WO2017022690A1 - 光学積層体、光学積層体の製造方法、光学部材、画像表示装置 - Google Patents

光学積層体、光学積層体の製造方法、光学部材、画像表示装置 Download PDF

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Publication number
WO2017022690A1
WO2017022690A1 PCT/JP2016/072417 JP2016072417W WO2017022690A1 WO 2017022690 A1 WO2017022690 A1 WO 2017022690A1 JP 2016072417 W JP2016072417 W JP 2016072417W WO 2017022690 A1 WO2017022690 A1 WO 2017022690A1
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Prior art keywords
layer
void
void layer
present
adhesive
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PCT/JP2016/072417
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English (en)
French (fr)
Japanese (ja)
Inventor
大輔 服部
裕宗 春田
恒三 中村
武本　博之
Original Assignee
日東電工株式会社
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Priority claimed from JP2016149060A external-priority patent/JP6713871B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020177035011A priority Critical patent/KR102324896B1/ko
Priority to US15/749,250 priority patent/US11460610B2/en
Priority to EP16832969.6A priority patent/EP3321082B1/en
Priority to CN201680037716.6A priority patent/CN111093971B/zh
Priority to EP20189340.1A priority patent/EP3760433A1/en
Publication of WO2017022690A1 publication Critical patent/WO2017022690A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C09J2400/243—Presence of a foam in the substrate

Definitions

  • the present invention relates to an optical laminate, a method for producing an optical laminate, an optical member, an image display device, a method for producing an optical member, and a method for producing 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.
  • an optical member such as a film is generally used in a laminated structure in which an adhesive layer or an adhesive layer (hereinafter sometimes collectively referred to as “adhesive layer”) is used.
  • adhesive layer an adhesive layer or an adhesive layer
  • Patent Document 1 a laminate of an organic-inorganic composite film having voids and a connection layer containing an adhesive or an adhesive has been proposed.
  • the conventional void layer has a problem that the film strength is not sufficient and it is easily peeled off from the adhesive layer (a layer containing an adhesive or an adhesive).
  • the adhesive layer a layer containing an adhesive or an adhesive.
  • the void ratio is decreased and the refractive index is increased, so that it is difficult to achieve both high strength and low refractive index.
  • the present invention provides an optical laminate that has excellent film strength and is difficult to peel off the void layer and the adhesive layer, an optical laminate manufacturing method, an optical member, an image display device, an optical member manufacturing method, and an image display device. It aims at providing the manufacturing method of this.
  • a gap layer, an intermediate layer, and an adhesive layer are laminated in the order, and the adhesive layer is formed on the gap layer.
  • This is an optical laminate in which the intermediate layer is formed.
  • the method for producing an optical laminate of the present invention includes: The void layer, the intermediate layer, and the adhesive layer are a method for producing an optical laminate in which the gap layer is laminated in the order, A void layer forming step of forming the void layer; An adhesive layer forming step of forming the adhesive layer on the void layer; and An intermediate layer forming step of forming the intermediate layer; It is characterized by including.
  • the optical member of the present invention is an optical member including the optical laminate of the present invention.
  • the image display device of the present invention is an image display device including the optical member of the present invention.
  • the method for producing an optical member of the present invention is a method for producing an optical member including an optical laminate, and includes a step of producing by the method for producing an optical laminate of the present invention.
  • the method for manufacturing an image display device according to the present invention is a method for manufacturing an image display device including an optical member, and includes the step of manufacturing the optical member by the method for manufacturing an optical member according to the present invention. .
  • the optical layered body of the present invention has excellent film strength, and the void layer and the adhesive layer are difficult to peel off. Moreover, according to the manufacturing method of the optical laminated body of this invention, it is excellent in film
  • the optical layered body of the present invention further includes, for example, a resin film, and the gap layer, the intermediate layer, and the adhesive layer are stacked in the above order on the resin film. Although it may be a laminate (hereinafter sometimes referred to as “laminated film of the present invention”), it is not limited thereto.
  • laminate hereinafter sometimes referred to as “laminated film of the present invention”
  • the optical layered body of the present invention can be used for, for example, the optical member and image display apparatus 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 21, an intermediate layer 22, and an adhesive layer 30 on a resin film 10 in the present invention.
  • FIG. 2 schematically shows a part of a process in a method for producing a roll-shaped laminated film of the present invention (hereinafter sometimes referred to as “laminated 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 film roll of the present invention, and another example of an apparatus used therefor.
  • 4A is a cross-sectional photograph of the laminated film produced in Example 1.
  • FIG. 4B is a cross-sectional photograph of the laminated film produced in Example 7.
  • FIG. 1 is a process cross-sectional view schematically showing an example of a method for forming a void layer 21, an intermediate layer 22, and an adhesive layer 30 on a resin film 10 in the present invention.
  • the gap layer may have a thickness in the range of 0.01 to 1000 ⁇ m.
  • the intermediate layer may have a thickness in the range of 0.001 to 10 ⁇ m.
  • the refractive index of the void layer is 1.25 or less.
  • the thickness of the intermediate layer is equal to or less than the thickness of the gap layer.
  • the void ratio of the void layer is 40% by volume or more.
  • the haze value of the void layer is less than 5%.
  • the void layer may be a porous body in which fine pore particles are chemically bonded.
  • the optical layered body of the present invention further includes a resin film, and the gap layer, the intermediate layer, and the adhesive layer are stacked in the above order on the resin film.
  • An optical laminate laminate (laminated film of the present invention) may also be used.
  • the resin film may be a long resin film
  • the laminated film may be a long laminated film roll.
