細孔粒子を含む多孔体により形成された層である。前記微細孔粒子としては、例えば、ゲル状化合物の粉砕物が挙げられる。前記多孔体は、例えば、前記粉砕物同士が化学的に結合している。本発明の空隙層において、前記粉砕物同士の化学的な結合(化学結合)の形態は、特に制限されず、前記化学結合の具体例は、例えば、架橋結合等が挙げられる。なお、前記粉砕物同士を化学的に結合させる方法は、本発明の製造方法において、詳細を述べる。 The void layer of the present invention is a layer formed of, for example, a porous body containing fine pore particles. Examples of the fine pore particles include a pulverized product of a gel compound. In the porous body, for example, the pulverized materials are chemically bonded to each other. In the void layer of the present invention, 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.
 前記ゲル状化合物のゲル形態は、特に制限されない。「ゲル」とは、一般に、溶質が、相互作用のために独立した運動性を失って集合した構造をもち、固化した状態をいう。また、ゲルの中でも、一般に、ウェットゲルは、分散媒を含み、分散媒中で溶質が一様な構造をとるものをいい、キセロゲルは、溶媒が除去されて、溶質が、空隙を持つ網目構造をとるものをいう。本発明において、前記ゲル状化合物は、例えば、ウェットゲルでもよいし、キセロゲルでもよい。 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. In addition, among gels, generally, 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 one that takes In the present invention, the gel compound may be, for example, a wet gel or a xerogel.
 前記ゲル状化合物は、例えば、モノマー化合物をゲル化したゲル化物が挙げられる。前記ゲル状化合物は、例えば、ゲル状ケイ素化合物であっても良い。具体的に、前記ゲル状ケイ素化合物は、例えば、前記モノマーのケイ素化合物が互いに結合したゲル化物、具体例として、前記モノマーのケイ素化合物が互いに水素結合または分子間力結合したゲル化物が挙げられる。前記結合は、例えば、脱水縮合による結合が挙げられる。前記ゲル化の方法は、本発明の製造方法において後述する。 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. Specifically, 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.
 本発明の空隙層において、前記微細孔粒子の粒度バラツキを示す体積平均粒子径は、特に制限されず、その下限が、例えば、0.1μm以上、0.2μm以上、0.4μm以上であり、その上限が、例えば、2μm以下、1.5μm以下、1μm以下であり、その範囲が、例えば、0.1μm~2μm、0.2μm~1.5μm、0.4μm~1μmである。前記体積平均粒子径は、例えば、動的光散乱法、レーザー回折法等の粒度分布評価装置、および走査型電子顕微鏡(SEM)、透過型電子顕微鏡(TEM)等の電子顕微鏡等により測定することができる。 In the void layer 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 μm or more, 0.2 μm or more, 0.4 μm or more, The upper limit is, for example, 2 μm or less, 1.5 μm or less, 1 μm or less, and the range is, for example, 0.1 μm to 2 μm, 0.2 μm to 1.5 μm, or 0.4 μm to 1 μm. 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.
 また、前記微細孔粒子の粒度バラツキを示す粒度分布は、特に制限されず、例えば、粒径0.4μm~1μmの粒子が、50~99.9重量%、80~99.8重量%、90~99.7重量%であり、または、粒径1μm~2μmの粒子が、0.1~50重量%、0.2~20重量%、0.3~10重量%である。前記粒度分布は、例えば、粒度分布評価装置または電子顕微鏡により測定することができる。 The particle size distribution showing the particle size variation of the fine pore particles is not particularly limited. For example, particles having a particle size of 0.4 μm to 1 μm are 50 to 99.9% by weight, 80 to 99.8% by weight, 90%. Or particles having a particle size of 1 μm to 2 μm 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.
 本発明の空隙層において、前記ゲル状化合物の種類は、特に制限されない。前記ゲル状化合物としては、例えば、ゲル状ケイ素化合物が例示できる。以下に、ゲル状化合物がゲル状ケイ素化合物である場合を例として説明するが、本発明は、これには制限されない。 In the void layer of the present invention, the type of the gel compound is not particularly limited. Examples of the gel compound include a gel silicon compound. Hereinafter, a case where the gel compound is a gel silicon compound will be described as an example, but the present invention is not limited thereto.
 前記架橋結合は、例えば、シロキサン結合である。シロキサン結合は、例えば、以下に示す、T2の結合、T3の結合、T4の結合が例示できる。本発明の空隙層がシロキサン結合を有する場合、例えば、いずれか一種の結合を有してもよいし、いずれか二種の結合を有してもよいし、三種全ての結合を有してもよい。前記シロキサン結合のうち、T2およびT3の比率が多いほど、可撓性に富み、ゲル本来の特性を期待できるが、膜強度が脆弱になる。一方で、前記シロキサン結合のうちT4比率が多いと、膜強度を発現しやすいが、空隙サイズが小さくなり、可撓性が脆くなる。このため、例えば、用途に応じて、T2、T3、T4比率を変えることが好ましい。 The cross-linking is, for example, a siloxane bond. Examples of the siloxane bond include T2 bond, T3 bond, and T4 bond shown below. When the void layer of the present invention has a siloxane bond, for example, it may have any one kind of bond, may have any two kinds of bonds, or may have all three kinds of bonds. Good. Among 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. On the other hand, when 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.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
 本発明の空隙層が前記シロキサン結合を有する場合、T2、T3およびT4の割合は、例えば、T2を「1」として相対的に表した場合、T2:T3:T4=1:[1~100]:[0~50]、1:[1~80]:[1~40]、1:[5~60]:[1~30]である。 When the void layer of the present invention has the siloxane bond, the ratio of T2, T3, and T4 is, for example, when T2 is relatively expressed as “1”, T2: T3: T4 = 1: [1 to 100] : [0-50], 1: [1-80]: [1-40], 1: [5-60]: [1-30].
 また、本発明の空隙層は、例えば、含まれるケイ素原子がシロキサン結合していることが好ましい。具体例として、前記空隙層に含まれる全ケイ素原子のうち、未結合のケイ素原子(つまり、残留シラノール)の割合は、例えば、50%未満、30%以下、15%以下である。 Further, in the void layer of the present invention, for example, it is preferable that contained silicon atoms have siloxane bonds. As a specific example, 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.
 前記ゲル状化合物が、前記ゲル状ケイ素化合物の場合、前記モノマーのケイ素化合物は、特に制限されない。前記モノマーのケイ素化合物は、例えば、下記式(1)で表される化合物が挙げられる。前記ゲル状ケイ素化合物が、前述のように、モノマーのケイ素化合物が互いに水素結合または分子間力結合したゲル化物の場合、式(1)のモノマー間は、例えば、それぞれの水酸基を介して水素結合できる。 When the gel compound is the gel silicon compound, the monomer silicon compound is not particularly limited. Examples of the silicon compound of the monomer include a compound represented by the following formula (1). In the case where 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.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
 前記式(1)中、例えば、Xは、2、3または4であり、Rは、直鎖もしくは分枝アルキル基、である。前記Rの炭素数は、例えば、1~6、1~4、1~2である。前記直鎖アルキル基は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられ、前記分枝アルキル基は、例えば、イソプロピル基、イソブチル基等が挙げられる。前記Xは、例えば、3または4である。 In the formula (1), for example, X is 2, 3 or 4, and R 1 is a linear or branched alkyl group. The carbon number of 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.
 前記式(1)で表されるケイ素化合物の具体例としては、例えば、Xが3である下記式(1’)に示す化合物が挙げられる。下記式(1’)において、Rは、前記式(1)と同様であり、例えば、メチル基である。Rがメチル基の場合、前記ケイ素化合物は、トリス(ヒドロキシ)メチルシランである。前記Xが3の場合、前記ケイ素化合物は、例えば、3つの官能基を有する3官能シランである。 Specific examples of the silicon compound represented by the formula (1) include a compound represented by the following formula (1 ′) in which X is 3. In the following formula (1 ′), R 1 is the same as in the above formula (1), and is, for example, a methyl group. When R 1 is a methyl group, the silicon compound is tris (hydroxy) methylsilane. When X is 3, the silicon compound is, for example, a trifunctional silane having three functional groups.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
 また、前記式(1)で表されるケイ素化合物の具体例としては、例えば、Xが4である化合物が挙げられる。この場合、前記ケイ素化合物は、例えば、4つの官能基を有する4官能シランである。 Further, specific examples of the silicon compound represented by the formula (1) include a compound in which X is 4. In this case, the silicon compound is, for example, a tetrafunctional silane having four functional groups.
 前記モノマーのケイ素化合物は、例えば、ケイ素化合物前駆体の加水分解物でもよい。前記ケイ素化合物前駆体としては、例えば、加水分解により前記ケイ素化合物を生成できるものであればよく、具体例として、下記式(2)で表される化合物が挙げられる。 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).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
 前記式(2)中、例えば、Xは、2、3または4であり、
 RおよびRは、それぞれ、直鎖もしくは分枝アルキル基であり、
 RおよびRは、同一でも異なっていても良く、
 Rは、Xが2の場合、互いに同一でも異なっていても良く、
 Rは、互いに同一でも異なっていても良い。
In the formula (2), for example, X is 2, 3 or 4,
R 1 and R 2 are each a linear or branched alkyl group,
R 1 and R 2 may be the same or different,
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.
 前記XおよびRは、例えば、前記式(1)におけるXおよびRと同じである。また、前記Rは、例えば、式(1)におけるRの例示が援用できる。 Wherein X and R 1 are, for example, the same as X and R 1 in the formula (1). In addition, the R 2 is, for example, can be exemplified for R 1 is incorporated in the formula (1).
 前記式(2)で表されるケイ素化合物前駆体の具体例としては、例えば、Xが3である下記式(2’)に示す化合物が挙げられる。下記式(2’)において、RおよびRは、それぞれ、前記式(2)と同様である。RおよびRがメチル基の場合、前記ケイ素化合物前駆体は、トリメトキシ(メチル)シラン(以下、「MTMS」ともいう)である。 Specific examples of the silicon compound precursor represented by the formula (2) include compounds represented by the following formula (2 ′) in which X is 3. In the following formula (2 ′), R 1 and R 2 are the same as those in the formula (2), respectively. When R 1 and R 2 are methyl groups, the silicon compound precursor is trimethoxy (methyl) silane (hereinafter also referred to as “MTMS”).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 前記モノマーのケイ素化合物は、例えば、低屈折率性に優れる点から、前記3官能シランが好ましい。また、前記モノマーのケイ素化合物は、例えば、強度(例えば、耐擦傷性)に優れる点から、前記4官能シランが好ましい。また、前記ゲル状ケイ素化合物の原料となる前記モノマーのケイ素化合物は、例えば、一種類のみを使用してもよいし、二種類以上を併用してもよい。具体例として、前記モノマーのケイ素化合物として、例えば、前記3官能シランのみを含んでもよいし、前記4官能シランのみを含んでもよいし、前記3官能シランと前記4官能シランの両方を含んでもよいし、さらに、その他のケイ素化合物を含んでもよい。前記モノマーのケイ素化合物として、二種類以上のケイ素化合物を使用する場合、その比率は、特に制限されず、適宜設定できる。 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). Moreover, as for 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. As a specific example, as 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. In addition, other silicon compounds may be included. When two or more types of silicon compounds are used as the silicon compound of the monomer, the ratio is not particularly limited and can be set as appropriate.
 前記空隙層は、例えば、前記微細な空隙構造を形成する一種類または複数種類の構成単位同士を化学的に結合させるための触媒を含んでいても良い。前記触媒の含有率は、特に限定されないが、前記構成単位の重量に対し、例えば、0.01~20重量%、0.05~10重量%、または0.1~5重量%である。 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.
 また、前記空隙層は、例えば、さらに、前記微細な空隙構造を形成する一種類または複数種類の構成単位同士を間接的に結合させるための架橋補助剤を含んでいても良い。前記架橋補助剤の含有率は、特に限定されないが、例えば、前記構成単位の重量に対して0.01~20重量%、0.05~15重量%、または0.1~10重量%である。 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. .
[カバー層]
 本発明において、前記カバー層は、特に限定されない。本発明において、「カバー層」は、例えば、前記空隙層を被覆する層(被覆層)であり、例えば、耐擦傷性を有する層(オーバーコート層)である。
[Cover layer]
In the present invention, the cover layer is not particularly limited. In the present invention, 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).
 本発明において、前記カバー層は、前記空隙層上に直接形成される。ここでいう、「直接形成する」とは、例えば、後述するように、前記空隙層上に前記カバー層を塗工することにより形成してもよいが、例えば、前記空隙層と前記カバー層とを別々に作製し、カバー層を前記空隙層上に転写させることも含む。 In the present invention, the cover layer is formed directly on the gap layer. As used herein, “directly forming” may be formed, for example, by coating the cover layer on the gap layer, as described later. For example, the gap layer and the cover layer Are prepared separately, and the cover layer is transferred onto the gap layer.
 前記カバー層は、例えば、前記空隙層の耐溶剤性が低いため、前記耐溶剤性に対する影響を抑制する観点から、ヘキサン等の炭化水素系溶媒または水を溶媒とするカバー層組成液が挙げられる。前記空隙層は、例えば、水を溶媒とするカバー層組成液である。前記組成液中の組成物としては、例えば、前記空隙層の組成物(形成材料)で例示したものであってもよい。 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. As a composition in the said composition liquid, what was illustrated by the composition (formation material) of the said space | gap layer may be used, for example.
 前記カバー層としては、例えば、水性塗料の塗工により形成された層である。これにより、前記カバー層は、水溶性であるため、空隙層の高い撥水性により、前記カバー層の形成材料が前記空隙層の構造を埋めることをより抑制することができる。前記水性塗料とは、例えば、水溶媒の塗工液であり、前記水溶媒の塗工液は、溶液または分散液の形態であってもよい。前記水性塗料の具体的な形成材料は、特に制限されず、例えば、前記空隙層の形成材料として例示したものであってもよい。 The cover layer is, for example, a layer formed by applying a water-based paint. Thereby, since the said cover layer is water-soluble, it can suppress more that the formation material of the said cover layer fills the structure of the said void layer by the high water repellency of a void layer. The 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.
