CN107148350A - It is laminated film coiled material and its manufacture method - Google Patents

It is laminated film coiled material and its manufacture method Download PDF

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Publication number
CN107148350A
CN107148350A CN201580071024.9A CN201580071024A CN107148350A CN 107148350 A CN107148350 A CN 107148350A CN 201580071024 A CN201580071024 A CN 201580071024A CN 107148350 A CN107148350 A CN 107148350A
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China
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mentioned
refractive index
extra
coiled material
low refractive
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CN201580071024.9A
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CN107148350B (en
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春田裕宗
武本博之
服部大辅
中村恒三
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Nitto Denko Corp
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • 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
    • G02B1/11—Anti-reflection 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
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

It is an object of the invention to provide can for example substitute air layer and show low refrangible new type of component.The stacking film coiled material of the present invention can obtain a kind of stacking film coiled material of strip, it is characterised in that it is that the extra-low refractive index layer that refractive index is less than 1.20 is folded on resin film upper strata.Moreover, the manufacture method of the stacking film coiled material of the strip of the present invention is characterised by, such as comprising following processes：The process for making the liquid containing micropore particle；Aforesaid liquid is painted on to the process on resin film；And the process that the liquid of institute's application is dried.

Description

It is laminated film coiled material and its manufacture method
Technical field
The present invention relates to one kind stacking film coiled material and its manufacture method.
Background technology
If 2 substrates are vacated into certain intervals and configured, the space between two substrates turns into air layer.Like this, The air layer between aforesaid substrate is formed at as example by the forming low-refractive-index layer function of light total reflection.If thus, for example light Film is learned, then is configured by making the components such as prism, polarizing coating and polarizer that there is certain distance, so that between above-mentioned component It is set to the air layer of low-index layer.But, must just have certain distance due to like this in order to form air layer Each component is configured, so component can not be stacked gradually, it is fairly time consuming laborious in manufacture.
In order to solve this problem, it is try to develop a kind of components such as low refrangible film of display to substitute by component Between space formed by air layer.For above-mentioned component, as the example for taking into account high void content and intensity, there are confrontation lens anti- Penetrate the application example of layer (referring for example to patent document 1~4).This method is to be formed on lens after void layer, for a long time 150 Burnt till at a high temperature of more than DEG C, but because the pliability of obtained void layer is poor, so the resin of softness can not be formed at On film, and presence can not be with roll quantity-produced problem.On the other hand, there is the application without burning till the void layer of processing Example (referring for example to non-patent literature 1).But, for this method, because the film-strength of obtained void layer is poor, so can not Impact resistance is assigned, can not be with roll quantity-produced problem or exist.
In addition, having the example for the method for formation silica aerogel film on the resin supporter of strip that discloses (for example With reference to patent document 5 and 6).But, because the refractive index of silica aerogel film obtained herein is more than 1.30, thus eventually without Method replaces air layer.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-297329 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-221144 publications
Patent document 3：Japanese Unexamined Patent Publication 2006-011175 publications
Patent document 4：Japanese Unexamined Patent Publication 2008-040171 publications
Patent document 5：Japanese Unexamined Patent Publication 2006-096019 publications
Patent document 6：Japanese Unexamined Patent Publication 2006-096967 publications
Non-patent literature
Non-patent literature 1：J.Mater.Chem.,2011,21,14830-14837
The content of the invention
Invent problem to be solved
Pliability and film-strength can be taken into account and can contain ultralow folding with roll quantity-produced by not reporting still Penetrate the stacking film coiled material of the strip of rate layer.Then, it is an object of the invention to provide a kind of for example containing air layer can be turned into The stacking film coiled material of the strip for the extra-low refractive index layer that the refractive index of sub is less than 1.20.
Used in the means of the problem of solution
In order to reach above-mentioned purpose, stacking film coiled material of the invention is characterised by, it is penetrated resin film upper strata is folded Rate is less than 1.20 extra-low refractive index layer.
The stacked film of the present invention is characterised by that it is that the ultralow refraction that refractive index is less than 1.20 is folded on resin film upper strata Rate layer, for above-mentioned extra-low refractive index layer, represent the scratch resistance obtained by Bemcot (registration mark) of film-strength Property be 60~100%, represent pliability to test obtained folding number by MIT be more than 100 times.