  • the optical laminate is an optical laminate in which the gap layer, the intermediate layer, and the adhesive layer are laminated in the order described above on a resin film. Yes, in the gap layer forming step, the gap layer may be formed on the resin film.
  • the intermediate layer forming step after the adhesive layer forming step, a part of the gap layer is reacted with a part of the adhesive layer, and the intermediate layer is formed. It may be a step of forming.
  • the intermediate layer may be formed by heating the gap layer and the adhesive layer.
  • the method for producing an optical layered body of the present invention further includes a precursor forming step of forming a void structure that is a precursor of the void layer prior to the void layer forming step, wherein the precursor is formed of the void layer.
  • a precursor forming step of forming a void structure that is a precursor of the void layer prior to the void layer forming step, wherein the precursor is formed of the void layer.
  • the strength improver may be generated by light irradiation or heating.
  • the strength improver may contain, for example, an acid or a basic substance.
  • the gap layer includes, for example, a portion in which one or a plurality of types of structural units forming a fine void structure are directly or indirectly chemically bonded. It may be included. 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 porous void layer in which the fine pore particles are chemically bonded to each other will be mainly described.
  • the microporous particles are microporous particles of a silicon compound, and the porous body is a silicone porous body.
  • the fine pore particles of the silicon compound may include, for example, a pulverized body of a gel silica compound.
  • the porous structure of the porous body may be an open cell structure having a continuous pore structure.
  • the method for producing an optical laminate of the present invention includes, for example, A containing liquid preparation step for preparing a containing liquid containing the fine pore particles; A coating step of coating the liquid on the resin film; and A drying step of drying the applied liquid containing the coating,
  • 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 a base catalyst (basic catalyst), and the containing liquid contains a base generator that generates the base catalyst by light or heat. good.
  • the void layer may be formed by chemically bonding the fine pore particles by light irradiation.
  • the void layer may be formed by chemically bonding the microporous particles by heating.
  • the refractive index of the void layer after forming the intermediate layer is not more than a numerical value obtained by adding 0.1 to the refractive index of the void layer before forming the intermediate layer. Also good.
  • the gap layer may be formed so that the refractive index is 1.25 or less.
  • the void layer may be formed so that the porosity is 40% by volume or more.
  • the gap layer may be formed to have a thickness of 0.01 to 100 ⁇ m.
  • the void layer may be formed so that the haze value is less than 5%.
  • the method for producing an optical layered body of the present invention may further include, for example, a crosslinking reaction step for causing a crosslinking reaction inside the void layer.
  • the crosslinking reaction step may be, for example, a strength improving step for improving the strength of the void layer.
  • a crosslinking reaction accelerator that promotes the crosslinking reaction may be used, or a substance that generates the crosslinking reaction accelerator by light or heat may be used.
  • the crosslinking reaction accelerator may be, for example, a strength improver that increases (improves) the strength of the void layer.
  • the optical laminate is an optical laminate in which the gap layer, the intermediate layer, and the adhesive layer are laminated in the order on a resin film, and the gap layer forming step
  • the void layer may be formed on the resin film
  • the crosslinking reaction step may be an adhesive peel strength improving step of improving the adhesive peel strength of the void layer with respect to the resin film.
  • the intermediate layer forming step may also serve as the crosslinking reaction step.
  • the optical layered body is formed by laminating the gap layer, the intermediate layer, and the adhesive layer in the above order on a long resin film.
  • the gap layer is continuously formed on the elongated resin film
  • the viscosity layer is formed on the gap layer.
  • the adhesive layer may be formed continuously.
  • the optical layered body of the present invention is manufactured by, for example, the method for manufacturing an optical layered body of the present invention.
  • the optical layered body of the present invention is excellent in film strength, and the void layer and the adhesive layer are difficult to peel off.
  • the reason (mechanism) is unknown, but is presumed to be due to, for example, the throwing property (throwing effect) of the intermediate layer.
  • the anchoring property is that the interface is firmly fixed in the vicinity of the interface between the void layer and the intermediate layer because the intermediate layer is embedded in the void layer.
  • this reason (mechanism) is an example of a presumed reason (mechanism), and does not limit the present invention.
  • the optical layered body of the present invention further includes a resin film, and the gap layer, the intermediate layer, and the adhesive layer are stacked in the above order on the resin film.
  • An optical laminate laminate (laminated film of the present invention) may also be used.
  • the optical laminate of the present invention is not limited to this and may be an optical laminate that does not include a resin film. However, in the following, the laminate film of the present invention (an optical laminate including a resin film) will be mainly described. . About the optical laminated body of this invention which does not contain a resin film, unless otherwise indicated, the description of the laminated film of this invention below can be used.
  • the laminated film of the present invention may be a roll-shaped laminated film (the laminated film roll of the present invention).
  • the laminated film roll of the present invention For example, a part of the laminated film roll of the present invention may be cut out and used as the laminated film of the present invention.
  • laminated film of the present invention includes the laminated film roll of the present invention unless otherwise specified.
  • the laminated film of the present invention is excellent in film strength and the gap layer and the adhesive layer are difficult to peel off, for example, it can be made into a roll-shaped laminated film (laminated film roll of the present invention), and the production efficiency is high. There are advantages such as good and easy to handle.
  • the laminated film of the present invention can be continuously produced as a roll-shaped product by being formed on a soft resin film due to the high flexibility of the void layer, for example, and is easy to handle as a roll.
  • multilayer film of this invention is not specifically limited, For example, it can manufacture with the manufacturing method of the said laminated
  • the resin film is not particularly limited, and types of the resin include, for example, polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP), and triacetate.