 前記カバー層は、特には、水溶性架橋体および水溶性ポリマーの少なくとも一方を含んでいる形態が好ましい。空隙層の高い撥水性から、カバー層の原料である水性塗料がモノマーやオリゴマーのみで構成され低粘度であると、塗工時にハジキが出てしまい空隙層上にカバー層が形成出来ないおそれがある。一方、水溶性架橋体や水溶性ポリマーを含むことで前記水性塗料が高粘度化しハジキが起きにくくすることが可能となる。前記水溶性架橋体および水溶性ポリマーとしては、特に制限されず、例えば、前記空隙層の形成材料として例示した水溶性架橋体および水溶性ポリマーであってもよい。前記水溶性架橋体としては、例えば、無機有機ハイブリッドである水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方から形成された架橋体(以下、「水溶性シラン架橋体」ということがある)等が挙げられる。前記水溶性シラン架橋体としては、特に制限されず、例えば、前記シロキサン結合により架橋したシリカ化合物等が挙げられ、例えば、前記T2の結合、前記T3の結合、前記T4の結合を有するシリカ化合物が挙げられる。 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. Examples of 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.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 前記水溶性ポリマーとしては、アクリル系、ビニルアルコール系、シリコーン系、ポリエステル系、ポリウレタン系、ポリエーテル系等のポリマーが挙げられ、例えば、シリコーン系ポリマーであり、前記シリコーン系ポリマーとしては、例えば、前記式(2)で表されるアルコキシシランのポリマー等が挙げられる。特にはポリビニルアルコール系もしくはポリウレタン系、自己架橋型アクリルエマルジョン等がポリマー水溶液の安定性や高粘度化可能な点から好ましい。 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). In particular, 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.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
 前記カバー層に、前記水溶性架橋体および水溶性ポリマーの少なくとも一方を含むことにより、例えば、前記空隙層の構成物質との間に水素結合を形成し、前記空隙層と前記カバー層の密着性を向上することができる。さらには、前記カバー層中にシランモノマーおよび/もしくはシランオリゴマーを含ませることにより、カバー層と空隙層を相溶させて密着性を向上させることも可能である。 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.
 これら水溶性架橋体および水溶性ポリマーの少なくとも一方は、1種類のみ用いても、複数種類を併用(例えば、混合、積層等)しても良い。 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.).
 前記カバー層は、例えば、前記カバー層の原料を含むカバー層原料液を前記空隙層上に塗工し、乾燥させた後、加熱および光照射の少なくとも一方を行うことで形成された層である。前記カバー層原料液は、例えば、さらに、加熱または光照射により分解し塩基を発生する化合物を含む液(以下、単に「塩基発生化合物」という)、または、無機有機ハイブリッドである水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方を含む液であり、前記塩基発生化合物並びに前記水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方の双方を含む液であってもよい。 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.
 前記塩基発生化合物としては、特に制限されず、前記空隙層の形成材料として例示したものであってもよく、具体的には、例えば、熱により塩基性触媒を発生する物質(熱塩基発生剤)、光照射により塩基性触媒を発生する物質(光塩基発生剤)等が挙げられ、例えば、光塩基発生剤である。前記熱塩基発生剤としては、例えば、尿素等が挙げられる。前記光塩基発生剤としては、例えば、9-アントリルメチル N,N-ジエチルカルバメート(9-anthrylmethyl N,N-diethylcarbamate、商品名WPBG-018)、(E)-1-[3-(2-ヒドロキシフェニル)-2-プロペノイル]ピペリジン((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine、商品名WPBG-027)、1-(アントラキノン-2-イル)エチル イミダゾールカルボキシレート(1-(anthraquinon-2-yl)ethyl imidazolecarboxylate、商品名WPBG-140)、2-ニトロフェニルメチル 4-メタクリロイルオキシピペリジン-1-カルボキシラート(商品名WPBG-165)、1,2-ジイソプロピル-3-〔ビス(ジメチルアミノ)メチレン〕グアニジウム 2-(3-ベンゾイルフェニル)プロピオナート(商品名WPBG-266)、1,2-ジシクロヘキシル-4,4,5,5-テトラメチルビグアニジウム n-ブチルトリフェニルボラート(商品名WPBG-300)、および 2-(9-オキソキサンテン-2-イル)プロピオン酸1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(東京化成製)、4-ピペリジンメタノールを含む化合物(商品名HDPD-PB100:ヘレウス社製)等が挙げられる。なお、前記「WPBG」を含む商品名は、いずれも和光純薬工業株式会社の商品名である。 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. Examples of the thermal base generator 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-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate (trade name WPBG-300) and 2- (9-oxoxanthen-2-yl) propionic acid 1, 5,7-triazabicyclo [4.4.0] dec-5-ene (manufactured by Tokyo Chemical Industry), compounds containing 4-piperidinemethanol (trade name HDPD-PB100: manufactured by Heraeus), and the like. The trade names including “WPBG” are trade names of Wako Pure Chemical Industries, Ltd.
 前記水溶性アルコキシシランのモノマーとしては、特に制限されず、前記空隙層の形成材料として例示したものであってもよく、具体的には、例えば、前記式(2)で表されるケイ素化合物等が挙げられ、前記水溶性アルコキシシランのオリゴマーとしては、例えば、前記式(2)で表されるケイ素化合物のオリゴマー等が挙げられる。 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).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
 前記カバー層に、例えば、前記塩基発生化合物を含むことにより、例えば、前記光塩基発生剤を用いた触媒反応により、前記カバー層中の化合物(例えば、前記水溶性アルコキシシランのモノマーおよびオリゴマー等)と、前記空隙層の前記微細孔粒子との化学的な結合(例えば、架橋反応)が進み、前記カバー層と前記空隙層との密着性がより向上する。 For example, by including 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.
 前記空隙層および前記カバー層の形成にあたり、例えば、後述するように、前記形成した空隙層について強度向上工程(空隙層強度向上工程)を行った後、前記カバー層を形成し、前記形成したカバー層について強度向上工程(カバー層強度向上工程)を行ってもよい。このように、空隙層強度向上工程およびカバー層強度向上工程をそれぞれ分けて行ってもよいが、例えば、前記空隙層強度向上工程に先立ち、前記カバー層を形成し、前記カバー層強度向上工程を行うことに伴い、前記空隙層強度向上工程が行われてもよい。すなわち、前記両工程を別々に行ってもよいし、両工程を同時に行ってもよい。これにより、前記空隙層および前記カバー層の強度向上工程(エージング工程)を同時に行うため、例えば、前記カバー層中の化合物および前記空隙層の前記微細孔粒子を同時にゲル化することができ、前記カバー層と前記空隙層との密着性が向上するとともに、前記カバー層の耐擦傷性もまた向上する。 In forming the gap layer and the cover layer, for example, as described later, 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. Thus, the gap layer strength improving step and the cover layer strength improving step may be performed separately. For example, prior to the gap layer strength improving step, the cover layer is formed, and the cover layer strength improving step is performed. In connection with performing, the said space | gap layer strength improvement process may be performed. That is, both the steps may be performed separately, or both steps may be performed simultaneously. Thereby, in order to simultaneously perform the strength improvement step (aging step) of the void layer and the cover layer, for example, 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.
 前記カバー層の厚みは、特に制限されないが、例えば、50nm~10000nm、100nm~5000nm、150nm~4000nm、または200nm~3000nmである。 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.
 前記カバー層の空隙率は、特に制限されず、例えば、耐擦傷性を向上する観点から、例えば10体積%以下、好ましくは、9体積%以下、8体積%以下である。前記空隙率は、前述した前記空隙層の膜密度に基づいた方法により測定できる。 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.
 本発明の積層光学フィルムは、例えば、ロール体である。また、本発明の積層光学フィルムは、例えば、前述のように、さらに樹脂フィルムを含み、長尺な前記樹脂フィルム上に、前記空隙層が形成されてもよい。この場合、本発明の積層光学フィルムには別の長尺フィルムが積層されていてもよく、前記樹脂フィルムと前記空隙層とを含む本発明の積層光学フィルムに、別の長尺樹脂フィルム(例えば、合紙、離型フィルム、表面保護フィルム等)を積層した後、ロール体に巻かれた形態であってもよい。 The laminated optical film of the present invention is, for example, a roll body. Moreover, 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. In this case, 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.
 本発明の積層光学フィルムの製造方法は、特に制限されないが、例えば、以下に示す本発明の製造方法により製造することができる。 Although 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.
[2.積層光学フィルムの製造方法の概要および詳細]
 本発明の積層光学フィルムの製造方法は、前述のとおり、前記樹脂フィルム上に前記空隙層を形成する空隙層形成工程、および、前記空隙層上に前記カバー層を直接形成する前記カバー層形成工程を含むことを特徴とする。なお、本発明の製造方法は、特に記載しない限り、前記本発明の積層光学フィルムの説明を援用できる。
[2. Outline and Details of Manufacturing Method of Laminated Optical Film]
As described above, 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. In addition, unless otherwise indicated, the description of the laminated | multilayer optical film of the said invention can be used for the manufacturing method of this invention.
[2.1 空隙層形成工程の概要]
 本発明の積層光学フィルムの製造方法においては、前記空隙層は、例えば、微細孔粒子同士が化学的に結合している多孔体であり、前記空隙層形成工程において、例えば、前記微細孔粒子同士を化学的に結合させる。本発明の積層光学フィルムの製造方法は、例えば、前述のとおり、前記微細孔粒子を含む含有液を作製する含有液作製工程、前記樹脂フィルム上に前記含有液を塗工する塗工工程、および、塗工した前記含有液を乾燥させる乾燥工程をさらに含み、前記空隙層形成工程において、例えば、前記微細孔粒子同士を化学的に結合させて前記多孔体を形成してもよい。また、前記空隙層形成工程において、前記微細孔粒子同士を触媒の作用により化学的に結合させて前記空隙層を形成してもよい。この場合、前記触媒は、例えば、塩基性触媒であり、前記含有液が、光または熱により前記塩基性触媒を発生する塩基発生剤を含む。また、前記空隙層形成工程において、光照射または加熱により、前記微細孔粒子同士を化学的に結合させて前記空隙層を形成する化学処理工程を含んでもよいし、前記空隙層を加熱等により強度を向上させる強度向上工程(エージング工程)を行ってもよい。また、前記空隙層の別形態として、ナノファイバー等の繊維状物質からなり、前記繊維状物質が絡まり合い空隙を含む形で層を成している空隙層がある。製造方法においては、前記微細孔粒子と同様である。さらに他にも、中空ナノ粒子やナノクレイを用いた空隙層、中空ナノバルーンやフッ化マグネシウムを用いて形成した空隙層も含まれる。
[2.1 Outline of void layer forming process]
In the method for producing a laminated optical film of the present invention, the void layer is, for example, a porous body in which fine pore particles are chemically bonded. In the void layer forming step, for example, 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. In the void layer forming step, the void layer may be formed by chemically bonding the fine pore particles by the action of a catalyst. In this case, the catalyst is, for example, a basic catalyst, and 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 | strength improvement process (aging process) which improves this. Further, as another form of 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. In addition, a void layer using hollow nanoparticles and nanoclay, and a void layer formed using hollow nanoballoons and magnesium fluoride are also included.
 前記微細孔粒子を含む含有液(以下、「微細孔粒子含有液」または単に「含有液」という場合がある。)は、特に限定されないが、例えば、前記微細孔粒子を含む懸濁液である。なお、以下において、主に、前記微細孔粒子が、ゲル状化合物の粉砕物であり、前記空隙層がゲル状化合物の粉砕物を含む多孔体(好ましくはシリコーン多孔体)である場合について説明する。ただし、本発明は、前記微細孔粒子が、ゲル状化合物の粉砕物以外である場合も、同様に実施することができる。 The liquid containing the microporous particles (hereinafter, sometimes referred to as “microporous particle-containing liquid” or simply “containing liquid”) is not particularly limited, and is, for example, a suspension containing the microporous particles. . In the following, the case where 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. . However, 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.
 本発明の製造方法によれば、例えば、優れた低屈折率を示す空隙層が形成される。その理由は、例えば、以下のように推測されるが、本発明は、この推測には制限されない。 According to the production method of the present invention, for example, 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.
 本発明の製造方法で使用する前記微細孔粒子は、例えば、前記ゲル状ケイ素化合物を粉砕したものであるため、前記粉砕前のゲル状ケイ素化合物の三次元構造が、三次元基本構造に分散された状態となっている。そして、本発明の製造方法では、前記ゲル状ケイ素化合物の粉砕物を前記基材上に塗工することで、前記三次元基本構造に基づく多孔性構造の前駆体が形成される。つまり、本発明の製造方法によれば、前記ゲル状ケイ素化合物の三次元構造とは異なる、前記三次元基本構造の前記粉砕物から形成された新たな多孔構造が形成される。このため、最終的に得られる前記空隙層は、例えば、空気層と同程度に機能する低屈折率を奏することができる。また、本発明の製造方法においては、さらに、例えば、前記微細孔粒子同士を化学的に結合させるため、前記新たな三次元構造が固定化される。このため、最終的に得られる前記空隙層は、空隙を有する構造であるが、十分な強度と可撓性とを維持できる。このように、本発明の製造方法により得られる空隙層は、例えば、前記空気層の代替品として、低屈折性という機能の面において、また、強度と可撓性においても、有用である。また、前記空気層の場合、例えば、部材と部材とを、両者の間にスペーサー等を介することで間隙を設けて積層することにより、前記部材間に空気層を形成する必要があった。しかし、本発明の製造方法により得られる空隙層は、例えば、目的の部位に配置するのみで、前記空気層と同程度に機能する低屈折性を発揮させることができる。したがって、前述のように、前記空気層を形成するよりも、容易且つ簡便に、前記空気層と同程度に機能する低屈折性を、例えば、光学部材に付与することができる。 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 | coating the ground material of the said gel-like silicon compound on the said base material. That is, according to the production method of the present invention, a new porous structure formed from the pulverized product of the three-dimensional basic structure, which is different from the three-dimensional structure of the gel silicon compound, is formed. For this reason, the said void layer finally obtained can show the low refractive index which functions to the same extent as an air layer, for example. Further, in the production method of the present invention, for example, the new three-dimensional structure is fixed in order to chemically bond the microporous particles. For this reason, although the said void layer finally obtained is a structure which has a space | gap, it can maintain sufficient intensity | strength and flexibility. Thus, 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. Further, in the case of 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. However, 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.
 本発明の製造方法により形成される空隙層は、例えば、前述のように孔構造(多孔質構造)を有していてもよく、例えば、前記孔構造が連続した連泡構造体であってもよい。前記連泡構造体とは、例えば、前記シリコーン多孔体において、三次元的に、孔構造が連なっていることを意味し、前記孔構造の内部空隙が連続している状態ともいえる。多孔質体が連泡構造を有する場合、これにより、バルク体中に占める空孔率を高めることが可能であるが、中空シリカのような独泡粒子を使用する場合は、連泡構造を形成できない。これに対して、本発明の空隙層は、例えば、シリカゾル粒子(ゾルを形成するゲル状ケイ素化合物の粉砕物)を使用する場合、前記粒子が三次元の樹状構造を有するために、塗工膜(前記ゲル状ケイ素化合物の粉砕物を含むゾルの塗工膜)中で、前記樹状粒子が沈降・堆積することで、容易に連泡構造を形成することが可能である。また、本発明の空隙層は、より好ましくは、連泡構造が複数の細孔分布を有するモノリス構造を形成することが好ましい。前記モノリス構造は、例えば、ナノサイズの微細な空隙が存在する構造と、同ナノ空隙が集合した連泡構造として存在する階層構造を指す。前記モノリス構造を形成する場合、例えば、微細な空隙で膜強度を付与しつつ、粗大な連泡空隙で高い空孔率を付与し、膜強度と高空孔率とを両立することができる。それらのモノリス構造を形成するには、例えば、まず、前記シリカゾル粒子に粉砕する前段階のゲル(ゲル状ケイ素化合物)において、生成する空隙構造の細孔分布を制御することが好ましい。また、例えば、前記ゲル状ケイ素化合物を粉砕する際、粉砕後のシリカゾル粒子の粒度分布を所望のサイズに制御することで、前記モノリス構造を形成させることができる。 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. Good. 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. When 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. On the other hand, 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. In the film (sol coating film containing a pulverized product of the gel-like silicon compound), 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. In the case of forming 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. In order to form these monolithic structures, for example, it is preferable to first control the pore distribution of the generated void structure in the gel (gel-like silicon compound) before pulverization into the silica sol particles. For example, when the gel-like silicon compound is pulverized, the monolith structure can be formed by controlling the particle size distribution of the pulverized silica sol particles to a desired size.