The manufacture method of the stacking film coiled material of the present invention is characterised by, includes following processes：Make to contain and form fine The process of the liquid of one or more Component units of gap structure；Aforesaid liquid is coated on to the process on resin film；And will The process that the liquid of institute's application is dried.
The optical component of the present invention is characterised by, ultralow in stacking film coiled material or stacked film containing the invention described above Index layer.
Invention effect
Characteristic of the stacking film coiled material of the present invention by display as described above, can for example realize can turn into air layer The refractive index of replacement is less than 1.20 extra-low refractive index, while can continuously be produced with roll.It is therefore not necessary in order to obtain Extra-low refractive index and multiple components are configured at a certain distance to set air layer, can by desired position configure this The extra-low refractive index layer of invention assigns extra-low refractive index, while the continuous production of low cost can be realized.Therefore, it is of the invention Stacking film coiled material be highly useful in such as the optical component for needing extra-low refractive index.
Brief description of the drawings
Fig. 1 is an example for showing schematically the method for forming extra-low refractive index layer 20 in the present invention on resin film 10 Process sectional view.
Fig. 2 be show schematically the present invention stacking film coiled material manufacture method in process a part and wherein use Device an example figure.
Fig. 3 be show schematically the present invention stacking film coiled material manufacture method in process a part and wherein use Device another example figure.
Fig. 4 is the work for another example for showing schematically the method for forming extra-low refractive index layer in the present invention on base material Sequence sectional view.
Fig. 5 be show schematically the present invention extra-low refractive index layer manufacture method in process a part and wherein make The figure of another example again of device.
Fig. 6 be show schematically the present invention extra-low refractive index layer manufacture method in process a part and wherein make The figure of another example again of device.
Fig. 7 is another example again for showing schematically the method for forming extra-low refractive index layer in the present invention on base material Process sectional view.
Fig. 8 be show schematically the present invention extra-low refractive index layer manufacture method in process a part and wherein make The figure of another example again of device.
Fig. 9 be show schematically the present invention extra-low refractive index layer manufacture method in process a part and wherein make The figure of another example again of device.
Embodiment
The stacking film coiled material of the present invention represents (being noted by Bemcot for film-strength for example in above-mentioned extra-low refractive index layer Volume trade mark) obtained marresistance is 60~100%, the obtained folding number of being tested by MIT for representing pliability is 100 times More than.
In the stacking film coiled material of the present invention, for example fine voids structure can also be formed in above-mentioned extra-low refractive index layer One or more Component units are chemically bonded each other.Above-mentioned Component units can for example contain Direct Bonding each other, also may be used To contain indirect linkage.In addition, in the above-mentioned extra-low refractive index layer of the stacking film coiled material of the present invention, above-mentioned one or more structures Into unit, as long as example, at least a part is chemically bonded each other.Specifically, for example there can also be Component units each other The part not also being chemically bonded even if contact.In addition, in the present invention Component units " indirect linkage " refers to Component units each other It is bonded each other by a small amount of adhesive ingredients below Component units amount." Direct Bonding " refers to constitute list Component units each other The member not Direct Bonding via adhesive ingredients etc. each other.
In the above-mentioned extra-low refractive index layer of the stacking film coiled material of the present invention, such as the above-mentioned mutual bonding of Component units can be with Contain hydrogen bond or covalent bond.Above-mentioned Component units for example can also be by with particle shape, threadiness, flat at least one shape The structure of shape is constituted.Above-mentioned particle shape and flat Component units can also be for example made up of inorganic matter.In addition, above-mentioned particle The constitution element of shape Component units can also for example contain at least one in the group being made up of Si, Mg, Al, Ti, Zn and Zr Plant element.The structure (Component units) for forming particle shape can be that solid particle can also be hollow granule, specifically may be used Include organic silicon particle or organic silicon particle, silicon dioxide hollow nano-particle or silicon dioxide hollow with micropore are received Rice ball (nanoballoon) etc..Fibrous Component units are, for example, the nanofiber of a diameter of nano-scale, specifically may be used Include cellulose nano-fibrous or alumina nano fiber etc..Flat Component units can for example include nanoclay, The bentonite (such as Kunipia F [trade name]) of nano-scale can specifically be included.Above-mentioned fibrous composition is single Member is not particularly limited, for example, can also be selected from by carbon nano-fiber, cellulose nano-fibrous, alumina nano fiber, first Chitin nanofiber, chitosan nano fiber, polymer nanofiber, glass nano-fibre and silica nano fibrous composition At least one of group fibrous material.