  • types of the resin include, for example, polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer (COP), and triacetate.
  • thermoplastic resins having excellent transparency such as (TAC), polyethylene naphthalate (PEN), polyethylene (PE), and polypropylene (PP).
  • the gap layer (hereinafter referred to as “the gap layer of the invention”) in the laminated film roll or laminated film of the present invention may be laminated directly on the resin film, for example, or laminated via another layer. May be.
  • the laminated film of the present invention includes, for example, the void layer, the intermediate layer, the adhesive layer, and the resin film, wherein the void layer is laminated on the resin film, and has the above characteristics. It can also be called a low refractive material.
  • the residual rate in the scratch resistance test by Bencot indicating the film strength is 60 to 100%.
  • the lower limit of the scratch resistance is, for example, 60% or more, 80% or more, 90% or more
  • the upper limit thereof is, for example, 100% or less, 99% or less, 98% or less, and the range is For example, they are 60 to 100%, 80 to 99%, 90 to 98%.
  • the scratch resistance can be measured by, for example, the following method.
  • the laminated film of the present invention is sampled in a circular shape having a diameter of 15 mm, and a sliding test (scratch resistance test) using Bencot (registered trademark) is performed on the void layer.
  • the sliding condition is a weight of 100 g and 10 reciprocations.
  • the scratch resistance is visually evaluated for the void layer after the scratch resistance test of (1). If the number of scratches after the scratch resistance test is 0 to 9, it is evaluated as ⁇ if it is 10 to 29, and ⁇ if it is 30 or more.
  • the laminated film roll or laminated film of the present invention has, for example, a folding resistance of 100 times or more by an MIT test showing flexibility. By having such flexibility, it is excellent in handleability at the time of winding or use during continuous production.
  • the lower limit of the folding endurance number is, for example, 100 times or more, 500 times or more, 1000 times or more, and the upper limit is not particularly limited, for example, 10,000 times or less, and the range is, for example, 100 10000 times, 500 times to 10000 times, 1000 times to 10000 times.
  • the flexibility means, for example, ease of deformation of the substance.
  • the folding endurance by the MIT test can be measured by the following method, for example.
  • the void layer (the void layer of the present invention) is cut into a 20 mm ⁇ 80 mm strip and then attached to an MIT folding tester (manufactured by Tester Sangyo Co., Ltd .: BE-202), and a load of 1.0 N is applied.
  • the chuck part that embeds the gap layer uses R 2.0 mm, performs the folding endurance up to 10,000 times, and sets the number of times when the gap layer is broken as the number of folding endurances.
  • the film density is not particularly limited, and the lower limit thereof is, for example, 1 g / cm 3 or more, 10 g / cm 3 or more, 15 g / cm 3 or more, and the upper limit thereof is, for example, 50 g / cm 3. cm 3 or less, 40 g / cm 3 or less, 30 g / cm 3 or less, 2.1 g / cm 3 or less, and the range is, for example, 5 to 50 g / cm 3 , 10 to 40 g / cm 3 , 15 to 30 g / cm 3 , 1 to 2.1 g / cm 3 .
  • the lower limit of the porosity based on the film density is, for example, 50% or more, 70% or more, 85% or more, and the upper limit thereof is, for example, 98% or less, 95
  • the range is, for example, 50 to 98%, 70 to 95%, and 85 to 95%.
  • the film density can be measured by the following method, for example, and the porosity can be calculated as follows based on the film density, for example.
  • 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 void layer of the present invention may have, for example, a pore structure (porous structure) as described above, for example, an open cell structure in which the pore structure is continuous.
  • 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 haze indicating transparency is not particularly limited, and the upper limit is, for example, less than 5% or 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, 1.25 or less, 1.20 or less, or 1.15 or less, and the lower limit thereof is, for example, 1.05 or more, 1.06 or more, 1
  • the range is, for example, 1.05 or more and 1.25 or less, 1.06 or more and 1.20 or less, and 1.07 or more and 1.15 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 x 50 mm, and this is bonded to the surface of a glass plate (thickness: 3 mm) with an adhesive 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 adhesive peel strength showing the adhesion between the void layer of the present invention and the adhesive layer laminated thereon is not particularly limited, and the lower limit thereof is, for example, 1 N / 25 mm or more, 1.3 N / 25 mm. Above, 1.5N / 25mm or more, 2N / 25mm or more, 3N / 25mm or more, the upper limit is, for example, 30N / 25mm or less, 20N / 25mm or less, 10N / 25mm or less, and the range is, for example, 1 to 30 N / 25 mm, 2 to 20 N / 25 mm, and 3 to 10 N / 25 mm.
  • the method for measuring the adhesive peel strength is not particularly limited, and can be measured, for example, by the following method.
  • the laminated film of the present invention is sampled into a 50 mm ⁇ 140 mm strip, and the sample is fixed to a stainless steel plate with a double-sided tape.
  • An acrylic adhesive layer (thickness 20 ⁇ m) is bonded to a PET film (T100: manufactured by Mitsubishi Plastics Film Co., Ltd.), and an adhesive tape piece cut to 25 mm ⁇ 100 mm is attached to the opposite side to the resin film in the laminated film of the present invention. And laminating with the PET film.
  • the sample is chucked with an autograph tensile tester (manufactured by Shimadzu Corporation: AG-Xplus) so that the distance between chucks becomes 100 mm, and then a tensile test is performed at a tensile speed of 0.3 m / min. .
  • the average test force which performed the 50 mm peel test be adhesive peel strength.
  • 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 of the present invention includes, for example, a pulverized product of a gel compound as described above, and the pulverized product is 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.