 前記空隙層形成工程においては、例えば、光塩基発生剤を用いた触媒反応により、前記微細孔粒子同士を化学的に結合させて前記空隙層を形成する。そして、例えば、前記光塩基発生剤から発生した塩基触媒が前記前駆体中に残留していることにより、前記カバー層形成工程における加熱等で、前記微細孔粒子同士の化学的な結合(例えば架橋反応)がさらに進む。これにより、前記空隙層の強度が向上すると考えられる。具体例として、前記微細孔粒子が、ケイ素化合物の微細孔粒子(例えばゲル状シリカ化合物の粉砕体)であって、前記空隙層中に残留シラノール基(OH基)が存在する場合、前記残留シラノール基同士が架橋反応により化学的に結合すると考えられる。ただし、この説明も例示であり、本発明を限定しない。 In the void layer forming step, for example, the void layer is formed by chemically bonding the microporous particles by a catalytic reaction using a photobase generator. For example, when 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. As a specific example, when 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. However, this description is also an example and does not limit the present invention.
[2.2 カバー層形成工程の概要]
 また、本発明の製造方法においては、前記カバー層形成工程は、例えば、前記空隙層上に前記カバー層の原料を含むカバー層原料液を直接塗工するカバー層原料液塗工工程、および、塗工した前記カバー層の原料を含む液を乾燥するカバー層原料液乾燥工程を含み、さらに、前記カバー層原料液乾燥工程後に、加熱および光照射の少なくとも一方により前記カバー層を形成する化学処理工程、前記カバー層原料液乾燥工程後に、80℃以下で1時間以上加熱して前記カバー層を形成する強度向上工程を含んでもよい。
[2.2 Outline of cover layer forming process]
In the manufacturing method of the present invention, 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.
 前記カバー層原料液(以下、単に「原料液」という場合がある。)は、特に限定されないが、例えば、加熱または光照射により分解し塩基を発生する化合物(以下、単に「塩基発生化合物」ということがある)を含む液、または、水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方を含む液であり、前記カバー層原料液は、前記塩基発生化合物並びに前記水溶性アルコキシシランのモノマーおよびオリゴマーの少なくとも一方の双方を含んでもよい。前記塩基発生化合物としては、本発明の積層光学フィルムの前記カバー層において、例示した塩基発生化合物が挙げられ、前記水溶性アルコキシシランのモノマーおよびオリゴマーとしては、本発明の積層光学フィルムの前記カバー層において、例示した前記水溶性アルコキシシランのモノマーおよびオリゴマーが挙げられる。 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.
 本発明の製造方法は、特に記載しない限り、前記本発明の積層光学フィルムの説明を援用できる。 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.
 本発明の製造方法において、前記微細孔粒子、前記モノマー化合物および前記モノマー化合物の前駆体は、前記本発明の空隙層における説明を援用できる。 In the production method of the present invention, 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.
[2.3 積層光学フィルムの製造方法の詳細]
 本発明の積層光学フィルムの製造方法は、例えば、以下のようにして行うことができるが、これには限定されない。
[2.3 Details of Manufacturing Method of Laminated Optical Film]
Although the manufacturing method of the laminated optical film of this invention can be performed as follows, for example, it is not limited to this.
[2.3.1 空隙層形成工程の詳細]
 以下では、まず、本発明の空隙層形成工程について説明する。例えば、シリカ粒子の多孔質体による空隙層について説明するが、空隙層の形成方法はこれに限定されない。
[2.3.1 Details of gap layer forming step]
Hereinafter, first, the void layer forming step of the present invention will be described. For example, 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.
[2.3.1.1 含有液作製工程]
 本発明の積層光学フィルムの製造方法は、例えば、前述のように、前記微細孔粒子を含む含有液を作製する含有液作製工程を有する。前記微細孔粒子がケイ素化合物の微細孔粒子である場合は、ゲル状シリカ化合物の粉砕物を含む。前記粉砕物は、例えば、ゲル状のケイ素化合物(ゲル状ケイ素化合物)を粉砕して得られる。前記ゲル状シリカ化合物の粉砕によって、前述のように、前記ゲル状化合物の三次元構造が破壊され、三次元基本構造に分散される。
[2.3.1.1 Containing liquid preparation process]
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. When the fine pore particles are fine pore particles of a silicon compound, 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). By the pulverization of the gel-like silica compound, as described above, the three-dimensional structure of the gel-like compound is destroyed and dispersed into the three-dimensional basic structure.
 以下に、前記ケイ素化合物のゲル化による前記ゲル状シリカ化合物の生成、前記ゲル状シリカ化合物の粉砕による粉砕物の調製について、例を挙げて説明するが、本発明は、以下の例示には制限されない。 Hereinafter, the production of the gel-like silica compound by gelation of the silicon compound and the preparation of the pulverized product by pulverization of the gel-like silica compound will be described with examples, but the present invention is limited to the following examples. Not.
 前記ケイ素化合物のゲル化は、例えば、前記ケイ素化合物を、互いに水素結合させることまたは分子間力結合させることで行うことができる。 The gelation of the silicon compound can be performed, for example, by hydrogen bonding or intermolecular force bonding of the silicon compounds.
 前記ケイ素化合物は、例えば、前記本発明の空隙層において述べた前記式(1)で表されるケイ素化合物が挙げられる。 Examples of the silicon compound include a silicon compound represented by the formula (1) described in the void layer of the present invention.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
 前記式(1)のケイ素化合物は、水酸基を有するため、前記式(1)のモノマー間は、例えば、それぞれの水酸基を介して、水素結合または分子間力結合が可能である。 Since the silicon compound of the formula (1) has a hydroxyl group, the monomers of the formula (1) can be hydrogen bonded or intermolecularly bonded via, for example, each hydroxyl group.
 また、前記ケイ素化合物は、前述のように、前記ケイ素化合物前駆体の加水分解物でもよく、例えば、前記本発明の空隙層において述べた前記式(2)で表されるケイ素化合物前駆体を、加水分解して生成してもよい。 Further, as described above, the silicon compound may be a hydrolyzate of the silicon compound precursor. For example, the silicon compound precursor represented by the formula (2) described in the void layer of the present invention, It may be produced by hydrolysis.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
 前記ケイ素化合物前駆体の加水分解の方法は、特に制限されず、例えば、触媒存在下での化学反応により行うことができる。前記触媒としては、例えば、シュウ酸、酢酸等の酸等が挙げられる。前記加水分解反応は、例えば、シュウ酸の水溶液を、前記ケイ素化合物とジメチルスルホキシドとの混合液(例えば懸濁液)に、室温環境下でゆっくり滴下混合させた後に、そのまま30分程度撹拌することで行うことができる。前記ケイ素化合物前駆体を加水分解する際は、例えば、前記ケイ素化合物前駆体のアルコキシ基を完全に加水分解することで、その後のゲル化・熟成・空隙構造形成後の加熱・固定化を、さらに効率良く発現することができる。 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. Examples of the catalyst include acids such as oxalic acid and acetic acid. In the hydrolysis reaction, for example, 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. When 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.
 前記ケイ素化合物のゲル化は、例えば、前記モノマー間の脱水縮合反応により行うことができる。前記脱水縮合反応は、例えば、触媒存在下で行うことが好ましく、前記触媒としては、例えば、塩酸、シュウ酸、硫酸等の酸触媒、およびアンモニア、水酸化カリウム、水酸化ナトリウム、水酸化アンモニウム等の塩基触媒等の、脱水縮合触媒が挙げられる。前記脱水縮合触媒は、塩基触媒が特に好ましい。前記脱水縮合反応において、前記ケイ素化合物に対する前記触媒の添加量は、特に制限されず、前記ケイ素化合物1モルに対して、触媒は、例えば、0.1~10モル、0.05~7モル、0.1~5モルである。 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. Examples of 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. And a dehydration condensation catalyst such as a base catalyst. The dehydration condensation catalyst is particularly preferably a base catalyst. In the dehydration condensation reaction, 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.
 前記ケイ素化合物のゲル化は、例えば、溶媒中で行うことが好ましい。前記溶媒における前記モノマー化合物の割合は、特に制限されない。前記溶媒は、例えば、ジメチルスルホキシド(DMSO)、N-メチルピロリドン(NMP)、N,N-ジメチルアセトアミド(DMAc)、ジメチルホルムアミド(DMF)、γ-ブチルラクトン(GBL)、アセトニトリル(MeCN)、エチレングリコールエチルエーテル(EGEE)等が挙げられる。前記溶媒は、例えば、1種類でもよいし、2種類以上を併用してもよい。前記ゲル化に使用する溶媒を、以下、「ゲル化用溶媒」ともいう。 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. Examples of the solvent include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF), γ-butyllactone (GBL), acetonitrile (MeCN), ethylene Examples thereof include glycol ethyl ether (EGEE). For example, one type of solvent may be used, or two or more types may be used in combination. Hereinafter, the solvent used for the gelation is also referred to as “gelling solvent”.
 前記ゲル化の条件は、特に制限されない。前記モノマー化合物を含む前記溶媒に対する処理温度は、例えば、20~30℃、22~28℃、24~26℃であり、処理時間は、例えば、1~60分、5~40分、10~30分である。前記脱水縮合反応を行う場合、その処理条件は、特に制限されず、これらの例示を援用できる。前記ゲル化を行うことで、例えば、シロキサン結合が成長し、シリカ一次粒子が形成され、さらに反応が進行することで、前記一次粒子同士が、数珠状に連なり三次元構造のゲルが生成される。 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. When performing the said dehydration condensation reaction, the process conditions in particular are not restrict | limited, These illustrations can be used. By performing the gelation, for example, a siloxane bond grows, silica primary particles are formed, and further, the reaction proceeds, whereby the primary particles are linked in a bead shape to generate a three-dimensional gel. .
 前記ゲル化により得られた前記ゲル状シリカ化合物は、ゲル化反応の後、熟成処理を施すことが好ましい。前記熟成処理により、例えば、ゲル化で得られた三次元構造を有するゲルの一次粒子をさらに成長させることで、粒子自体のサイズを大きくすることが可能であり、結果的には、粒子同士が接触しているネック部分の接触状態を、点接触から面接触に増やすことができる。上記のような熟成処理を行ったゲルは、例えば、ゲル自体の強度が増加し、結果的には、粉砕を行った後の三次元基本構造の強度を向上できる。これにより、例えば、前記粉砕物を塗工した後の乾燥工程において、前記三次元基本構造が堆積した空隙構造の細孔サイズが、乾燥過程の溶媒揮発に伴って収縮することを抑制できる。 The gel-like silica compound obtained by the gelation is preferably subjected to an aging treatment after the gelation reaction. By 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. Thereby, for example, in the drying step after applying the pulverized product, 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.
 前記熟成処理は、例えば、所定の温度で所定の時間、前記ゲル状シリカ化合物をインキュベートすることにより行える。前記所定の温度は、特に制限されず、その下限が、例えば、30℃以上、35℃以上、40℃以上であり、その上限が、例えば、80℃以下、75℃以下、70℃以下であり、その範囲が、例えば、30~80℃、35~75℃、40~70℃である。前記所定の時間は、特に制限されず、その下限が、例えば、5時間以上、10時間以上、15時間以上であり、その上限が、例えば、50時間以下、40時間以下、30時間以下であり、その範囲が、例えば、5~50時間、10~40時間、15~30時間である。なお、熟成の最適な条件については、例えば、前記のシリカ一次粒子サイズの増大、およびネック部分の接触面積の増大が得られる条件が主目的である。さらには、使用している溶媒の沸点を考慮することが好ましく、例えば、熟成温度が高すぎると、溶媒が過剰に揮発してしまい、塗工液(ゲル液)濃度の濃縮により三次元空隙構造の細孔が閉口する等の不具合が生じる可能性がある。一方で、例えば、熟成温度が低すぎる場合は、前記の熟成による効果が十分に得られないばかりでなく、量産プロセスの経時での温度バラツキが増大することとなり、品質に劣る製品ができる可能性がある。 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. Note that 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. For example, if 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. On the other hand, for example, when 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.
 前記熟成処理は、例えば、前記ゲル化処理と同じ溶媒を使用でき、具体的には、前記ゲル化処理後の反応物(つまり、前記ゲル状シリカ化合物を含む前記溶媒)に対して、そのまま施すことが好ましい。ゲル化後の熟成処理を終えた前記ゲル(前記ゲル状シリカ化合物、例えば、前記ゲル状ケイ素化合物)に含まれる残留シラノール基のモル数は、例えば、添加した原材料(例えば、前記ケイ素化合物前駆体)のアルコキシ基のモル数を100とした場合の残留シラノール基の割合であり、その下限が、例えば、50%以上、40%以上、30%以上であり、その上限が、例えば、1%以下、3%以下、5%以下であり、その範囲が、例えば、1~50%、3~40%、5~30%である。ゲルの硬度を上げる目的では、例えば、残留シラノール基のモル数が低いほど好ましい。シラノール基のモル数が高すぎると、例えば、シリコーン多孔体の前駆体が架橋されるまでに、空隙構造を保持できなくなる可能性がある。一方で、シラノール基のモル数が低すぎると、例えば、前記微細孔粒子含有液(例えば懸濁液)を作製する工程および/またはその後の工程において、ゲル状化合物の粉砕物を架橋できなくなり、十分な膜強度を付与できなくなる可能性がある。なお、上記はシラノール基の例であるが、例えば、モノマーのケイ素化合物を各種反応性官能基で修飾した場合は、各々の官能基に対しても同様の現象を適用できるものとする。 In the aging treatment, for example, 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) ) When the number of moles of the alkoxy group is 100, the lower limit is, for example, 50% or more, 40% or more, 30% or more, and the upper limit is, for example, 1% or less. 3% or less, 5% or less, and the range is, for example, 1 to 50%, 3 to 40%, or 5 to 30%. For the purpose of increasing the hardness of the gel, for example, 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. Although the above is an example of 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.