The stacking film coiled material of the present invention is, for example, above-mentioned porous body of the extra-low refractive index layer containing micropore particle.In addition, In the present invention, the shape of " particle " (for example, above-mentioned micropore particle etc.) is not particularly limited, for example can be spherical, Can be non-spherical system etc..In addition, above-mentioned micropore particle is for example as described above in the present invention, or collosol and gel is read Beaded particles, nano-particle (hollow Nano silica nanosphere particle), nanofiber etc..
In the stacking film coiled material of the present invention, such as the voidage of above-mentioned extra-low refractive index layer is more than 40%.
In the stacking film coiled material of the present invention, the void size in such as hole is 2~200nm.
In the stacking film coiled material of the present invention, such as thickness is 0.01~100 μm.
In the stacking film coiled material of the present invention, for example, represent that the mist degree of the transparency is less than 5%.
The manufacture method of the stacking film coiled material of the present invention is for example further contained in the process for making aforesaid liquid State the process that the catalyst for making above-mentioned micropore particle be chemically bonded each other is added in liquid.
In the manufacture method of the stacking film coiled material of the present invention, such as above-mentioned catalyst is to promote micropore particle is mutual to hand over Join the catalyst of bonding.
In the manufacture method of the stacking film coiled material of the present invention, for example, above-mentioned Component units are made to be bonded and be formed directly with one another State extra-low refractive index layer.
The present invention stacking film coiled material manufacture method in, for example make above-mentioned Component units each other indirect linkage and formed State extra-low refractive index layer.
In the manufacture method of the stacking film coiled material of the present invention, for example, contain hydrogen bond according to the mutual bonding of above-mentioned Component units Or the mode of covalent bond forms above-mentioned extra-low refractive index layer.
In the manufacture method of the stacking film coiled material of the present invention, such as above-mentioned Component units are selected from by particle shape, threadiness And the Component units of at least one of group shape that tabular is constituted.Above-mentioned particle shape and flat Component units are for example It can be made up of inorganic matter.In addition, the constitution element of for example above-mentioned particle shape Component units can also contain be selected from by Si, Mg, At least one of the group that Al, Ti, Zn and Zr are constituted element.In addition, above-mentioned Component units for example can also be micropore particle.
Hereinafter, further it is specifically described for present invention citing.But, the present invention do not limited by following explanation and Limitation.
[1. stacking film coiled material]
The stacking film coiled material of the present invention is that the ultralow refraction that refractive index is less than 1.20 is folded on resin film upper strata as described above Rate layer.Or, the present invention can also substitute for following stacked films to it, and the stacked film is in tree as described above It is less than 1.20 extra-low refractive index layer that refractive index is folded on adipose membrane upper strata, also, represents (being noted by Bemcot for film-strength Volume trade mark) obtained marresistance is 60~100%, the obtained folding number of being tested by MIT for representing pliability is 100 times More than.
Above-mentioned resin film is not particularly limited, and the species of above-mentioned resin can for example include polyethylene terephthalate (PET), acrylic acid, cellulose-acetate propionate (CAP), cyclic olefin polymer (COP), triacetate (TAC), poly- naphthalenedicarboxylic acid second Excellent thermoplastic resin of the transparency such as diol ester (PEN), polyethylene (PE), polypropylene (PP) etc..
(hereinafter also referred to " of the invention is super for above-mentioned extra-low refractive index layer in the stacking film coiled material or stacked film of the present invention Low-index layer ") for example can directly it be layered on above-mentioned resin film, above-mentioned resin film can also be layered in via other layers On.
When the extra-low refractive index layer of the present invention is for example formed on above-mentioned resin film, the present invention is for example referred to as following Low refraction material, the low refraction material is characterised by, contains above-mentioned extra-low refractive index layer and above-mentioned resin film, and above-mentioned ultralow folding Rate layer stackup is penetrated on above-mentioned resin film and with above-mentioned characteristic.
The present invention extra-low refractive index layer as described above, represent film-strength by Bemcot (registration mark) obtain it is resistance to Scratch resistance is 60~100%.The present invention due to such film-strength, therefore batching when can also for example be resistant to manufacture or Physical impact when using etc..In above-mentioned marresistance, its lower limit is, for example, more than 60%, more than 80%, more than 90%, thereon Limit is, for example, less than 100%, less than 99%, less than 98%, and its scope is, for example, 60~100%, 80~99%, 90~98%.