  • 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 pulverized product is not particularly limited, and the lower limit thereof is, for example, 0.10 ⁇ m or more, 0.20 ⁇ m or more, 0.40 ⁇ m or more,
  • the upper limit is, for example, 2.00 ⁇ m or less, 1.50 ⁇ m or less, 1.00 ⁇ m or less, and the ranges are, for example, 0.10 ⁇ m to 2.00 ⁇ m, 0.20 ⁇ m to 1.50 ⁇ m, 0.40 ⁇ m to 1. 00 ⁇ m.
  • the particle size distribution can be measured by, for example, a particle size distribution evaluation apparatus such as a dynamic light scattering method or a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). .
  • a particle size distribution evaluation apparatus such as a dynamic light scattering method or a laser diffraction method
  • an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
  • the particle size distribution showing the particle size variation of the pulverized product 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 to 90%. It is 99.7% by weight, or particles having a particle size of 1 ⁇ m to 2 ⁇ m are 0.1 to 50% by weight, 0.2 to 20% by weight, and 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 case where the gel compound is a gel 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 expressed, 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 further contains, for example, a crosslinking aid for indirectly bonding one or more types of structural units forming the fine void structure. Also good.
  • 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 adhesive layer is not particularly limited.
  • the “adhesive layer” is, for example, a layer containing at least one of a pressure-sensitive adhesive and an adhesive, and may be, for example, a pressure-sensitive adhesive layer or an adhesive layer.
  • “adhesive” and “adhesive layer” refer to, for example, an agent or layer premised on re-peeling of the adherend.
  • “adhesive” and “adhesive layer” refer to, for example, an agent or a layer that does not assume re-peeling of the adherend.
  • the adhesive or adhesive which forms the said adhesive layer is not specifically limited, For example, a general adhesive or adhesive etc. can be used.
  • the pressure-sensitive adhesive or adhesive include acrylic-based, vinyl alcohol-based, silicone-based, polyester-based, polyurethane-based, and polyether-based adhesives, rubber-based adhesives, and the like.
  • the adhesive agent comprised from the water-soluble crosslinking agent of vinyl alcohol polymers, such as glutaraldehyde, melamine, and oxalic acid, etc. are mentioned.
  • the thickness of the adhesive layer is not particularly limited, and is, for example, 0.1 to 100 ⁇ m, 5 to 50 ⁇ m, 10 to 30 ⁇ m, or 12 to 25 ⁇ m.
  • the intermediate layer is not particularly limited.
  • the intermediate layer is a layer formed by joining a part of the gap layer with a part of the adhesive layer.
  • the thickness of the intermediate layer is not particularly limited, and is, for example, 1 to 1500 nm, 5 to 1000 nm, 10 to 800 nm, or 20 to 500 nm.
  • the form of the laminated film of the present invention is not particularly limited, but the film shape is normal.
  • the laminated film of the present invention is, for example, a roll body.
  • the laminated film of this invention may contain a resin film further as mentioned above, for example, and the said space
  • another long film may be laminated on the laminated film of the present invention, and another long resin film (for example, a composite film) is added to the laminated film of the present invention including the resin film and the gap layer.
  • the paper may be in a form wound on a roll body after laminating paper, a release film, a surface protective film, and the like.
  • the manufacturing method of the laminated 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. Moreover, about the manufacturing method of the optical laminated body of this invention which does not contain a resin film, unless otherwise indicated, it can carry out similarly to the manufacturing method of the laminated film of this invention except not using a resin film.
  • the gap layer, the intermediate layer, and the adhesive layer are laminated in the order, and the gap layer and the adhesive layer are formed by the intermediate layer.
  • a method for producing a laminated film wherein a void layer forming step for forming the void layer, an adhesive layer forming step for forming the adhesive layer on the void layer, and the void layer, An intermediate layer forming step of forming the intermediate layer by reacting with the adhesive layer.
  • the void layer is a porous body in which fine pore particles are chemically bonded to each other, and in the void layer forming step, the fine pore particles are formed. Chemically bond together.
  • the method for producing a laminated 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 The method further includes a drying step of drying the coated liquid, and in the void layer forming step, the fine pore particles are chemically bonded to form the porous body.
  • 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 pulverized product used in the production method of the present invention is obtained by pulverizing the gel silicon compound, the three-dimensional structure of the gel silicon compound before pulverization is dispersed in a three-dimensional basic structure. It has become. 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 pulverized products.
  • 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 is reacted with the adhesive layer to form the intermediate layer (intermediate layer forming step).
  • the intermediate layer makes it difficult for the gap layer and the adhesive layer to peel off.
  • the reason (mechanism) is unknown, but as described above, for example, it is presumed to be due to the throwing property (throwing effect) of the intermediate layer.
  • the reaction between the void layer and the adhesive layer is not particularly limited, and may be a reaction by catalytic action, for example.
  • the reaction between the void layer and the adhesive layer may be, for example, a reaction (for example, a crosslinking reaction) in which a new chemical bond is generated.
  • the intermediate layer forming step may also serve as a step of improving the strength of the void layer.
  • the mechanism by which the strength of the void layer is improved by the intermediate layer forming step is unknown, but is estimated as follows, for example. That is, in the intermediate layer forming step, the intermediate layer is formed by applying energy to the void layer and the adhesive layer, for example, by heating to cause a reaction. It is considered that the energy of the heating or the like increases the number of crosslinks (chemical bonds) inside the void layer and improves the strength of the void layer. In addition, this reaction proceeds, for example, by the action of a catalyst, a crosslinking reaction accelerator, or a strength improver contained in the void layer. Alternatively, the sol content in the pressure-sensitive adhesive enters the voids in the void layer, and the anchoring effect of the intermediate layer is improved by the anchor effect. However, these are examples of mechanisms that can be estimated and do not limit the present invention.