 前記ケイ素化合物を前記ゲル化用溶媒中でゲル化した後、得られたゲル状シリカ化合物を粉砕する。前記粉砕は、例えば、前記ゲル化用溶媒中のゲル状シリカ化合物に対して、そのまま粉砕処理を施してもよいし、前記ゲル化用溶媒を他の溶媒に置換してから、前記他の溶媒中のゲル状シリカ化合物に対して、粉砕処理を施してもよい。また、例えば、ゲル化反応に用いた触媒および用いた溶媒が、熟成工程後も残存することで、液の経時ゲル化(ポットライフ)、乾燥工程時の乾燥効率低下を発生させる場合は、他の溶媒に置換することが好ましい。前記他の溶媒を、以下、「粉砕用溶媒」ともいう。 After the silicon compound is gelled in the gelling solvent, the gel silica compound obtained is pulverized. In the pulverization, for example, 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 | pulverize with respect to the gelatinous silica compound in it. In addition, for example, when the catalyst used in the gelation reaction and the solvent used remain after the ripening process, causing the gelation of the liquid over time (pot life) and a decrease in the drying efficiency during the drying process, It is preferable to substitute the above solvent. Hereinafter, the other solvent is also referred to as a “grinding solvent”.
 前記粉砕用溶媒は、特に制限されず、例えば、有機溶媒が使用できる。前記有機溶媒は、例えば、沸点130℃以下、沸点100℃以下、沸点85℃以下の溶媒が挙げられる。具体例としては、例えば、イソプロピルアルコール(IPA)、エタノール、メタノール、ブタノール、プロピレングリコールモノメチルエーテル(PGME)、メチルセロソルブ、アセトン、ジメチルホムアミド(DMF)等が挙げられる。前記粉砕用溶媒は、例えば、1種類でもよいし、2種類以上の併用でもよい。 The solvent for grinding is not particularly limited, and for example, an organic solvent can be used. Examples of the organic solvent include solvents having a boiling point of 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.
 前記ゲル化用溶媒と前記粉砕用溶媒との組合せは、特に制限されず、例えば、DMSOとIPAとの組合せ、DMSOとエタノール、DMSOとメタノール、DMSOとブタノールの組合せ等が挙げられる。このように、前記ゲル化用溶媒を前記粉砕用溶媒に置換することで、例えば、後述する塗膜形成において、より均一な塗工膜を形成することができる。 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. Thus, by replacing the gelling solvent with the pulverizing solvent, a more uniform coating film can be formed, for example, in coating film formation described below.
 前記ゲル状シリカ化合物の粉砕方法は、特に制限されず、例えば、超音波ホモジナイザー、高速回転ホモジナイザー、その他のキャビテーション現象を用いる粉砕装置もしくは高圧で液同士を斜向衝突させる粉砕装置等により行うことができる。ボールミル等のメディア粉砕を行う装置は、例えば、粉砕時にゲルの空隙構造を物理的に破壊するのに対し、ホモジナイザー等の本発明に好ましいキャビテーション方式粉砕装置は、例えば、メディアレス方式のため、ゲル三次元構造にすでに内包されている比較的弱い結合のシリカ粒子接合面を、高速のせん断力で剥離する。これにより、得られるゾル三次元構造は、例えば、一定範囲の粒度分布をもつ空隙構造を保持することができ、塗工・乾燥時の堆積による空隙構造を再形成できる。前記粉砕の条件は、特に制限されず、例えば、瞬間的に高速の流れを与えることで、溶媒を揮発させることなくゲルを粉砕することができることが好ましい。例えば、前述のような粒度バラツキ(例えば、体積平均粒子径または粒度分布)の粉砕物となるように粉砕することが好ましい。仮に粉砕時間・強度等の仕事量が不足した場合は、例えば、粗粒が残ることとなり緻密な細孔を形成できないばかりか外観欠点も増加し高い品質を得ることができない可能性がある。一方で、仕事量が過多な場合は、例えば、所望の粒度分布よりも微細なゾル粒子となり、塗工・乾燥後に堆積した空隙サイズが微細となり、所望の空孔率に満たない可能性がある。 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, whereas 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. Thereby, 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. For example, it is preferable that the gel can be pulverized without volatilizing the solvent by instantaneously applying a high-speed flow. For example, it is preferable to grind so as to obtain a pulverized product having a particle size variation as described above (for example, a volume average particle size or a particle size distribution). If the amount of work such as pulverization time and strength is insufficient, for example, coarse grains remain and not only fine pores cannot be formed, but also appearance defects may increase and high quality may not be obtained. On the other hand, when 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. .
 以上のようにして、前記微細孔粒子(例えば、ゲル状シリカ化合物の粉砕物)を含む液(例えば懸濁液)を作製することができる。さらに、前記微細孔粒子を含む液を作製した後に、または作製工程中に、前記微細孔粒子同士を化学的に結合させる触媒を加えることにより、前記微細孔粒子および前記触媒を含む含有液を作製することができる。前記触媒の添加量は、特に限定されないが、前記微細孔粒子の重量に対し、例えば、0.01~20重量%、0.05~10重量%、または0.1~5重量%である。前記触媒は、例えば、前記微細孔粒子同士の架橋結合を促進する触媒であっても良い。前記微細孔粒子同士を化学的に結合させる化学反応としては、シリカゾル分子に含まれる残留シラノール基の脱水縮合反応を利用することが好ましい。シラノール基の水酸基同士の反応を前記触媒で促進することで、短時間で空隙構造を硬化させる連続成膜が可能である。前記触媒としては、例えば、光活性触媒および熱活性触媒が挙げられる。前記光活性触媒によれば、例えば、前記空隙層形成工程において、加熱によらずに前記微細孔粒子同士を化学的に結合(例えば架橋結合)させることができる。これによれば、例えば、前記空隙層形成工程において、前記空隙層全体の収縮が起こりにくいため、より高い空隙率を維持できる。また、前記触媒に加え、またはこれに代えて、触媒を発生する物質(触媒発生剤)を用いても良い。例えば、前記光活性触媒に加え、またはこれに代えて、光により触媒を発生する物質(光触媒発生剤)を用いても良いし、前記熱活性触媒に加え、またはこれに代えて、熱により触媒を発生する物質(熱触媒発生剤)を用いても良い。前記光触媒発生剤としては、特に限定されないが、例えば、光塩基発生剤(光照射により塩基性触媒を発生する物質)、光酸発生剤(光照射により酸性触媒を発生する物質)等が挙げられ、光塩基発生剤が好ましい。前記光塩基発生剤としては、例えば、9-アントリルメチル N,N-ジエチルカルバメート(9-anthrylmethyl N,N-diethylcarbamate、商品名WPBG-018)、(E)-1-[3-(2-ヒドロキシフェニル)-2-プロペノイル]ピペリジン((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine、商品名WPBG-027)、1-(アントラキノン-2-イル)エチル イミダゾールカルボキシレート(1-(anthraquinon-2-yl)ethyl imidazolecarboxylate、商品名WPBG-140)、2-ニトロフェニルメチル 4-メタクリロイルオキシピペリジン-1-カルボキシラート(商品名WPBG-165)、1,2-ジイソプロピル-3-〔ビス(ジメチルアミノ)メチレン〕グアニジウム 2-(3-ベンゾイルフェニル)プロピオナート(商品名WPBG-266)、1,2-ジシクロヘキシル-4,4,5,5-テトラメチルビグアニジウム n-ブチルトリフェニルボラート(商品名WPBG-300)、および2-(9-オキソキサンテン-2-イル)プロピオン酸1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン(東京化成製)、4-ピペリジンメタノールを含む化合物(商品名HDPD-PB100:ヘレウス社製)等が挙げられる。なお、前記「WPBG」を含む商品名は、いずれも和光純薬工業株式会社の商品名である。前記光酸発生剤としては、例えば、トリアリルスルホニル化合物等が挙げられる。また、前記微細孔粒子同士を化学的に結合させる触媒は、前記光活性触媒および前記光触媒発生剤に限定されず、例えば、熱活性触媒または尿素のような熱触媒発生剤でも良い。前記微細孔粒子同士を化学的に結合させる触媒は、例えば、水酸化カリウム、水酸化ナトリウム、水酸化アンモニウム等の塩基触媒、塩酸、酢酸、シュウ酸等の酸触媒等が挙げられる。これらの中で、塩基触媒が好ましい。前記微細孔粒子同士を化学的に結合させる触媒もしくは触媒発生剤は、例えば、前記粉砕物(微細孔粒子)を含むゾル粒子液(例えば懸濁液)に、塗工直前に添加して使用する、または前記触媒もしくは触媒発生剤を溶媒に混合した混合液として使用することができる。前記混合液は、例えば、前記ゾル粒子液に直接添加して溶解した塗工液、前記触媒もしくは触媒発生剤を溶媒に溶解した溶液、または、前記触媒もしくは触媒発生剤を溶媒に分散した分散液でもよい。前記溶媒は、特に制限されず、例えば、水、緩衝液、各種有機溶剤等が挙げられる。 As described above, a liquid (for example, a suspension) containing the fine pore particles (for example, a pulverized product of a gel-like silica compound) can be produced. Furthermore, after producing the liquid containing the fine pore particles or during the production process, 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. 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. Examples of 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. In addition to or instead of the catalyst, a substance that generates a catalyst (catalyst generator) may be used. For example, in addition to or instead of the photoactive catalyst, a substance that generates a catalyst by light (photocatalyst generator) may be used, or in addition to or instead of the thermally active catalyst A substance that generates water (thermal catalyst generator) 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-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate (trade name WPBG-300) and 2- (9-oxoxanthen-2-yl) propionic acid 1, 5,7-triazabicyclo [4.4.0] dec-5-ene (manufactured by Tokyo Chemical Industry), compounds containing 4-piperidinemethanol (trade name HDPD-PB100: manufactured by Heraeus), and the like. 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. Alternatively, 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. But you can. The solvent is not particularly limited, and examples thereof include water, buffer solutions, and various organic solvents.
 また、例えば、前記微細孔粒子が、3官能以下の飽和結合官能基を少なくとも含むケイ素化合物から得られたゲル状ケイ素化合物の粉砕物である場合、前記微細孔粒子を含む液を作製した後に、または作製工程中に、さらに、前記微細孔粒子同士を間接的に結合させるための架橋補助剤を添加してもよい。この架橋補助剤が、粒子同士の間に入り込み、粒子と架橋補助剤が各々相互作用もしくは結合することで、距離的に多少離れた粒子同士も結合させることが可能であり、効率よく強度を上げることが可能となる。前記架橋補助剤としては、多架橋シランモノマーが好ましい。前記多架橋シランモノマーは、具体的には、例えば、2以上3以下のアルコキシシリル基を有し、アルコキシシリル基間の鎖長が炭素数1以上10以下であっても良く、炭素以外の元素も含んでもよい。前記架橋補助剤としては、例えば、ビス(トリメトキシシリル)エタン、ビス(トリエトキシシリル)エタン、ビス(トリメトキシシリル)メタン、ビス(トリエトキシシリル)メタン、ビス(トリエトキシシリル)プロパン、ビス(トリメトキシシリル)プロパン、ビス(トリエトキシシリル)ブタン、ビス(トリメトキシシリル)ブタン、ビス(トリエトキシシリル)ペンタン、ビス(トリメトキシシリル)ペンタン、ビス(トリエトキシシリル)ヘキサン、ビス(トリメトキシシリル)ヘキサン、ビス(トリメトキシシリル)-N-ブチル-N-プロピル-エタン-1,2-ジアミン、トリス-(3-トリメトキシシリルプロピル)イソシアヌレート、トリス-(3-トリエトキシシリルプロピル)イソシアヌレート等が挙げられる。この架橋補助剤の添加量としては、特に限定されないが、例えば、前記ケイ素化合物の微細孔粒子の重量に対して0.01~20重量%、0.05~15重量%、または0.1~10重量%である。 For example, when 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, after preparing a liquid containing the microporous particles, Alternatively, 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. As the crosslinking aid, a polycrosslinked silane monomer is preferable. Specifically, 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. Examples of the crosslinking aid 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) -N-butyl-N-propyl-ethane-1,2-diamine, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) ) Isocyanurate and the like. The addition amount of the crosslinking aid is not particularly limited, and for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 0.1% by weight with respect to the weight of the fine pore particles of the silicon compound. 10% by weight.
[2.3.1.2 塗工工程の詳細]
 つぎに、樹脂フィルム(以下「基材」という場合がある。)上に前記微細孔粒子を含む含有液(例えば懸濁液)を塗工する(塗工工程)。前記塗工は、例えば、後述する各種塗工方式を用いることができ、また、これらに限定されない。前記微細孔粒子(例えばゲル状シリカ化合物の粉砕物)を含む含有液を、前記樹脂フィルム上に直接塗工することにより、前記微細孔粒子および前記触媒を含む塗工膜を形成することができる。前記塗工膜は、例えば、塗工層ということもできる。また、以下において、前記塗工膜(塗工層)を「未架橋膜」という場合がある。前記塗工膜(未架橋膜)を形成することにより、例えば、前記三次元構造が破壊された前記粉砕物が沈降・堆積することによって、新たな三次元構造が構築される。なお、例えば、前記微細孔粒子を含む含有液が、前記微細孔粒子同士を化学的に結合させる触媒を含まなくても良い。例えば、後述するように、前記塗工膜(未架橋膜)に、前記微細孔粒子同士を化学的に結合させる触媒を吹き付けてから、または吹き付けながら前記空隙層形成工程を行っても良い。しかし、前記微細孔粒子を含む含有液が、前記微細孔粒子同士を化学的に結合させる触媒を含み、前記塗工膜(未架橋膜)中に含まれる前記触媒の作用により、前記微細孔粒子同士を化学的に結合させて前記多孔体(空隙層)を形成してもよい。
[2.3.1.2 Details of coating process]
Next, 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). For the coating, 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. In the following, the coating film (coating layer) may be referred to as an “uncrosslinked film”. By forming the coating film (uncrosslinked film), for example, the pulverized material in which the three-dimensional structure is destroyed settles and deposits, whereby a new three-dimensional structure is constructed. For example, the liquid containing the fine pore particles may not contain a catalyst that chemically bonds the fine pore particles. For example, as will be described later, 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). However, 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.
 前記溶媒(以下、「塗工用溶媒」ともいう)は、特に制限されず、例えば、有機溶媒が使用できる。前記有機溶媒は、例えば、沸点130℃以下の溶媒が挙げられる。具体例としては、例えば、IPA、エタノール、メタノール、ブタノール等が挙げられ、また、前記粉砕用溶媒と同様のものが使用できる。本発明が、前記ゲル状シリカ化合物を粉砕する工程を含む場合、前記塗工膜(未架橋膜)の形成工程においては、例えば、前記ゲル状シリカ化合物の粉砕物を含む前記粉砕用溶媒を、そのまま使用してもよい。 The solvent (hereinafter also referred to as “coating solvent”) is not particularly limited, and for example, an organic solvent can be used. Examples of the organic solvent include solvents having a boiling point of 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. When 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.