For the stacking film coiled material or stacked film of the present invention, such as in above-mentioned extra-low refractive index layer, represent film-strength The marresistance obtained by Bemcot (registration mark) is 60~100%, and represent pliability tests obtain resistance to by MIT It is more than 100 times to roll over number of times.Above-mentioned marresistance, can be by following for example when above-mentioned extra-low refractive index layer contains silicon (Si) Method is measured.In addition, when above-mentioned extra-low refractive index layer contains the element beyond silicon (Si), for example can be according to following methods It is measured.
(evaluation of marresistance)
(1) by coating film forming in the void layer (of the invention extra-low refractive index layer) on acrylic film with a diameter of 15mm The round shape of left and right is sampled.
(2) then, for above-mentioned sample with fluorescent X-ray (Shimadzu Seisakusho Ltd.'s company system：ZSXPrimusII) identification silicon with Determine Si coating weights (Si0).Then, will from the above-mentioned vicinity sampled for the above-mentioned void layer on aforesaid propylene sorrel After above-mentioned void layer cuts into 50mm × 100mm and is fixed on glass plate (thickness is 3mm), pass through Bemcot (registrations Trade mark) carry out sliding test.Sliding condition be set as counterweight 100g, 10 come and go.
(3) sampled by the above-mentioned void layer slided from end in the same manner as above-mentioned (1) and fluorescence X is determined, determined Si remaining quantities (Si after scoring test1).Marresistance with pass through Bemcot (registration mark) carry out sliding test before and after Si Survival rate (%) is defined, and can be represented with following formula.
Marresistance (%)=[remaining Si amounts (Si1)/Si coating weights (Si0)] × 100 (%)
The extra-low refractive index layer of the present invention is for example as described above, represent the folding time obtained by MIT experiments of pliability Number is more than 100 times.The present invention is due to this pliability, so processing when batching or using etc. in continuous manufacture Property is excellent.
Its lower limit of above-mentioned folding number is, for example, more than 100 times, more than 500 times, more than 1000 times, and its upper limit is not special Limitation, for example, less than 10000 times, its scope is, for example, 100~10000 times, 500~10000 times, 1000~10000 times.
Above-mentioned pliability refers to the dimensional instability of such as material.Obtained folding number is tested above by MIT for example may be used To be measured by following such method.
(evaluation of folding resistant test)
Above-mentioned void layer (extra-low refractive index layer of the invention) is cut into after 20mm × 80mm strip, is arranged on MIT fold testers (TESTER SANGYO company systems：BE-202 on), and 1.0N load is applied.Wrap into above-mentioned void layer Chuck portion uses R2.0mm, and folding number is at most carried out 10000 times, and using above-mentioned void layer be broken time point number of times as Folding number.
In the extra-low refractive index layer of the present invention, film density is not particularly limited, and its lower limit is, for example, 1g/cm3More than, 10g/cm3Above, 15g/cm3More than, its upper limit is, for example, 50g/cm3Below, 40g/cm3Below, 30g/cm3Below, 2.1g/ cm3Hereinafter, its scope is, for example, 5~50g/cm3, 10~40g/cm3, 15~30g/cm3, 1~2.1g/cm3.In addition, in this hair In bright extra-low refractive index layer, the lower limit of the void content based on above-mentioned film density be, for example, more than 50%, more than 70%, 85% with On, its upper limit is, for example, less than 98%, less than 95%, and its scope is, for example, 50~98%, 70~95%, 85~95%.
Above-mentioned film density can be for example measured by following such method, and above-mentioned void content can for example be based on upper Film density is stated according to calculating as follows.
(film density, the evaluation of void content)
Formed on base material (acrylic film) after void layer (extra-low refractive index layer of the invention), in the layered product Above-mentioned void layer uses X-ray diffraction device (RIGAKU company systems：RINT-2000 the X ray reflection in total reflection region) is determined Rate.Then, after Intensity (intensity) and 2 θ fitting is carried out, from the total reflection of above-mentioned layered product (void layer base material) Critical angle calculates film density (g/cm3), and then, void content (P%) is calculated by following formula.