  • the void layer is formed by chemically bonding the microporous particles by a catalytic reaction using a photobase generator. And, for example, the base catalyst (crosslinking reaction accelerator) generated from the photobase generator remains in the precursor, so that the chemistry of the fine pore particles is caused by heating or the like in the intermediate layer forming step. Bond (for example, cross-linking 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 production method of the present invention can use the explanation of the laminated film of the present invention unless otherwise specified.
  • the description in the void layer of the present invention can be used for the gel compound and the pulverized product thereof, the monomer compound and the precursor of the monomer compound.
  • the method for producing a laminated film of the present invention can be performed, for example, as follows, but is not limited thereto.
  • the method for producing a laminated 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.
  • the fine pore particles are a pulverized product of a gel compound
  • the pulverized product can be obtained, for example, by pulverizing the gel compound.
  • the three-dimensional structure of the gel-like compound is destroyed and dispersed into the three-dimensional basic structure.
  • the gelation of the monomer compound can be performed, for example, by hydrogen bonding or intermolecular force bonding of the monomer compounds.
  • Examples of the monomer 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 monomer 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 monomer 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 monomer 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 monomer compound. 0.1 to 5 moles.
  • the gelation of the monomer 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 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 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.
  • the same solvent as in the gelation treatment can be used, and specifically, the reaction product after the gelation treatment (that is, the solvent containing the gel compound) is applied as it is.
  • the number of moles of residual silanol groups contained in the gel (the gel-like compound, for example, the gel-like silicon compound) after the aging treatment after gelation is, for example, the added raw material (for example, the monomer 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, 3% or less, 5% 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 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.
  • 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 obtained gel compound is pulverized.
  • the gel compound in the gelling solvent may be pulverized as it is, or after the gelation solvent is replaced with another solvent, A pulverization treatment may be applied to the gel compound.
  • 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.
  • 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 compound is not particularly limited, and can 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 high pressure.
  • 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.
  • 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
  • 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 amount of the catalyst to be added is not particularly limited, but is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.0. 1 to 5% by weight.
  • the catalyst may be, for example, a catalyst (crosslinking reaction accelerator) that promotes cross-linking between the microporous particles, or may be a strength improver that improves the strength of the void layer.
  • An agent may also serve as the hardness improver.
  • 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.
  • the catalyst may be a catalyst (crosslinking reaction accelerator) that promotes cross-linking between the microporous particles, or may be a strength improver that improves the strength of the void layer.
  • the crosslinking accelerator may also serve as the hardness improver.
  • the catalyst generator may be a substance that generates a catalyst that functions as the crosslinking reaction accelerator or the strength improver.
  • 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 aromatic sulfonium salts (trade name SP-170: ADEKA), triarylsulfonium salts (trade name CPI101A: San Apro), and aromatic iodonium salts (trade name Irgacure 250: Ciba Japan). Company).
  • 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.
  • the catalyst that chemically bonds the fine pore particles examples 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.
  • the solvent is not particularly limited, and examples thereof include various organic solvents, water, and a buffer solution.
  • 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.
  • a new three-dimensional structure is constructed by the sedimentation and deposition of the pulverized material in which the three-dimensional structure is destroyed.
  • the liquid containing the fine pore particles may not contain a catalyst that chemically bonds the fine pore particles.
  • the precursor forming step may be performed after or while spraying a catalyst for chemically bonding the fine pore particles to the coating film.
  • the liquid containing the fine pore particles contains a catalyst that chemically bonds the fine pore particles, and the fine pore particles are chemically separated by the action of the catalyst contained in the coating film.
  • the precursor of the porous body may be formed by bonding.
  • 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 150 ° C. or lower. Specific examples include, for example, IPA, ethanol, methanol, n-butanol, 2-butanol, isobutyl alcohol, pentanol and the like, and the same solvents as the above grinding solvent can be used.
  • this invention includes the process of grind
  • 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 production method of the present invention has a drying step of drying a coating film produced by coating a liquid containing fine pore particles, for example, as described above.
  • a drying process in the drying step for example, not only the solvent (solvent contained in the sol particle liquid) in the coating film is removed, but also the sol particles are settled and deposited during the drying process, thereby forming a void structure.
  • the purpose is to form.
  • 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 porous body is formed by chemically bonding the fine pore particles by the action of the catalyst (void layer forming step).
  • the catalyst may be, for example, a crosslinking accelerator that promotes a crosslinking reaction between the microporous particles.
  • 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
  • a relatively low drying temperature of about 100 ° C. and several without causing damage to the base material (resin film)
  • 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 (crosslinking reaction accelerator) is a photoactive catalyst, and in the void layer forming step, the fine pore particles are chemically bonded to each other by light irradiation to form the porous body (void layer). ) May be formed.
  • 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.
  • the catalyst may be, for example, a crosslinking reaction accelerator that promotes a crosslinking reaction between the sol particles, or may be a strength improver that improves the strength of the void layer, and the crosslinking accelerator serves as the hardness improver. You may also serve.
  • 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.
  • 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. .
  • the pulverized product (fine pore particles) may be further bonded to each other by further heating the coating film after the drying step.
  • 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.
  • this assumption does not limit the present invention in any way.
  • 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.
  • the adhesive layer is formed on the void layer (adhesive layer forming step).
  • the adhesive layer may be formed by applying (coating) a pressure-sensitive adhesive or an adhesive onto the gap layer.