 前記塗工工程においては、例えば、前記溶媒に分散させたゾル状の前記粉砕物(以下、「ゾル粒子液」ともいう)を、前記基材上に塗工することが好ましい。本発明のゾル粒子液は、例えば、基材上に塗工・乾燥した後に、前記化学架橋を行うことで、一定レベル以上の膜強度を有する空隙層を、連続成膜することが可能である。なお、本発明における「ゾル」とは、ゲルの三次元構造を粉砕することで、空隙構造の一部を保持したナノ三次元構造のシリカゾル粒子が溶媒中に分散して流動性を示す状態をいう。 In the coating step, for example, 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.
 前記溶媒における前記粉砕物の濃度は、特に制限されず、例えば、0.3~50%(v/v)、0.5~30%(v/v)、1.0~10%(v/v)である。前記粉砕物の濃度が高すぎると、例えば、前記ゾル粒子溶液の流動性が著しく低下し、塗工時の凝集物・塗工スジを発生させる可能性がある。一方で、前記粉砕物の濃度が低すぎると、例えば、前記ゾル粒子液の溶媒の乾燥に相当の時間がかかるだけでなく、乾燥直後の残留溶媒も高くなるために、空孔率が低下してしまう可能性がある。 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). When the 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. On the other hand, if the 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.
 前記ゾルの物性は、特に制限されない。前記ゾルのせん断粘度は、例えば、10001/sのせん断速度において、例えば、粘度100cPa・s以下、粘度10cPa・s以下、粘度1cPa・s以下である。せん断粘度が高すぎると、例えば、塗工スジが発生し、グラビア塗工の転写率の低下等の不具合が見られる可能性がある。逆に、せん断粘度が低すぎる場合は、例えば、塗工時のウェット塗布(塗工)厚みを厚くすることができず、乾燥後に所望の厚みが得られない可能性がある。 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.
 前記基材に対する前記粉砕物の塗工量は、特に制限されず、例えば、所望の前記シリコーン多孔体の厚み等に応じて、適宜設定できる。具体例として、厚み0.1~1000μmの前記シリコーン多孔体を形成する場合、前記基材に対する前記粉砕物の塗工量は、前記基材の面積1mあたり、例えば、0.01~60000μg、0.1~5000μg、1~50μgである。前記ゾル粒子液の好ましい塗工量は、例えば、液の濃度や塗工方式等と関係するため、一義的に定義することは難しいが、生産性を考慮すると、できるだけ薄層で塗工することが好ましい。塗工量(塗布量)が多すぎると、例えば、溶媒が揮発する前に乾燥炉で乾燥される可能性が高くなる。これにより、溶媒中でナノ粉砕ゾル粒子が沈降・堆積し、空隙構造を形成する前に、溶媒が乾燥することで、空隙の形成が阻害されて空孔率が大きく低下する可能性がある。一方で、塗工量が薄過ぎると、基材の凹凸・親疎水性のバラツキ等により塗工ハジキが発生するリスクが高くなる可能性がある。 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. As a specific example, when the porous silicone body having a thickness of 0.1 to 1000 μm is formed, the amount of the pulverized material applied to the base material is, for example, 0.01 to 60000 μg per 1 m 2 of the base material. 0.1 to 5000 μg and 1 to 50 μg. 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. If 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. On the other hand, if 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.
[2.3.1.3 乾燥工程の詳細]
 さらに、本発明の製造方法は、例えば、前述のように、微細孔粒子含有液を塗工して作製された塗工膜(未架橋膜)を乾燥させる乾燥工程を有する。前記乾燥工程における乾燥処理によって、例えば、前記塗工膜(未架橋膜)中の前記溶媒(前記ゾル粒子液に含まれる溶媒)を除去するだけでなく、乾燥処理中に、ゾル粒子を沈降・堆積させ、空隙構造を形成させることを目的としている。前記乾燥処理の温度は、例えば、50~250℃、60~150℃、70~130℃であり、前記乾燥処理の時間は、例えば、0.1~30分、0.2~10分、0.3~3分である。乾燥処理温度、および時間については、例えば、連続生産性や高い空孔率の発現の関連では、より低く短いほうが好ましい。条件が厳しすぎると、例えば、基材が樹脂フィルムの場合、前記基材のガラス転移温度に近づくことで、前記基材が乾燥炉の中で伸展してしまい、塗工直後に、形成された空隙構造にクラック等の欠点が発生する可能性がある。一方で、条件が緩すぎる場合、例えば、乾燥炉を出たタイミングで残留溶媒を含むため、次工程でロールと擦れた際に、スクラッチ傷が入る等の外観上の不具合が発生する可能性がある。
[2.3.1.3 Details of drying process]
Furthermore, the manufacturing method of this invention has a drying process which dries the coating film (non-crosslinked film | membrane) produced by applying the fine pore particle containing liquid as mentioned above, for example. By 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., and 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.
 前記乾燥処理は、例えば、自然乾燥でもよいし、加熱乾燥でもよいし、減圧乾燥でもよい。前記乾燥方法は、特に制限されず、例えば、一般的な加熱手段が使用できる。前記加熱手段は、例えば、熱風器、加熱ロール、遠赤外線ヒーター等が挙げられる。中でも、工業的に連続生産することを前提とした場合は、加熱乾燥を用いることが好ましい。また、使用される溶媒については、乾燥時の溶媒揮発に伴う収縮応力の発生、それによる空隙層(前記シリコーン多孔体)のクラック現象を抑える目的で、表面張力が低い溶媒が好ましい。前記溶媒としては、例えば、イソプロピルアルコール(IPA)に代表される低級アルコール、ヘキサン、ペルフルオロヘキサン等が挙げられるが、これらに限定されない。また、上記IPA等にペルフルオロ系界面活性剤もしくはシリコン系界面活性剤を少量添加し表面張力を低下させてもよい。 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. Examples of the heating means include a hot air fan, a heating roll, and a far infrared heater. Above all, when it is premised on industrial continuous production, it is preferable to use heat drying. As the solvent used, 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). Examples of the solvent 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.
 さらに、本発明の積層光学フィルムの製造方法は、例えば、前記微細孔粒子同士を前記触媒の作用により化学的に結合させて前記多孔体(空隙層)を形成する(空隙層形成工程)。これにより、例えば、前記塗工膜(未架橋膜)における前記粉砕物の三次元構造が、固定化される。従来の焼結による固定化を行う場合は、例えば、200℃以上の高温処理を行うことで、シラノール基の脱水縮合、シロキサン結合の形成を誘発する。本発明においては、上記の脱水縮合反応を触媒する各種添加剤を反応させることで、例えば、前記基材(樹脂フィルム)にダメージを起こすことなく、100℃前後の比較的低い乾燥温度、および数分未満の短い処理時間で、連続的に空隙構造を形成、固定化することができる。 Furthermore, in the method for producing a laminated optical film of the present invention, for example, the fine pore particles are chemically bonded by the action of the catalyst to form the porous body (void layer) (void layer forming step). Thereby, for example, the three-dimensional structure of the pulverized product in the coating film (uncrosslinked film) is fixed. When fixing by conventional sintering, for example, high temperature treatment at 200 ° C. or higher induces dehydration condensation of silanol groups and formation of siloxane bonds. In the present invention, by reacting 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.
 前記化学的に結合させる方法は、特に制限されず、例えば、前記ゲル状ケイ素化合物の種類に応じて、適宜決定できる。具体例として、前記化学的な結合は、例えば、前記粉砕物同士の化学的な架橋結合により行うことができ、その他にも、例えば、酸化チタン等の無機粒子等を、前記粉砕物に添加した場合、前記無機粒子と前記粉砕物とを化学的に架橋結合させることも考えられる。また、酵素等の生体触媒を担持させる場合も、触媒活性点とは別の部位と前記粉砕物とを化学架橋結合させる場合もある。したがって、本発明は、例えば、前記ゾル粒子同士で形成する空隙層(シリコーン多孔体)だけでなく、有機無機ハイブリッド空隙層、ホストゲスト空隙層等の応用展開が考えられるが、これらに限定されない。 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. As a specific example, 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. In addition, when a biocatalyst such as an enzyme is supported, a site other than the catalytic active site and the pulverized product may be chemically crosslinked. Therefore, 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.
 前記触媒存在下での化学反応(空隙層形成工程)は、本発明の製造方法におけるどの段階で行う(起こる)かは、特に限定されない。例えば、本発明の積層光学フィルムの製造方法では、前記乾燥工程が前記空隙層形成工程を兼ねていても良い。また、例えば、前記乾燥工程後に、さらに、前記微細孔粒子同士を前記触媒の作用により化学的に結合させる前記空隙層形成工程を行っても良い。例えば、前述のとおり、前記触媒が光活性触媒であり、前記空隙層形成工程において、光照射により、前記微細孔粒子同士を化学的に結合させて前記多孔体(空隙層)を形成しても良い。また、前記触媒が、熱活性触媒であり、前記空隙層形成工程において、加熱により、前記微細孔粒子同士を化学的に結合させて前記多孔体(空隙層)を形成しても良い。 It is not particularly limited at which stage the chemical reaction (void layer forming step) in the presence of the catalyst is performed (occurs) in the production method of the present invention. For example, in the method for producing a laminated optical film of the present invention, the drying step may also serve as the gap layer forming step. Further, for example, after the drying step, the void layer forming step of chemically bonding the fine pore particles by the action of the catalyst may be performed. For example, as described above, 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.
 前記化学反応は、例えば、事前に前記ゾル粒子液(例えば懸濁液)に添加された前記触媒もしくは触媒発生剤を含む前記塗工膜に対し光照射もしくは加熱、または、前記塗工膜に、前記触媒を吹き付けてから光照射もしくは加熱、または、前記触媒もしくは触媒発生剤を吹き付けながら光照射もしくは加熱することによって、行うことができる。前記光照射における積算光量は、特に限定されないが、@360nm換算で、例えば、200~800mJ/cm、250~600mJ/cm、または300~400mJ/cmである。照射量が十分でなく触媒発生剤の光吸収による分解が進まず効果が不十分となることを防止する観点からは、200mJ/cm以上の積算光量が良い。また、空隙層下の基材にダメージがかかり熱ジワが発生することを防止する観点からは、800mJ/cm以下の積算光量が良い。前記加熱処理の条件は、特に制限されず、前記加熱温度は、例えば、50~250℃、60~150℃、70~130℃であり、前記加熱時間は、例えば、0.1~30分、0.2~10分、0.3~3分である。または、前述のとおり塗工された前記ゾル粒子液(例えば懸濁液)を乾燥する工程が、前記触媒存在下での化学反応を行う工程を兼ねていても良い。すなわち、塗工された前記ゾル粒子液(例えば懸濁液)を乾燥する工程において、前記触媒存在下での化学反応により、前記粉砕物(微細孔粒子)同士を化学的に結合させても良い。この場合において、前記乾燥工程後に前記塗工膜をさらに加熱することにより、前記粉砕物(微細孔粒子)同士をさらに強固に結合させても良い。さらに、前記触媒存在下での化学反応は、前記微細孔粒子含有液(例えば懸濁液)を作製する工程、および、前記微細孔粒子含有液を塗工する工程においても起こる場合があると推測される。しかしながら、この推測は、本発明を何ら限定しない。また、使用される溶媒については、例えば、乾燥時の溶媒揮発に伴う収縮応力の発生、それによる空隙層のクラック現象を抑える目的で、表面張力が低い溶媒が好ましい。例えば、イソプロピルアルコール(IPA)に代表される低級アルコール、ヘキサン、ペルフルオロヘキサン等が挙げられるが、これらに限定されない。 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,. From the viewpoint of preventing the irradiation amount from being insufficient and the decomposition due to light absorption of the catalyst generator from proceeding and preventing the effect from becoming insufficient, 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. Alternatively, 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. However, this assumption does not limit the present invention in any way. As the solvent used, for example, 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.
[2.3.1.4 強度向上工程(エージング工程)の詳細]
 さらに、本発明の空隙層に対し、例えば、加熱エージング等の処理をして強度を向上させる強度向上工程(エージング工程)を行ってもよい。前記強度向上工程(エージング工程)においては、例えば、本発明の空隙層を加熱してもよい。前記強度向上工程(エージング工程)における温度は、例えば30~80℃、35~70℃、40~60℃、または50~60℃である。前記エージング工程を行う時間は、例えば1~50hr、3~40hr、5~30hr、または7~25hrである。前記エージング工程においては、例えば、加熱温度を低温にすることで、前記空隙層の収縮を抑制しながら粘着ピール強度を向上させ、高空隙率と強度の両立を達成できる。
[2.3.1.4 Details of Strength Improvement Process (Aging Process)]
Furthermore, you may perform the intensity | strength improvement process (aging process) which processes a void layer of this invention, for example, heat-aging, etc., and improves an intensity | strength. In the strength improving step (aging step), for example, 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. In the aging step, for example, by lowering the heating temperature, the adhesive peel strength can be improved while suppressing the shrinkage of the void layer, and both high porosity and strength can be achieved.
[2.3.2 カバー層形成工程の詳細]
 つぎに、前記空隙層上に、前記カバー層を直接形成する(カバー層形成工程)。前記カバー層形成工程において、前記カバー層を、前記空隙層上に貼り合せることにより、前記空隙層上に前記カバー層を形成してもよい。前記カバー層形成工程は、特に限定されず、例えば、前記カバー層原料液塗工工程、前記カバー層原料液乾燥工程、および前記カバー層強度向上工程(エージング工程)を含む。
[2.3.2 Details of cover layer forming process]
Next, the cover layer is directly formed on the gap layer (cover layer forming step). In the 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).
[2.3.2.1 カバー層原料液塗工工程の詳細]
 まず、例えば、前記空隙層上に前記カバー層の原料を含む前記カバー層原料液を直接塗工する(カバー層原料液塗工工程)。前記カバー層原料液塗工工程は、前記空隙層形成工程における塗工工程と同様の塗工方式を用いてもよい。また、前記カバー層原料液塗工工程において、塗工用溶媒は、前記空隙層形成工程における前記塗工用溶媒で例示した溶媒を用いてもよい。
[2.3.2.1 Details of Cover Layer Raw Material Coating Process]
First, for example, the 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. In the cover layer raw material liquid coating step, the solvent exemplified in the coating solvent in the void layer forming step may be used as the coating solvent.
[2.3.2.2 カバー層原料液乾燥工程の詳細]
 次に、例えば、前記塗工した前記カバー層の原料を含む液を乾燥する(カバー層原料液乾燥工程)。前記乾燥処理の温度および時間は、前記空隙層形成工程における乾燥工程で例示した温度および時間であってもよい。
[Details of 2.3.2.2 Cover Layer Raw Material Drying Process]
Next, for example, 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.
 前記カバー層形成工程において、前記カバー層原料液乾燥工程後に、加熱および光照射の少なくとも一方により前記カバー層を形成する。前記カバー層形成工程において、例えば、光照射により、前記カバー層中の化合物と、前記空隙層の前記微細孔同士を化学的に結合させてもよいし、前記触媒が、熱活性触媒であり、前記カバー層形成工程において、加熱により、前記カバー層中の化合物と、前記微細孔粒子とを化学的に結合させてもよい。前記光照射における光照射量、前記加熱処理の温度、前記加熱時間は、特に制限されず、前記空隙層形成工程において例示したものと同様であってもよい。 In the cover 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. In the cover layer forming step, for example, the compound in the cover layer and the micropores of the void layer may be chemically bonded by light irradiation, and the catalyst is a thermally active catalyst, In 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.