Void content (P%)=45.48 × film density (g/cm3)+100 (%)
The present invention extra-low refractive index layer have pore structure, the void size in hole refer to the major axis in space (hole) diameter and The diameter of above-mentioned major axis in the diameter of short axle.It is preferred that emptying aperture size be, for example, 2nm~500nm.Under above-mentioned void size Limit for example, more than 2nm, more than 5nm, more than 10nm, more than 20nm, its upper limit be, for example, below 500nm, below 200nm, Below 100nm, its scope is, for example, 2nm~500nm, 5nm~500nm, 10nm~200nm, 20nm~100nm.Void size Due to determining preferred void size according to the purposes using gap structure, so must for example be adjusted to the phase according to purpose The void size of prestige.Void size can for example be evaluated by following methods.
(evaluation of void size)
In the present invention, above-mentioned void size can be quantified by BET test method(s)s.Specifically, in specific area measuring Device (Micromeritics company systems：Trade name ASAP2020) capillary in put into sample (extra-low refractive index of the invention Layer) after 0.1g, carry out being dried under reduced pressure 24 hours at room temperature, the gas in gap structure is de-gassed.Then, by making nitrogen Aspiration is attached on above-mentioned sample, draws adsorption isotherm, obtains broad pore distribution.It is possible thereby to evaluate void size.
As long as the extra-low refractive index layer of the present invention for example has pore structure (porous structure) as described above, such as It can be the open-celled structure body of above-mentioned pore structure continuously.Above-mentioned open-celled structure body for example refers in the ultralow of the invention described above Index layer (such as organosilicon porous body) central hole structure is connected with three-dimensional, it may also be said to be the internal voids company of above-mentioned pore structure Continuous state.When porous plastid has open-celled structure, it is possible thereby to void content shared in blocks is improved, but using such as sky As the heart silica during closed pore particle, it is impossible to form open-celled structure.In contrast, the extra-low refractive index layer of the present invention is for example When using silica sol particles (crushed material for forming the gel silicon compound of colloidal sol), because above-mentioned particle has three The tree of dimension, so can be with coated film (coated film of the colloidal sol of the crushed material containing above-mentioned gel silicon compound) Deposited by above-mentioned tree-shaped particle precipitation and be readily formed open-celled structure.In addition, the extra-low refractive index layer of the present invention is more excellent Form slection has monoblock (monolith) structure of multiple broad pore distributions into open-celled structure.Above-mentioned en-block construction, which refers to for example exist, to be received The hierarchy that the structure in the fine space of meter ruler cun and the open-celled structure being gathered into as identical nanovoids are present. When forming above-mentioned en-block construction, for example, film-strength can be assigned with fine space, and height is assigned with thick perforate space Void content, can take into account film-strength and high void content.In order to form these en-block constructions, for example, first, preferably on being ground into State the pore point of the gap structure of control generation in the gel (gel silicon compound) of the last stage of silica sol particles Cloth.In addition, for example when crushing above-mentioned gel silicon compound, by the way that the granularity of the silica sol particles after crushing is divided Cloth is controlled in desired size, can form above-mentioned en-block construction.
In the extra-low refractive index layer of the present invention, represent that the mist degree of the transparency is not particularly limited, its upper limit is such as less than 5%, preferably shorter than 3%.In addition, its lower limit is, for example, more than 0.1%, more than 0.2%, its scope be, for example, more than 0.1% and Less than 5%, 0.2% less than 3%.
Above-mentioned mist degree can be for example measured by following methods.
(evaluation of mist degree)
Void layer (extra-low refractive index layer of the invention) is cut into 50mm × 50mm size and installed in haze meter (village Upper color technical research institute company system：HM-150 on), mist degree is determined.On haze value, it can be calculated with following formula.
Mist degree (%)=[diffused transmission rate (%)/full light transmittance (%)] × 100 (%)
Above-mentioned refractive index is usually the ratio by the transmission speed on the corrugated of the light in vacuum and the spread speed in medium The referred to as refractive index of the medium.The upper limit of the refractive index of the extra-low refractive index layer of the present invention is, for example, less than 1.20, less than 1.15, Its lower limit is, for example, more than 1.05, more than 1.06, more than 1.07, its scope be, for example, less than more than 1.05~1.20,1.06 with Upper less than~1.20, less than more than 1.07~1.15.
In the present invention, unless otherwise specified, above-mentioned refractive index refers to the refractive index measured under wavelength 550nm.This Outside, the assay method of refractive index is not particularly limited, for example, can be determined by following methods.