  • the adhesive layer is formed on the gap layer by bonding the adhesive layer side of the adhesive tape or the like on which the adhesive layer is laminated on the base material. You may do it.
  • the base material such as the adhesive tape may be left as it is or may be peeled off from the adhesive layer.
  • multilayer film of this invention may or may not contain arbitrary components other than the said resin film, the said space
  • the optional component is, for example, a layer other than the resin film, the void layer, the intermediate layer, and the adhesive layer, and may be a base material such as the adhesive tape, for example.
  • the void layer is reacted with the adhesive layer to form the intermediate layer (intermediate layer forming step).
  • This step is not particularly limited.
  • the intermediate layer may be formed by reacting by heating the void layer and the adhesive layer.
  • the reaction temperature is, for example, 40 to 80 ° C., 50 to 70 ° C., 55 to 65 ° C.
  • the reaction time is, for example, 5 to 30 hours, 7 to 25 hours, or 10 to 20 hours.
  • the intermediate layer By forming the intermediate layer, it is possible to form the laminated film of the present invention in which the void layer and the adhesive layer are difficult to peel off.
  • the reason (mechanism) is unknown, but it is presumed that, for example, as described above, it depends on the throwing property (throwing effect) of the intermediate layer. However, this reason (mechanism) is an example of a presumed reason (mechanism), and does not limit the present invention.
  • the mechanism by which the intermediate layer is formed is also unclear.
  • the catalyst present in the void layer is not particularly limited, and may be, for example, a basic catalyst or an acidic catalyst.
  • the basic catalyst (base catalyst) is not particularly limited.
  • the photobase generator may be a basic catalyst generated by light irradiation.
  • the acid catalyst is not particularly limited, but for example, the photoacid generator may be an acidic catalyst generated by light irradiation.
  • the reaction between the void layer and the adhesive layer may be, for example, a reaction in which a new chemical bond is generated (for example, a crosslinking reaction).
  • the intermediate layer forming step may also serve as a crosslinking reaction step for causing a crosslinking reaction inside the void layer.
  • the strength of the gap layer is improved, the film strength is further improved, and the gap film and the adhesive layer are difficult to peel off.
  • the crosslinking reaction that occurs in the void layer proceeds by the action of the catalyst (crosslinking reaction accelerator or strength improver) contained in the void layer.
  • this description does not limit the present invention.
  • the method for producing a laminated film of the present invention can be performed. Since the laminated film produced by the production method of the present invention is excellent in strength, for example, it can be made into a roll-shaped porous body, and has advantages such as good production efficiency and easy handling.
  • the laminated film (void layer) of the present invention thus obtained may be laminated with another film (layer), for example, to form a laminated structure including the porous structure.
  • each component in the laminated structure, 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 base material may be the resin film described above in the description of the laminated 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 an example of a process in the production method of the present invention in which the gap layer, the intermediate layer, and the adhesive layer are laminated in the order on the base material (resin film) is schematically illustrated.
  • the gap layer is formed by applying a sol particle solution 20 ′′ of the pulverized gel compound to a base material (resin film) 10 to form a coating film.
  • a sol particle solution 20 ′′ of the pulverized gel compound to a base material (resin film) 10 to form a coating film.
  • chemical treatment for example, cross-linking treatment.
  • a chemical treatment step for example, a crosslinking step (3) for forming the void layer 20, an adhesive layer coating step for applying the adhesive layer 30 on the void layer 20 (adhesive layer forming step) (4) and an intermediate layer forming step (5) in which the gap layer 20 is reacted with the adhesive layer 30 to form the intermediate layer 22.
  • the chemical treatment step (crosslinking step) (3) corresponds to the “void layer forming step” in the method for producing a laminated film of the present invention.
  • the intermediate layer forming step (5) (hereinafter sometimes referred to as “aging step”) is a step of improving the strength of the void layer 20 (crosslinking reaction step causing a crosslinking reaction inside the void layer 20).
  • the void layer 20 is changed to a void layer 21 with improved strength.
  • this invention is not limited to this,
  • gap layer 20 does not need to change after an intermediate
  • the adhesive layer forming step is not limited to the application of the adhesive layer, and may be bonding of an adhesive tape having an adhesive layer.
  • the coating method of the sol particle liquid 20 '' is not particularly limited, and a general coating method can be adopted.
  • the coating method 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, and flexographic printing.
  • 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 coated film (precursor of the void layer) 20 after drying.
  • the conditions for the drying treatment are not particularly limited and are as described above.
  • the coating film 20 containing the catalyst or the catalyst generator added before coating for example, a photoactive catalyst, a photocatalyst generator, a thermal active catalyst, or a thermal catalyst generator.
  • light irradiation or heating is performed to chemically bond (for example, cross-link) the pulverized materials in the coating film 20 ′ to form the void layer 20.
  • the light irradiation or heating conditions in the chemical treatment step (3) are not particularly limited and are as described above.
  • the conditions of the adhesive layer coating step (adhesive layer forming step) (4) and the intermediate layer forming step (5) are not particularly limited, and 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.
  • This cross-linking treatment causes chemical bonding between the pulverized products in the coating film 20 ′, and the void layer 20 is cured and strengthened.
  • the chemical treatment step (3) is performed after the drying step (2).
  • 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 bond between the pulverized products.
  • 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 in the step prior to the drying step (2).
  • an adhesive or adhesive is applied (coated) on the void layer 20 by the adhesive layer coating means 131a in the adhesive layer coating zone 130a.