[2.3.2.3 強度向上工程の詳細]
 前記カバー層形成工程において、さらに、例えば、80℃以下で1時間以上加熱して前記形成されたカバー層の強度を向上してもよい(強度向上工程(エージング工程))。前記加熱温度の上限は、例えば、80℃以下であり、例えば、70℃以下、例えば、60℃以下であり、前記加熱温度の下限は、例えば30℃以上であり、例えば、35℃以上であり、例えば、40℃以上であり、その範囲は、例えば、30℃以上80℃以下であり、例えば、35℃以上70℃以下であり、例えば、40℃以上60℃以下である。前記加熱時間の下限は、1hr(時間)以上であり、例えば、3hr(時間)以上であり、例えば、4hr(時間)以上であり、その上限は、例えば、50hr以下であり、例えば、40hr以下であり、例えば、30hr以下であり、その範囲は、例えば、1hr以上50hr以下であり、例えば、3hr以上40hr以下であり、例えば、4hr以上30hr以下である。
[2.3.2.3 Details of Strength Improvement Process]
In the cover layer forming step, for example, 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, and the lower limit of the heating temperature is, for example, 30 ° C. or more, for example, 35 ° C. or more. For example, 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, and the upper limit is, for example, 50 hr or less, for example, 40 hr or less. For example, it is 30 hr or less, and 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.
 以上のようにして、本発明の積層光学フィルムの製造方法を行うことができる。本発明の製造方法により製造される積層光学フィルムは、例えば、ロール状の多孔体とすることができ、製造効率が良い、取り扱いやすい等の利点がある。 As described above, 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.
 このようにして得られる本発明の積層光学フィルム(空隙層)は、例えば、さらに、他のフィルム(層)と積層して、前記多孔質構造を含む積層構造体としてもよい。この場合、前記積層構造体において、各構成要素は、例えば、粘着剤または接着剤を介して積層させてもよい。 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. In this case, in the laminated structure, each component may be laminated via, for example, a pressure-sensitive adhesive or an adhesive.
[2.4 長尺フィルムを用いた積層光学フィルムの製造方法の詳細]
 前記各構成要素の積層は、例えば、効率的であることから、長尺フィルムを用いた連続処理(いわゆるRoll to Roll等)により積層を行ってもよく、基材が成形物・素子等の場合はバッチ処理を行ったものを積層してもよい。
[2.4 Details of Manufacturing Method of Laminated Optical Film Using Long Film]
For example, since the lamination of each constituent element is efficient, the lamination may be performed by continuous processing using a long film (so-called Roll to Roll, etc.). May be laminated with batch processing.
 以下に、基材(樹脂フィルム)上に前記本発明の空隙層およびカバー層を形成する方法について、連続処理工程に関して、図1~3を用いて例をあげて説明する。図2については、前記シリコーン多孔体を製膜した後に、保護フィルムを貼合して巻き取る工程を示しているが、別の機能性フィルムに積層を行う場合は、上記の手法を用いてもよいし、別の機能性フィルムを塗工、乾燥した後に、上記成膜を行った前記シリコーン多孔体を、巻き取り直前に貼り合せることも可能である。なお、図示した製膜方式はあくまで一例であり、これらに限定されない。 Hereinafter, a method for forming the void layer and the cover layer of the present invention on a substrate (resin film) will be described with reference to FIGS. About FIG. 2, although forming the said silicone porous body and showing the process of bonding and winding up a protective film, when laminating | stacking on another functional film, even if it uses said method Alternatively, after coating and drying another functional film, the silicone porous body on which the film has been formed can be bonded immediately before winding. The illustrated film forming method is merely an example, and the present invention is not limited thereto.
 なお、前記基材は、本発明の積層光学フィルムの説明において前述した樹脂フィルムでもよい。この場合、前記基材上への前記空隙層の形成により、本発明の空隙層が得られる。また、前記基材上で前記空隙層を形成した後、前記空隙層を、本発明の空隙層の説明において前述した樹脂フィルムに積層することによっても、本発明の空隙層が得られる。 The substrate may be the resin film described above in the explanation of the laminated optical film of the present invention. In this case, the void layer of the present invention is obtained by forming the void layer on the substrate. Moreover, after forming the said void layer on the said base material, the said void layer is laminated | stacked on the resin film mentioned above in description of the void layer of this invention, and the void layer of this invention is obtained.
 図1の断面図に、前記基材(樹脂フィルム)上に前記空隙層および前記カバー層が前記順序で積層された本発明の製造方法における工程の一例を、模式的に示す。図1において、前記空隙層の形成方法は、基材(樹脂フィルム)10上に、前記微細孔粒子のゾル粒子液20’’を塗工して塗工膜を形成する塗工工程(1)、ゾル粒子液20’’を乾燥させて、乾燥後の塗工膜20’を形成する乾燥工程(2)、塗工膜20’に化学処理(例えば、架橋処理)をして、空隙層20を形成する化学処理工程(例えば、架橋工程)(3)、空隙層20の強度を向上させ、強度が向上した空隙層21とする強度向上工程(4)、空隙層21上にカバー層原料液22’’を直接塗工するカバー層塗工工程(カバー層原料液塗工工程)(5)、塗工したカバー層原料液22’’を乾燥させて、乾燥後の塗工膜22’を形成する乾燥工程(6)、前記乾燥工程後に、化学処理(例えば、架橋処理)をして、カバー層22を形成する化学処理工程(例えば、架橋工程)(7)、カバー層22の強度を向上させ、強度が向上したカバー層23とする強度向上工程(8)を含む。以上の工程(1)~(8)により、図示のとおり、樹脂フィルム10上に、空隙層21と、カバー層23とが、前記順序で積層された積層光学フィルムを製造できる。さらに、本発明の積層光学フィルムの製造方法は、前記工程(1)~(8)以外の工程を、適宜含んでいても良いし、含んでいなくても良い。また、前記工程の(4)は、カバー層の工程(8)と兼任させてもよい。すなわち、前記カバー層の強度向上工程(8)において、同時に空隙層の強度を向上させても良い。 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). In FIG. 1, 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 | grain on the base material (resin film) 10, and forms a coating film. 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 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. A drying step (6) to be formed, and after the drying step, a chemical treatment (for example, a crosslinking treatment) is performed to form the cover layer 22 Forming chemical process (e.g., cross-linking step) (7), including to improve the strength of the cover layer 22, strength enhancing step to cover layer 23 the strength was improved (8). Through the above steps (1) to (8), as shown in the drawing, 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. Furthermore, 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.
 塗工工程(1)において、ゾル粒子液20’’の塗工方法は特に限定されず、一般的な塗工方法を採用できる。塗工方法(1)としては、例えば、スロットダイ法、リバースグラビアコート法、マイクログラビア法(マイクログラビアコート法)、ディップ法(ディップコート法)、スピンコート法、刷毛塗り法、ロールコート法、フレキソ印刷法、ワイヤーバーコート法、スプレーコート法、エクストルージョンコート法、カーテンコート法、リバースコート法等が挙げられる。これらの中で、生産性、塗膜の平滑性等の観点から、エクストルージョンコート法、カーテンコート法、ロールコート法、マイクログラビアコート法等が好ましい。前記ゾル粒子液20’’の塗工量は、特に限定されず、例えば、空隙層20の厚みが適切になるように、適宜設定可能である。空隙層21の厚みは、特に限定されず、例えば、前述の通りである。 In the coating step (1), the coating method of the sol particle liquid 20 ″ is not particularly limited, and a general coating method can be adopted. Examples of 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. Among these, 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.
 乾燥工程(2)において、ゾル粒子液20’’を乾燥し(すなわち、ゾル粒子液20’’に含まれる分散媒を除去し)、乾燥後の塗工膜(空隙層の前駆体)20’を形成する。乾燥処理の条件は、特に限定されず、前述の通りである。 In the drying step (2), 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 ′. Form. The conditions for the drying treatment are not particularly limited and are as described above.
 さらに、化学処理工程(3)において、塗工前に添加した前記触媒(例えば、光活性触媒、光触媒発生剤、熱活性触媒または熱触媒発生剤)を含む塗工膜20’に対し、光照射または加熱し、塗工膜20’中の前記微細孔粒子同士を化学的に結合させて(例えば、架橋させて)、空隙層20を形成する。前記化学処理工程(3)における光照射または加熱条件は、特に限定されず、前述の通りである。 Furthermore, in the chemical treatment step (3), the coating film 20 ′ containing the catalyst (for example, photoactive catalyst, photocatalyst generator, thermal active catalyst or thermal catalyst generator) added before coating is irradiated with light. Alternatively, 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.
 さらに、強度向上工程(4)において、空隙層20の強度を向上させる。強度向上工程(4)における処理温度および処理時間は、特に制限されず、前述の通りである。また、本工程(4)は、後述する工程(8)と同時に行なってもよく、工程(3)で処理工程を経た直後に、カバー層塗工工程(5)を行なってもよい。このとき、工程(5)の前に一度巻き取ってもよいし、巻き取らず連続的に塗工工程(5)を行なってもよい。 Further, in the strength improving step (4), 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. Moreover, 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.
 さらに、塗工工程(5)において、カバー層原料液22’’の塗工方法は、特に限定されず、塗工工程(1)で例示した方法を用いてもよい。また、カバー層原料液22’’の塗工量は、特に限定されず、カバー層22の厚みが適切になるように、適宜設定可能である。カバー層22の厚みは、特に限定されず、前述の通りである。 Furthermore, in the coating process (5), 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.
 さらに、乾燥工程(6)において、カバー層原料液22’’を乾燥するための乾燥処理の条件は、特に限定されず、乾燥工程(2)と同様の乾燥処理条件であってもよい。 Furthermore, in the drying step (6), 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).
 さらに、化学処理工程(7)において、光照射または加熱により、空隙層21の微細孔粒子とカバー層原料液22’’中の化合物とを化学的に結合させて(例えば、架橋させて)、カバー層22を形成する。化学処理工程(7)における光照射または加熱条件は、特に限定されず、化学処理工程(3)と同様としてもよい。 Furthermore, in the chemical treatment step (7), 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).
 さらに、強度向上工程(8)において、カバー層22の強度を向上させる。強度向上工程(8)における処理温度および処理時間は、特に限定されないが、例えば、前述の通りである。 Furthermore, in the strength improving step (8), 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.
 つぎに、図2に、スロットダイ法の塗工装置およびそれを用いた前記空隙層の形成方法の一例を模式的に示す。なお、図2は、断面図であるが、見易さのため、ハッチを省略している。 Next, FIG. 2 schematically shows an example of a slot die coating apparatus and a method for forming the void layer using the same. Although FIG. 2 is a cross-sectional view, hatching is omitted for easy viewing.
 図示のとおり、この装置を用いた方法における各工程は、基材10を、ローラによって一方向に搬送しながら行う。搬送速度は、特に限定されず、例えば、1~100m/分、3~50m/分、5~30m/分である。 As shown in the figure, 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.
 まず、送り出しローラ101から基材10を繰り出して搬送しながら、塗工ロール102において、基材10にゾル粒子液20’’を塗工する塗工工程(1)を行い、続いて、オーブンゾーン110内で乾燥工程(2)に移行する。図2の塗工装置では、塗工工程(1)の後、乾燥工程(2)に先立ち、予備乾燥工程を行う。予備乾燥工程は、加熱をせずに、室温で行うことができる。乾燥工程(2)においては、加熱手段111を用いる。加熱手段111としては、前述のとおり、熱風器、加熱ロール、遠赤外線ヒーター等を適宜用いることができる。また、例えば、乾燥工程(2)を複数の工程に分け、後の乾燥工程になるほど乾燥温度を高くしても良い。 First, 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. In 110, the process proceeds to the drying step (2). In the coating apparatus of FIG. 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. In the drying step (2), the heating means 111 is used. As 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. Further, for example, 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.
 乾燥工程(2)の後に、化学処理ゾーン120内で化学処理工程(3)を行う。化学処理工程(3)においては、例えば、乾燥後の塗工膜20’が光活性触媒を含む場合、基材10の上下に配置したランプ(光照射手段)121で光照射する。または、例えば、乾燥後の塗工膜20’が熱活性触媒を含む場合、ランプ(光照射装置)121に代えて熱風器(加熱手段)を用い、基材10の上下に配置した熱風器121で基材10を加熱する。この架橋処理により、塗工膜20’中の前記微細孔粒子同士の化学的結合が起こり、空隙層20が硬化・強化される。なお、本例では、乾燥工程(2)の後に化学処理工程(3)を行っているが、前述のとおり、本発明の製造方法のどの段階で前記微細孔粒子同士の化学的結合を起こさせるかは、特に限定されない。例えば、前述のように、乾燥工程(2)が化学処理工程(3)を兼ねていても良い。また、乾燥工程(2)において前記化学的結合が起こった場合でも、さらに化学処理工程(3)を行い、前記微細孔粒子同士の化学的結合を、さらに強固にしても良い。また、乾燥工程(2)よりも前の工程(例えば、予備乾燥工程、塗工工程(1)、塗工液(例えば懸濁液)を作製する工程等)において、前記粉砕物同士の化学的結合が起こっても良い。 After the drying step (2), the chemical treatment step (3) is performed in the chemical treatment zone 120. In the chemical treatment step (3), for example, when the dried coating film 20 ′ includes a photoactive catalyst, light irradiation is performed by lamps (light irradiation means) 121 disposed above and below the base material 10. Alternatively, for example, when the coating film 20 ′ after drying contains a thermally active catalyst, 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. To heat the substrate 10. By this crosslinking treatment, the fine pore particles in the coating film 20 ′ are chemically bonded to each other, and the void layer 20 is cured and strengthened. In this example, the chemical treatment step (3) is performed after the drying step (2). As described above, the chemical bonding between the microporous particles is caused at any stage of the production method of the present invention. There is no particular limitation. For example, as described above, the drying step (2) may also serve as the chemical treatment step (3). Further, even when the chemical bonding occurs in the drying step (2), the chemical treatment step (3) may be further performed to further strengthen the chemical bonding between the microporous particles. In addition, 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.
 化学処理工程(3)の後に、強度向上ゾーン130内で強度向上工程(4)を行う。強度向上工程(4)内においては、例えば、基材10の上に配置した熱風器(加熱手段)131を用いて、空隙層20を加熱してもよい。加熱温度、時間等は、特に限定されないが、例えば、前述のとおりである。 After the chemical treatment step (3), the strength improvement step (4) is performed in the strength improvement zone 130. In the strength improving step (4), for example, the air gap layer 20 may be heated using a hot air fan (heating means) 131 disposed on the base material 10. Although heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
 強度向上工程(4)の後に、カバー層塗工ゾーン140内で塗工工程(5)を行う。塗工工程(5)においては、例えば、カバー層塗工手段141により、空隙層20上にカバー層原料液を直接塗布(塗工)する。また、前述のとおり、カバー層原料液を塗布(塗工)に代えて、カバー層を有するテープ等の貼合(貼付)でもよい。 After the strength improving step (4), the coating step (5) is performed in the cover layer coating zone 140. In the coating step (5), for example, the cover layer raw material liquid is directly applied (coated) on the gap layer 20 by the cover layer coating means 141. 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.