(evaluation of refractive index)
Formed on acrylic film after void layer (extra-low refractive index layer of the invention), cut into 50mm × 50mm chi It is very little, and it is fitted in glass plate (thickness with adhesive layer：Surface 3mm).The back side central portion of above-mentioned glass plate is (a diameter of 20mm or so) filled with black magic ink, modulate will not above-mentioned glass plate backside reflection sample.Above-mentioned sample is installed In ellipsometer (J.A.Woollam Japan company systems：VASE on), under conditions of 50~80 degree of wavelength 500nm and incidence angle Refractive index is determined, and refractive index is used as using its average value.
When the extra-low refractive index layer of the present invention is for example formed on above-mentioned resin film, the adaptation with above-mentioned resin film is represented Bonding peel strength be not particularly limited, its lower limit is, for example, more than 1N/25mm, more than 2N/25mm, more than 3N/25mm%, Its upper limit is, for example, below 30N/25mm, below 20N/25mm, below 10N/25mm, and its scope is, for example, 1~30N/25mm, 2 ~20N/25mm, 3~10N/25mm.
In addition, the assay method of above-mentioned bonding peel strength is not particularly limited, for example can by following methods come Determine.
(evaluation of peel strength)
Formed after void layer (extra-low refractive index layer of the invention), be sampled on above-mentioned resin film (such as acrylic film) 50mm × 140mm short strip shape is simultaneously fixed above-mentioned sample on stainless steel with two-sided tape.In PET film (T100：Mitsubishi tree Adipose membrane society system) on laminating acrylic adhesive (thickness be 20 μm), and the gluing strap for cutting into 25mm × 100mm is fitted in On above-mentioned void layer before, it is laminated with above-mentioned PET film.Then, above-mentioned sample is turned into 100mm according to distance between chuck Mode be clamped in cupping machine (society of Shimadzu Seisakusho Ltd. system：AG-Xplus after on), enter under 0.3m/min draw speed Row tension test.Peel strength is used as to carry out the mean test force after 50mm disbonded tests.
The thickness of the extra-low refractive index layer of the present invention is not particularly limited, and its lower limit is, for example, more than 0.01 μm, 0.05 μm Above, more than 0.1 μm, more than 0.3 μm, its upper limit is, for example, less than 100 μm, less than 80 μm, less than 50 μm, less than 10 μm, its Scope is, for example, 0.01~100 μm.
The extra-low refractive index layer such as crushed material containing gel-thickened compound, and above-mentioned crushing as described above of the present invention Thing is chemically bonded each other.In the extra-low refractive index layer of the present invention, the above-mentioned mutual chemical bonding (chemical bond) of crushed material Form is not particularly limited, and the specific example of above-mentioned chemical bond is such as can include cross-bond.In addition, make above-mentioned crushed material that This method being chemically bonded will in detail be described in the manufacture method of the present invention.
The gel form of above-mentioned gel silicon compound is not particularly limited." gel ", which generally refers to solute, to be had because mutually The structure for losing independent motility and being gathered into is acted on, and the state of solidification is presented.In addition, in gel, it is however generally that, it is wet solidifying The gel that glue refers to containing decentralized medium and solute is the same structure in decentralized medium, xerogel refer to solvent be removed and Solute is the gel of the eyed structure with space.In the present invention, above-mentioned gel-thickened compound for example can be wet gel, It can be xerogel.
Above-mentioned gel-thickened compound can for example enumerate the gel compound for monomeric compound gelation of sening as an envoy to.It is specific and Speech, above-mentioned gel silicon compound can for example include the gel compound that the silicon compound of above-mentioned monomer bonds together, and make For specific example, the silicon compound that can include above-mentioned monomer carries out the gelation of hydrogen bonding or molecular separating force bonding each other Thing.Above-mentioned bonding can for example include the bonding using dehydrating condensation.Manufacture method of the method for above-mentioned gelation in the present invention In it is aftermentioned.
In the extra-low refractive index layer of the present invention, represent the uneven volume average particle size of the granularity of above-mentioned crushed material without spy Do not limit, its lower limit is, for example, more than 0.10 μm, more than 0.20 μm, more than 0.40 μm, its upper limit is, for example, less than 2.00 μm, Less than 1.50 μm, less than 1.00 μm, its scope is, for example, 0.10 μm~2.00 μm, 0.20 μm~1.50 μm, 0.40 μm~1.00 μ m.Above-mentioned size distribution can for example pass through dynamic light scattering method, laser diffractometry equigranular Evaluation on distribution device and sweep type Electron microscopes such as electron microscope (SEM), transmission electron microscope (TEM) etc. are measured.