  • An adhesive layer coating process (adhesive layer forming process) (4) for forming the adhesion layer 30 is performed. Further, as described above, instead of applying (coating) the pressure-sensitive adhesive or adhesive, bonding (sticking) such as a pressure-sensitive adhesive tape having the adhesive layer 30 may be used.
  • an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming zone (aging zone) 130, and the void layer 20 and the adhesive layer 30 are reacted to form the intermediate layer 22.
  • the void layer 20 becomes a void layer 21 in which a crosslinking reaction occurs inside and the strength is improved.
  • middle layer formation process (aging process) (5) is performed by heating the space
  • heating temperature, time, etc. are not specifically limited, For example, it is as above-mentioned.
  • the laminated body in which the gap layer 21 is formed on the substrate 10 is wound up by the winding roll 105.
  • the gap layer 21 of the laminate is covered and protected with a protective sheet fed from the roll 106.
  • the protective sheet instead of the protective sheet, another layer formed of a long film may be laminated on the gap layer 21.
  • 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 sol particle liquid 20 ′′ is applied by 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.
  • an adhesive or an adhesive is applied (coated) on the void layer 20 by the adhesive layer coating means 231a in the adhesive layer coating zone 230a.
  • An adhesive layer coating process (adhesive layer forming process) (4) for forming the adhesion layer 30 is performed. Further, as described above, instead of applying (coating) the pressure-sensitive adhesive or adhesive, bonding (sticking) such as a pressure-sensitive adhesive tape having the adhesive layer 30 may be used.
  • an intermediate layer forming step (aging step) (5) is performed in the intermediate layer forming zone (aging zone) 230, and the void layer 20 and the adhesive layer 30 are reacted to form the intermediate layer 22. Further, as described above, in this step, the void layer 20 becomes the void layer 21 with improved strength. Even if an intermediate
  • the laminated film in which the gap layer 21 is formed on the substrate 10 is wound up by the winding roll 251. Thereafter, for example, another layer may be laminated on the laminated film. Further, before the laminated film is taken up by the take-up roll 251, for example, another layer may be laminated on the laminated film.
  • the optical member of the present invention includes the optical laminate of the present invention.
  • the optical member of the present invention is characterized by including the optical laminate 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 optical laminate of the present invention, for example.
  • the optical member of the present invention includes, for example, the optical laminate 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 optical laminate of the present invention, for example.
  • the optical member of the present invention has a roll shape, for example.
  • Example 1 the laminated film (laminated film roll) of the present invention was produced as follows.
  • a homogenizer (trade name UH-50, manufactured by SMT Co., Ltd.) was used, and 1.18 g of gel and 1.14 g of IPA were weighed into a 5 cc screw bottle, and then for 2 minutes under the conditions of 50 W and 20 kHz. It was performed by crushing.
  • the gelled silicon compound in the mixed solution was pulverized by the pulverization treatment, whereby the mixed solution became a sol particle solution of the pulverized product.
  • the volume average particle size indicating the particle size variation of the pulverized product contained in the mixed solution was confirmed with a dynamic light scattering nanotrack particle size analyzer (manufactured by Nikkiso Co., Ltd., UPA-EX150 type), 0.50 to It was 0.70.
  • a photobase generator (Wako Pure Chemical Industries, Ltd .: trade name WPBG266, which generates a catalyst (a crosslinking reaction accelerator and a strength improver that improves the strength of the void layer) by light)
  • An IPA (isopropyl alcohol) solution of the substance) was prepared, and 0.031 g was added to 0.75 g of the sol particle solution to prepare a coating solution.
  • the above steps (1) to (3) correspond to the “containing liquid preparation step” in which the containing liquid containing the fine pore particles is prepared in the method for producing a laminated film of the present invention.
  • the coating liquid is applied to the surface of a polyethylene terephthalate (PET) substrate (resin film, 100 m long) by a bar coating method. (Coating) to form a coating film (coating process).
  • the application was performed with 6 ⁇ L of the sol particle liquid per 1 mm 2 of the surface of the substrate.
  • the coating film was treated at a temperature of 100 ° C. for 1 minute and dried to form a 1 ⁇ m-thick silicone porous film (drying process).
  • the porous membrane after drying was irradiated with UV to form a void layer (void layer forming step). The UV irradiation was 350 mJ / cm 2 (@ 360 nm).
  • Example 2 In the step of “(3) Grinding treatment and addition of photobase generator” in Example 1, 5% by weight of 1,2-bis (trimethoxysilyl) ethane was further added to the sol after the photobase generator solution was added.
  • a laminated film roll was manufactured in the same manner as in Example 1 except that 0.018 g was added to 0.75 g of the liquid and the coating liquid was adjusted.
  • Example 3 In the step of “(3) Grinding treatment and addition of photobase generator” in Example 1, except that the amount of photobase generator added was 0.054 g with respect to 0.75 g of the sol solution. The same operation as in Example 1 was performed to produce a laminated film roll.
  • Example 4 A laminated film roll was produced in the same manner as in Example 3 except that 1,2-bis (trimethoxysilyl) ethane used in Example 3 was changed to tris (trimethoxysilylpropyl) isocyanurate. .
  • Example 5 A laminated film roll was manufactured in the same manner as in Example 2 except that the sol particle liquid was changed to a pulverized alumina sol liquid.
  • the pulverized alumina sol solution was prepared by adding 13 parts by weight of water to 20 parts by weight of the alumina sol solution manufactured by Kawaken Fine Chemical Co., Ltd., heating at 80 ° C., and then adding 3 parts by weight of NH 3 at 80 ° C. It was heated for 10 hours to gel, and further pulverized. Further, in this example, the refractive index of the void layer (low refractive index film) obtained from the pulverized alumina sol solution was 1.24.