 塗工工程(5)の後に、オーブンゾーン150内で加熱手段151を用いて乾燥工程(6)を行う。乾燥工程(6)に先立ち、室温等で予備乾燥工程を行ってもよいし、乾燥工程(6)を複数の工程に分け、後の乾燥工程になるほど乾燥温度を高くしてもよい。加熱手段151としては、乾燥工程(2)において、例示した加熱手段111を用いてもよい。 After the coating step (5), the drying step (6) is performed using the heating means 151 in the oven zone 150. Prior to the drying step (6), 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. As the heating unit 151, the illustrated heating unit 111 may be used in the drying step (2).
 乾燥工程(6)の後に、化学処理ゾーン160内で光照射手段または加熱手段161を用いて化学処理工程(7)を行う。化学処理工程(7)においては、例えば、カバー層中の化合物と、空隙層中の前記微細孔粒子同士の化学的結合により架橋する。 After the drying step (6), the chemical treatment step (7) is performed using the light irradiation means or the heating means 161 in the chemical treatment zone 160. In 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.
 化学処理工程(7)の後に、強度向上ゾーン170内で加熱手段171により強度向上工程(8)を行う。前記強度向上工程(8)における加熱温度および処理時間は、前述のとおりである。 After the chemical treatment step (7), 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.
 前記空隙層および前記カバー層の形成にあたり、例えば、強度向上工程(エージング工程)(4)に先立ち、塗工工程(5)、乾燥工程(6)、および化学処理工程(7)を施した後、強度向上工程(エージング工程)(8)を施す際に、加熱手段171によりカバー層の強度が向上されるともに、加熱手段171により空隙層もまた加熱されることで、空隙層の強度向上工程(エージング工程)(4)が施されてもよい。これにより、例えば、前記カバー層中の化合物および前記空隙層の前記微細孔粒子を同時にゲル化することができ、前記カバー層と前記空隙層との密着性が向上するとともに、前記カバー層の耐擦傷性もまた向上する。 In forming the gap layer and the cover layer, for example, after applying the coating step (5), the drying step (6), and the chemical treatment step (7) prior to the strength improving step (aging step) (4) When 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. Thereby, for example, 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.
 そして、強度向上工程(8)の後、積層体を、巻き取りロール105により巻き取る。なお、例えば、積層体に、さらに、ロール106から繰り出される保護シートで被覆しても良く、または、前記保護シートに代えて、長尺フィルムから形成された他の層で被覆しても良い。 And after a strength improvement process (8), a laminated body is wound up with the winding roll 105. FIG. For example, 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.
 図3に、マイクログラビア法(マイクログラビアコート法)の塗工装置およびそれを用いた前記空隙層の形成方法の一例を模式的に示す。なお、同図は、断面図であるが、見易さのため、ハッチを省略している。 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. In addition, although the figure is sectional drawing, the hatch is abbreviate | omitted for legibility.
 図示のとおり、この装置を用いた方法における各工程は、図2と同様、基材10を、ローラによって一方向に搬送しながら行う。搬送速度は、特に限定されず、例えば、1~100m/分、3~50m/分、5~30m/分である。 As shown in the figure, 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.
 まず、送り出しローラ201から基材10を繰り出して搬送しながら、基材10にゾル粒子液20’’を塗工する塗工工程(1)を行う。ゾル20粒子液’’の塗工は、図示のとおり、液溜め202、ドクター(ドクターナイフ)203およびマイクログラビア204を用いて行う。具体的には、液溜め202に貯留されているゾル粒子液20’’を、マイクログラビア204表面に付着させ、さらに、ドクター203で所定の厚さに制御しながら、マイクログラビア204で基材10表面に塗工する。なお、マイクログラビア204は、例示であり、これに限定されるものではなく、他の任意の塗工手段を用いても良い。 First, 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. Specifically, 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.
 つぎに、乾燥工程(2)を行う。具体的には、図示のとおり、オーブンゾーン210中に、ゾル粒子液20’’が塗工された基材10を搬送し、オーブンゾーン210内の加熱手段211により加熱してゾル粒子液20’’を乾燥する。加熱手段211は、例えば、図2と同様でも良い。また、例えば、オーブンゾーン210を複数の区分に分けることにより、乾燥工程(2)を複数の工程に分け、後の乾燥工程になるほど乾燥温度を高くしても良い。乾燥工程(2)の後に、化学処理ゾーン220内で、化学処理工程(3)を行う。化学処理工程(3)においては、例えば、乾燥後の塗工膜20’が光活性触媒を含む場合、基材10の上下に配置したランプ(光照射手段)221で光照射する。または、例えば、乾燥後の塗工膜20’が熱活性触媒を含む場合、ランプ(光照射装置)221に代えて熱風器(加熱手段)を用い、基材10の上下に配置した熱風器(加熱手段)221で、基材10を加熱する。この架橋処理により、塗工膜20’中の前記粉砕物同士の化学的結合が起こり、空隙層20が形成される。 Next, 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. After the drying step (2), the chemical treatment step (3) is performed in the chemical treatment zone 220. In 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. Alternatively, for example, when the dried coating film 20 ′ includes a thermally active catalyst, 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. By this crosslinking treatment, the pulverized material in the coating film 20 ′ is chemically bonded to each other, and the void layer 20 is formed.
 化学処理工程(3)の後に、強度向上ゾーン230内で強度向上工程(4)を行う。強度向上工程(4)内においては、例えば、基材10の上下に配置した熱風器(加熱手段)231を用いて、空隙層20を加熱してもよい。加熱温度、時間等は、特に限定されないが、例えば、前述のとおりである。 After the chemical treatment step (3), the strength improvement step (4) is performed in the strength improvement zone 230. In the strength improving step (4), for example, the air gap layer 20 may be heated using hot air blowers (heating means) 231 disposed above and below the base material 10. Although heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
 強度向上工程(4)の後に、カバー層塗工ゾーン240内で塗工工程(5)を行う。塗工工程(5)においては、例えば、カバー層塗工手段241により、空隙層20上にカバー層原料液を直接塗布(塗工)する。また、前述のとおり、カバー層原料液を塗布(塗工)に代えて、カバー層を有するテープ等の貼合(貼付)でもよい。 After the strength improving step (4), the coating step (5) is performed in the cover layer coating zone 240. In the coating step (5), for example, 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.
 塗工工程(5)の後に、オーブンゾーン250内で加熱手段251を用いて乾燥工程(6)を行う。乾燥工程(6)に先立ち、室温等で予備乾燥工程を行ってもよいし、乾燥工程(6)を複数の工程に分け、後の乾燥工程になるほど乾燥温度を高くしてもよい。加熱手段251としては、乾燥工程(2)において、例示した加熱手段211を用いてもよい。 After the coating step (5), the drying step (6) is performed using the heating means 251 in the oven zone 250. Prior to the drying step (6), 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. As the heating means 251, the heating means 211 exemplified in the drying step (2) may be used.
 乾燥工程(6)の後に、化学処理ゾーン260内で光照射手段または加熱手段261を用いて化学処理工程(7)を行う。化学処理工程(7)においては、例えば、カバー層中の化合物と、空隙層中の前記微細孔粒子同士の化学的結合により架橋する。 After the drying step (6), the chemical treatment step (7) is performed using the light irradiation means or the heating means 261 in the chemical treatment zone 260. In 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.
 化学処理工程(7)の後に、強度向上ゾーン270内で強度向上工程(8)を行う。前記強度向上工程(8)における加熱温度および処理時間は、前述のとおりである。 After the chemical treatment step (7), 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.
[3. 光学部材]
 本発明の光学部材は、前述のように、本発明の積層光学フィルムを含むことを特徴とする。本発明の光学部材は、本発明の積層光学フィルムを含むことが特徴であって、その他の構成は何ら制限されない。本発明の光学部材は、例えば、前記本発明の積層光学フィルムの他に、他の層をさらに含んでもよい。
[3. Optical member]
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.
 また、本発明の光学部材は、例えば、前記本発明の積層光学フィルムを低反射層として含む。本発明の光学部材は、例えば、前記本発明の積層光学フィルムの他に、他の層をさらに含んでもよい。本発明の光学部材は、例えば、ロール状である。 Moreover, 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.
[4. 画像表示装置]
 本発明の画像表示装置は、前述のように、前記本発明の光学部材を含むことを特徴とする。本発明の画像表示装置は、本発明の光学部材を含むことが特徴であって、その他の構成は何ら制限されない。本発明の画像表示装置は、例えば、前記本発明の光学部材の他に、他の構成をさらに含んでもよい。
[4. Image display device]
As described above, 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.
 つぎに、本発明の実施例について説明する。ただし、本発明は、以下の実施例に限定されない。 Next, examples of the present invention will be described. However, the present invention is not limited to the following examples.
(実施例)
 本実施例では、以下のようにして本発明の積層光学フィルムを製造した。なお、製造に用いた物質の部数は、特に断らない限り、重量部(質量部)である。また、濃度(%)は、特に断らない限り、重量%である。
(Example)
In this example, the laminated optical film of the present invention was produced as follows. In addition, unless otherwise indicated, the number of parts of the substance used for manufacture is a weight part (mass part). The concentration (%) is% by weight unless otherwise specified.
[参考例1:空隙層の形成]
 DMSO 18部に、メチルトリメトキシシランを8部溶解させた。前記混合液に、0.01mol/Lのシュウ酸水溶液を4部添加し、室温で30分、撹拌を行うことで、メチルトリメトキシシランを加水分解させた。さらに、DMSO 65部、および28%濃度のアンモニア水3部、および純水2部を添加した後、室温で15分撹拌、40℃で20hr加熱エージングを行ない、ゲル状化合物を得た。そのゲル状化合物を、数mm~数cmサイズの顆粒状に砕きIPAをゲル量の4倍添加し、軽く撹拌した後、室温で6時間静置して、ゲル中の溶媒および触媒をデカンテーションした。同様のデカンテーション処理を3回繰り返し、溶媒置換を完了した。そのゲル状化合物に対し高圧メディアレス粉砕(ホモジナイザー(商品名UH-50、エスエムテー社製))を行ない、ゾル液を作製した。この時のゾル液の粒度バラツキを示す体積平均粒子径を、動的光散乱式ナノトラック粒度分析計(日機装社製、商品名UPA-EX150型)にて確認したところ、0.50~0.70であった。さらに、1.5重量%の光塩基発生触媒(和光純薬工業株式会社:商品名WPBG266)のIPA(イソプロピルアルコール)溶液を用意し、前記ゾル粒子液0.75部に対して0.031部添加、5%のビス(トリメトキシシリル)エタンを0.018部添加し塗工液を調製した。さらに、前記塗工液を、ポリエチレンテレフタレート基材(樹脂フィルム)の表面に塗工して、塗工膜を形成した。前記塗工膜を、温度100℃で1分処理して乾燥し、厚み1μmのシリコーン多孔体膜を形成した。その後、前記多孔体膜にUV照射(350mJ/cm(@360nm))を行ない、さらに60℃での加熱エージングを20hr行なって空隙層を得た。
[Reference Example 1: Formation of void layer]
8 parts of methyltrimethoxysilane was dissolved in 18 parts of DMSO. 4 parts of 0.01 mol / L oxalic acid aqueous solution was added to the mixed solution, and methyltrimethoxysilane was hydrolyzed by stirring at room temperature for 30 minutes. Further, 65 parts of DMSO, 3 parts of 28% strength aqueous ammonia, and 2 parts of pure water were added, followed by stirring at room temperature for 15 minutes and heat aging at 40 ° C. for 20 hours to obtain a gel-like compound. 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. 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. Further, 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. Further, 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 μm 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.
[参考例2:空隙層の形成]
 アルミナゾル液(4.9%濃度:川研ファインケミカル製)20部に、水13部添加し、80℃で加熱後、NHを3部添加した。さらに80℃で10hr加熱してゲル状化合物を得た。このゲル状化合物を参考例1のゲル状化合物に代えて用いた以外は、参考例1と同様の操作を行ない、屈折率1.24の低屈折率性空隙層を得た。
[Reference Example 2: Formation of void layer]
To 20 parts of an alumina sol solution (4.9% concentration: manufactured by Kawaken Fine Chemicals), 13 parts of water was added, heated at 80 ° C., and then 3 parts of NH 3 was added. Further, the mixture was heated at 80 ° C. for 10 hours to obtain a gel compound. A low refractive index void layer having a refractive index of 1.24 was obtained in the same manner as in Reference Example 1 except that this gel compound was used instead of the gel compound of Reference Example 1.
[参考例3:空隙層の形成]
 セルロースナノファイバーゾル液(2%濃度:スギノマシン製)に、n-ヘキサデシルトリメチルアンモニウムクロリドおよび尿素を溶解後、MTMSを加えて加水分解させた。その後、60℃20hr加熱してゲル状化合物を得た。このゲル状化合物を参考例1のゲル状化合物に代えて用いた以外は、参考例1と同様の操作を行ない、屈折率1.20の低屈折率性空隙層を得た。
[Reference Example 3: Formation of void layer]
After dissolving n-hexadecyltrimethylammonium chloride and urea in a cellulose nanofiber sol solution (2% concentration: manufactured by Sugino Machine), it was hydrolyzed by adding MTMS. Then, the gelled compound was obtained by heating at 60 ° C. for 20 hours. A low refractive index void layer having a refractive index of 1.20 was obtained in the same manner as in Reference Example 1 except that this gel compound was used instead of the gel compound of Reference Example 1.
[参考例4:空隙層の形成]
 参考例1のゲル状化合物を針状シリカゲルIPA-ST-UP(日産化学工業株式会社の商品名)の分散液に変更した以外は、参考例1と同様の操作を行ない、屈折率1.19の低屈折率性空隙層を得た。
[Reference Example 4: Formation of void layer]
The same procedure as in Reference Example 1 was performed, except that 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.
[実施例1]
 参考例1で得た前記空隙層上に、ポリビニルアルコール(商品名JC40:重合度4000)(9%水溶液)40部、メチルトリメトキシシラン60部、尿素15部、BYK333(商品名)4部を配合したカバー層組成水溶液(カバー層原料液)を塗工し、100℃で4min加熱乾燥した。さらに、60℃20hrエージングを行ない、積層光学フィルムを得た。この積層光学フィルムは、前記ポリエチレンテレフタレート基材(樹脂フィルム)上に前記空隙層が形成され、さらに、前記空隙層上に膜厚1μmのカバー層が直接形成された積層光学フィルムであった。この積層光学フィルムの評価結果を表1に示す。
[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 μm was directly formed on the gap layer. The evaluation results of this laminated optical film are shown in Table 1.