  • Example 6 A laminated film roll was manufactured in the same manner as in Example 2 except that the sol particle liquid was changed to a pulverized cellulose nanofiber sol liquid.
  • the pulverized cellulose nanofiber sol solution was prepared by dissolving n-hexadecyltrimethylammonium chloride and urea in cellulose nanofiber sol solution manufactured by Sugino Machine Co., Ltd., and then hydrolyzing with MTMS. The gel was produced by heating at 60 ° C. for 20 hours and then pulverized.
  • the refractive index of the void layer (low refractive index film) obtained from the pulverized cellulose nanofiber sol solution was 1.19.
  • Example 7 A laminated film roll was produced in the same manner as in Example 2 except that the sol particle liquid was changed to a dispersion of hollow nanoparticles (trade name: Surria 4320, manufactured by Nissan Chemical Industries, Ltd.).
  • the refractive index of the void layer (low refractive index film) obtained from the dispersion of the hollow nanoparticles was 1.19.
  • Example 8 A laminated film roll was produced in the same manner as in Example 2 except that the sol particle liquid was changed to a dispersion of nanoclay (manufactured by Nissan Chemical Industries, Ltd.).
  • the refractive index of the void layer (low refractive index film) obtained from the nanoclay dispersion was 1.24.
  • Example 9 A laminated film roll was manufactured in the same manner as in Example 2 except that the sol particle liquid was changed to a dispersion of nanoballoon (trade name of Grandex Co., Ltd.).
  • the refractive index of the void layer (low refractive index film) obtained from the nanoballoon dispersion was 1.15.
  • Example 10 The sol particle liquid is changed to a dispersion (concentration 15% by weight) of acicular silica gel IPA-ST-UP (trade name of Nissan Chemical Industries, Ltd.) and diluted to a concentration of 5% by adding IPA. Except for the above, the same operation as in Example 2 was performed to produce a laminated film roll. In this example, the refractive index of the void layer (low refractive index film) obtained from the dispersion was 1.19.
  • Example 2 In place of the long PET substrate, a section of the PET substrate was used, and no photobase generator was added in the step of “(3) Grinding treatment and addition of photobase generator” in Example 1. A laminated film was produced in the same manner as in Example 1 except that the heating aging step was omitted in the step of “(5) Formation of adhesive layer and intermediate layer”. The reason why the section of the PET base material was used in place of the long PET base material was that the strength and flexibility of the void layer were inferior and it was difficult to produce continuously in a roll shape.
  • Table 1 The test results of these examples and comparative examples are shown in Table 1 below.
  • the refractive index, adhesive peel strength, and haze were measured by the methods described above. Whether or not the intermediate layer was formed was confirmed by a cross-sectional photograph taken with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • 4A shows a cross-sectional photograph (cross-sectional SEM image) of the laminated film roll of Example 1
  • FIG. 4B shows a cross-sectional photograph (cross-sectional SEM image) of the laminated film roll of Example 7.
  • SEM scanning electron microscope
  • Examples 1 to 4 in which the intermediate layer forming step (aging step) was performed were compared with Comparative Example 1 in which the intermediate layer was not formed without performing the intermediate layer forming step (aging step).
  • the adhesive peel strength was improved.
  • Examples 1 to 4 had almost no difference in refractive index from Comparative Example 1, and maintained an extremely low refractive index of 1.14 to 1.16.
  • a low refractive index void layer (low refractive index film) was obtained. That is, according to the laminated film of the example, it was confirmed that both high porosity and film strength were possible.
  • the laminated films of Examples 1 to 4 maintain the same low transparency as Comparative Example 1 because the haze value also maintains the extremely low value of 0.4 as in Comparative Example 1.
  • the laminated films of Examples 7 and 10 also had a low haze value as shown in Table 1 above.
  • Examples 1 to 4, 7 and 10 were also excellent in storage stability of the coating solution, and it was also confirmed that stable quality laminated films could be produced efficiently.
  • Comparative Example 2 in which an intermediate layer was not formed and a photobase generator was not used as in Comparative Example 1, although a low refractive index and a low haze could be realized, the adhesive peel strength was extremely inferior. For this reason, in Comparative Example 2, continuous production as a roll-shaped product was difficult as described above, and it was not practically usable.
  • a manufacturing method and a manufacturing method of an image display device can be provided.
  • the optical layered body of the present invention can easily realize a low refractive index that can be an alternative to the air layer, for example, by exhibiting the above-described characteristics. For this reason, in order to obtain a low refractive index, it is not necessary to provide an air layer by arranging a plurality of members with a certain distance, and by arranging the optical laminate of the present invention at a desired site, Low refractive properties can be imparted.
  • the optical laminated body of this invention is useful for the optical member etc. for which a low refractive index is required, for example.
  • the optical laminated body of this invention can be used for the optical member and image display apparatus of this invention, for example, it is not limited to this and may be used for what kind of use.
PCT/JP2016/072417 2015-07-31 2016-07-29 光学積層体、光学積層体の製造方法、光学部材、画像表示装置 WO2017022690A1 (ja)

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US15/749,250 US11460610B2 (en) 2015-07-31 2016-07-29 Optical laminate, method of producing optical laminate, optical element, and image display
EP16832969.6A EP3321082B1 (en) 2015-07-31 2016-07-29 Optical laminate, optical member, and image display
CN201680037716.6A CN111093971B (zh) 2015-07-31 2016-07-29 光学层叠体、光学层叠体的制造方法、光学构件及图像显示装置
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