[実施例2]
 カバー層原料液のポリビニルアルコールとして、JC40に代えて重合度1000のVC-10(商品名)を用いた以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[実施例3]
 カバー層原料液のポリビニルアルコールおよびメチルトリメトキシシランの組成をポリビニルアルコール30部、メチルトリメトキシシラン70部にした以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[実施例4]
 カバー層原料液のポリビニルアルコールおよびメチルトリメトキシシランの組成をポリビニルアルコール70部、メチルトリメトキシシラン30部にした以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[実施例5]
 カバー層原料液の尿素をβ-ピコリン 7部に変更した以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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 β-picoline. The evaluation results of this laminated optical film are shown in Table 1.
[実施例6]
 カバー層原料液の組成をポリエステルポリオールウレタン系ポリマー(17.5%水溶液)(商品名x-7096:日華化学社製)95部、メチルトリメトキシシラン5部、尿素3部、BYK3500(商品名)4部に変更した以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[Example 6]
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.
[実施例7]
 カバー層原料液をカチオン系自己架橋型ナノエマルジョン(商品名UW-550CS :大成ファインケミカル)に変更した以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[実施例8]
 カバー層原料液の尿素をβ-ピコリン 7部に変更した以外は実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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 β-picoline. The evaluation results of this laminated optical film are shown in Table 1.
[実施例9]
 参考例1で得られた空隙層に代えて参考例2で得られた空隙層を用いた以外は、実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[実施例10]
 参考例1で得られた空隙層に代えて参考例3で得られた空隙層を用いた以外は、実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[実施例11]
 参考例1で得られた空隙層に代えて参考例4で得られた空隙層を用いた以外は、実施例1と同様の操作を行ない、積層光学フィルムを得た。この積層光学フィルムの評価結果を表1に示す。
[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.
[比較例1]
 参考例1で得られた空隙層上にカバー層を形成せずにそのまま評価を行なった。評価結果を表1に示す。
[Comparative Example 1]
Evaluation was carried out as it was without forming a cover layer on the gap layer obtained in Reference Example 1. The evaluation results are shown in Table 1.
[比較例2]
 参考例2で得られた空隙層上にカバー層を形成せずにそのまま評価を行なった。評価結果を表1に示す。
[Comparative Example 2]
Evaluation was carried out as it was without forming a cover layer on the gap layer obtained in Reference Example 2. The evaluation results are shown in Table 1.
[比較例3]
 参考例4で得られた空隙層上にカバー層を形成せずにそのまま評価を行なった。評価結果を表1に示す。
[Comparative Example 3]
Evaluation was carried out as it was without forming a cover layer on the gap layer obtained in Reference Example 4. The evaluation results are shown in Table 1.
[比較例4]
 参考例1で得られた空隙層に、メチルトリメトキシシラン100部のシクロヘキサン溶液(40%溶液)とTi触媒(商品名TA-25:マツモトファインケミカル)10部を配合した組成液を塗工し、100℃で4min加熱乾燥を行ない、カバー層を形成して積層光学フィルムを得た。この積層光学フィルムは、前記ポリエチレンテレフタレート基材(樹脂フィルム)上に前記空隙層が形成され、さらに、前記空隙層上に膜厚1μmのカバー層が直接形成された積層光学フィルムであった。この積層光学フィルムの評価結果を表1に示す。
[Comparative Example 4]
A composition solution in which 100 parts of methyltrimethoxysilane in a cyclohexane solution (40% solution) and 10 parts of a Ti catalyst (trade name TA-25: Matsumoto Fine Chemical) was applied to the void layer obtained in Reference Example 1, Heat drying was performed at 100 ° C. for 4 minutes to form a cover layer to obtain a laminated optical film. 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 μm was directly formed on the gap layer. The evaluation results of this laminated optical film are shown in Table 1.
[比較例5]
 参考例1で得られた空隙層に、脂環式エポキシモノマー(商品名セロキサイド:ダイセル製)80部、オキセタンモノマー(商品名OXT-221:東亜合成)20部、光カチオン開始剤(商品名CP-101A:サンアプロ製)4部を配合した組成液を塗工しUV1000mJ照射し、カバー層を形成して積層光学フィルムを得た。この積層光学フィルムは、前記ポリエチレンテレフタレート基材(樹脂フィルム)上に前記空隙層が形成され、さらに、前記空隙層上に膜厚1μmのカバー層が直接形成された積層光学フィルムであった。この積層光学フィルムの評価結果を表1に示す。なお、下記表1中、「耐擦傷性」は、カバー層の耐擦傷性である。「屈折率」および「空隙率」は、それぞれ、空隙層の屈折率および空隙率である。また、「接触角」は、空隙層における水の接触角である。空隙層の空隙率および水の接触角は、前述の方法で測定した。また、空隙層の屈折率およびカバー層の耐擦傷性は、下記の評価方法(測定方法)により測定した。
[Comparative Example 5]
In the void layer obtained in Reference Example 1, 80 parts of an alicyclic epoxy monomer (trade name Celoxide: manufactured by Daicel), 20 parts of oxetane monomer (trade name OXT-221: Toagosei Co., Ltd.), a photocation initiator (trade name CP) -101A (manufactured by San-Apro)) A composition solution containing 4 parts was applied and irradiated with UV 1000 mJ to form a cover layer to obtain a laminated optical film. 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 μm was directly formed on the gap layer. The evaluation results of this laminated optical film are shown in Table 1. In Table 1 below, “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).
(評価方法)
[屈折率]
 アクリルフィルムに空隙層(本発明の空隙層)を形成した後に、50mm×50mmのサイズにカットし、これを粘着層でガラス板(厚み:3mm)の表面に貼合した。前記ガラス板の裏面中央部(直径20mm程度)を黒マジックで塗りつぶして、前記ガラス板の裏面で反射しないサンプルを調製した。エリプソメーター(J.A.Woollam Japan社製:商品名VASE)に前記サンプルをセットし、500nmの波長、入射角50~80度の条件で、屈折率を測定し、その平均値を屈折率とした。
[耐擦傷性]
 スチールウール試験(φ25mm)100g荷重×10往復を行ない、キズの有無を目視確認した。
(Evaluation methods)
[Refractive index]
After forming a void layer (the void layer of the present invention) on the acrylic film, it was cut into a size of 50 mm × 50 mm, and this was bonded to the surface of a glass plate (thickness: 3 mm) with an adhesive layer. The back surface center part (diameter about 20 mm) of the said glass plate was painted with black magic, and the sample which does not reflect on the back surface of the said glass plate was prepared. The sample is set in an ellipsometer (JA Woollam Japan, trade name: 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. did.
[Abrasion resistance]
Steel wool test (φ25 mm) 100 g load × 10 reciprocation was performed, and the presence or absence of scratches was visually confirmed.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
 表1に示したとおり、本実施例によれば、高い空隙率(空孔率)および優れた耐擦傷性を両立可能な積層光学フィルムを得ることができた。なお、実施例1~11について、カバー層の空隙率を、空隙層の空隙率と同様の測定方法で測定したところ、いずれも10体積%以下であった。 As shown in Table 1, according to this example, a laminated optical film capable of achieving both a high porosity (porosity) and excellent scratch resistance could be obtained. In Examples 1 to 11, 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.
 以上、説明したとおり、本発明の積層光学フィルムは、高い空隙率(空孔率)および優れた耐擦傷性を両立可能である。また、本発明の積層光学フィルムの製造方法によれば、高い空隙率(空孔率)および優れた耐擦傷性を両立した本発明の積層光学フィルムを製造することができる。本発明の積層光学フィルムは、例えば、本発明の光学部材および画像表示装置に用いることができるが、これに限定されず、どのような用途に用いても良い。 As described above, 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.
10 基材
20 空隙層
20’ 塗工膜(乾燥後)
20’’ ゾル粒子液
21 強度が向上した空隙層
22 カバー層
22’ 塗工膜(乾燥後)
22’’ カバー層原料液
23 強度が向上したカバー層
101 送り出しローラ
102 塗工ロール
105 巻き取りロール
106 ロール
110 オーブンゾーン
111 熱風器(加熱手段)
120 化学処理ゾーン
121 ランプ(光照射手段)または熱風器(加熱手段)
130 強度向上ゾーン
131 熱風器(加熱手段)
140 カバー層塗工ゾーン
141 カバー層塗工手段
150 オーブンゾーン
151 加熱手段
160 化学処理ゾーン
161 加熱手段
170 強度向上ゾーン
171 加熱手段
201 送り出しローラ
202 液溜め
203 ドクター(ドクターナイフ)
204 マイクログラビア
210 オーブンゾーン
211 熱風器(加熱手段)
220 化学処理ゾーン
221 ランプ(光照射手段)または熱風器(加熱手段)
230 強度向上ゾーン
231 熱風器(加熱手段)
240 カバー層塗工ゾーン
241 カバー層塗工手段
250 オーブンゾーン
251 加熱手段
260 化学処理ゾーン
261 加熱手段
270 強度向上ゾーン
271 加熱手段
351 巻き取りロール
10 Substrate 20 Gap layer 20 ′ Coating film (after drying)
20 '' sol particle liquid 21 Strengthened void layer 22 Cover layer 22 'Coating film (after drying)
22 '' Cover layer raw material liquid 23 Cover layer 101 with improved strength Feed roller 102 Coating roll 105 Winding roll 106 Roll 110 Oven zone 111 Hot air blower (heating means)
120 Chemical treatment zone 121 Lamp (light irradiation means) or hot air device (heating means)
130 Strength Improvement Zone 131 Hot Air Fan (Heating means)
140 Cover layer coating zone 141 Cover layer coating means 150 Oven zone 151 Heating means 160 Chemical treatment zone 161 Heating means 170 Strength improvement zone 171 Heating means 201 Feeding roller 202 Liquid reservoir 203 Doctor (doctor knife)
204 Microgravure 210 Oven zone 211 Hot air (heating means)
220 Chemical treatment zone 221 Lamp (light irradiation means) or hot air blower (heating means)
230 Strength improvement zone 231 Hot air blower (heating means)
240 Cover layer coating zone 241 Cover layer coating means 250 Oven zone 251 Heating means 260 Chemical treatment zone 261 Heating means 270 Strength improvement zone 271 Heating means 351 Winding roll

Claims (14)

  1. 樹脂フィルム上に空隙層が形成され、
    さらに、前記空隙層上にカバー層が直接形成され、
    前記空隙層は、水の接触角が90°以上であり、かつ、空隙率が30体積%以上である積層光学フィルム。
    A void layer is formed on the resin film,
    Further, a cover layer is directly formed on the gap layer,
    The gap layer is a laminated optical film having a water contact angle of 90 ° or more and a porosity of 30% by volume or more.
  2. 前記カバー層の空隙率が、10体積%以下である請求項1記載の積層光学フィルム。 The laminated optical film according to claim 1, wherein a porosity of the cover layer is 10% by volume or less.
  3. 前記カバー層が、耐擦傷性を有する層である請求項1または2記載の積層光学フィルム。 The laminated optical film according to claim 1, wherein the cover layer is a layer having scratch resistance.
  4. 前記カバー層が、水溶性架橋体および水溶性ポリマーの少なくとも一方を含む請求項1から3のいずれか一項に記載の積層光学フィルム。 The laminated optical film according to any one of claims 1 to 3, wherein the cover layer contains at least one of a water-soluble crosslinked body and a water-soluble polymer.
  5. 前記空隙層の屈折率が、1.3以下である請求項1から4のいずれか一項に記載の積層光学フィルム。 The laminated optical film according to any one of claims 1 to 4, wherein a refractive index of the void layer is 1.3 or less.
  6. 前記空隙層は、微細な空隙構造を形成する一種類または複数種類の構成単位同士が直接的または間接的に化学的に結合している部分を含み、かつ、
    前記空隙層が、前記構成単位同士を間接的に結合させるための架橋補助剤を含む、請求項1から5のいずれか一項に記載の積層光学フィルム。
    The void layer includes a part in which one or a plurality of structural units forming a fine void structure are directly or indirectly chemically bonded, and
    The laminated optical film according to any one of claims 1 to 5, wherein the void layer contains a crosslinking aid for indirectly bonding the structural units.
  7. 前記空隙層中における前記架橋補助剤の含有率が、前記構成単位の重量に対して0.01~20重量%である請求項6記載の積層光学フィルム。 7. The laminated optical film according to claim 6, wherein the content of the crosslinking aid in the void layer is 0.01 to 20% by weight with respect to the weight of the structural unit.
  8. 前記樹脂フィルム上に前記空隙層を形成する空隙層形成工程、および、
    前記空隙層上に前記カバー層を直接もしくは転写により形成する前記カバー層形成工程を含む、
    請求項1から7のいずれか一項に記載の積層光学フィルムの製造方法。
    A void layer forming step of forming the void layer on the resin film, and
    Including the cover layer forming step of forming the cover layer directly or by transfer on the void layer,
    The manufacturing method of the laminated optical film as described in any one of Claim 1 to 7.
  9. 前記カバー層形成工程において、前記カバー層を、水性塗料の塗工により形成する請求項8記載の製造方法。 The manufacturing method according to claim 8, wherein in the cover layer forming step, the cover layer is formed by application of a water-based paint.
  10. 前記カバー層形成工程において、前記カバー層の原料を含むカバー層原料液を前記空隙層上に直接塗工成膜もしくは別基材上で塗工成膜し前記空隙層上に転写させた後、加熱および光照射の少なくとも一方を行うことで前記カバー層を形成する、請求項8または9記載の製造方法。 In the cover layer forming step, after the cover layer raw material liquid containing the cover layer raw material is applied directly on the gap layer or coated on another substrate and transferred onto the gap layer, The manufacturing method according to claim 8 or 9, wherein the cover layer is formed by performing at least one of heating and light irradiation.
  11. 前記空隙層形成工程において、微細な空隙構造を形成する一種類または複数種類の構成単位同士を、架橋補助剤により間接的に結合させて前記空隙層を形成する、請求項8から10のいずれか一項に記載の製造方法。 The said void layer formation process WHEREIN: One type or multiple types of structural units which form a fine void structure are indirectly combined with a crosslinking adjuvant, and the said void layer is formed. The manufacturing method according to one item.
  12. 前記架橋補助剤の添加量が、前記構造単位の重量に対して0.01~20重量%である請求項11記載の製造方法。 The production method according to claim 11, wherein the addition amount of the crosslinking aid is 0.01 to 20% by weight based on the weight of the structural unit.
  13. 請求項1から7のいずれか一項に記載の積層光学フィルムを含む光学部材。 An optical member comprising the laminated optical film according to claim 1.
  14. 請求項13記載の光学部材を含む画像表示装置。 An image display device comprising the optical member according to claim 13.
PCT/JP2016/072452 2015-08-24 2016-07-29 Laminated optical film, method for producing laminated optical film, optical member, and image display device WO2017033672A1 (en)

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