In addition, represent that the uneven size distribution of the granularity of above-mentioned crushed material is not particularly limited, such as μ of particle diameter 0.4 μm~1 M particle be 50~99.9 weight %, 80~99.8 weight %, 90~99.7 weight %, or 1 μm~2 μm of particle diameter particle For 0.1~50 weight %, 0.2~20 weight %, 0.3~10 weight %.Above-mentioned size distribution can for example pass through size distribution Evaluating apparatus or electron microscope are measured.
In the extra-low refractive index layer of the present invention, the species of above-mentioned gel-thickened compound is not particularly limited.As above-mentioned Gel-thickened compound, can exemplify such as gel silicon compound.Hereinafter, using gel-thickened compound as gel silicon compound Illustrated exemplified by situation, but the present invention is not restricted to this.
Above-mentioned cross-bond is, for example, siloxanes key.Siloxanes key can for example include T2 as shown below key, T3 key, T4 key.When the extra-low refractive index layer of the present invention has siloxanes key, for example, there can be any key, it is possible to have wantonly two Key is planted, the key can also with three kinds of wholes.In above-mentioned siloxanes key, T2 and T3 ratio are more, are more imbued with pliability, more can To expect characteristic that gel is original, but film-strength can become fragile.On the other hand, if the T4 ratios in above-mentioned siloxanes key are more, Although then easily embodying film-strength, void size can diminish, and pliability becomes fragile.It is therefore preferable that according to such as purposes come Change T2, T3, T4 ratio.
When the extra-low refractive index layer of the present invention has above-mentioned siloxanes key, T2, T3 and T4 ratio for example relatively with When " 1 " represents T2, T2：T3：T4=1：[1~100]：[0~50], 1：[1~80]：[1~40], 1：[5~60]：[1~30].
In addition, preferably for example contained silicon atom carries out siloxanes bonding to the extra-low refractive index layer of the present invention.As specific The ratio example of the silicon atom (i.e. residual silanol) not being bonded in example, above-mentioned extra-low refractive index layer in contained total silicon atom As being less than 50%, less than 30%, less than 15%.
When above-mentioned gel-thickened compound is above-mentioned gel silicon compound, the silicon compound of above-mentioned monomer is not limited especially System.The silicon compound of above-mentioned monomer can for example include the compound shown in following formula (1).Above-mentioned gel silicon compound is as above It is described be the silicon compound of monomer carry out each other hydrogen bonding or molecular separating force bonding gel compound when, the monomer of formula (1) Between for example can via respective hydroxyl carry out hydrogen bonding.
In above-mentioned formula (1), such as X is 2,3 or 4, R1For straight chained alkyl or branched alkyl.Above-mentioned R1Carbon number be, for example, 1~ 6th, 1~4,1~2.Above-mentioned straight chained alkyl is such as can include methyl, ethyl, propyl group, butyl, amyl group, hexyl, above-mentioned side chain Alkyl is such as can include isopropyl, isobutyl group.Above-mentioned X is, for example, 3 or 4.
As the specific example of the silicon compound shown in above-mentioned formula (1), it is 3 following formula (1 ') institute that can for example include X The compound shown.In following formula (1 '), R1It is identical with above-mentioned formula (1), for example, methyl.Work as R1During for methyl, above-mentioned silicon compound For three (hydroxyl) methyl-monosilanes.When above-mentioned X is 3, above-mentioned silicon compound is, for example, 3 functional silanes with 3 functional groups.
In addition, as the specific example of the silicon compound shown in above-mentioned formula (1), such as the compound that X is 4 can be included. Now, above-mentioned silicon compound is, for example, 4 functional silanes with 4 functional groups.
The silicon compound of above-mentioned monomer for example can also be the hydrolysate of silicon compound precursor.Before above-mentioned silicon compound Body, as long as example can be by hydrolyzing and generating the material of above-mentioned silicon compound, as specific example, can be included down State the compound shown in formula (2).
In above-mentioned formula (2), such as X is 2,3 or 4,
R1And R2Respectively straight chained alkyl or branched alkyl,
R1And R2It can be the same or different,
R1When X is 2, it can be the same or different each other,
R2It can be the same or different each other.
Above-mentioned X and R1For example with the X and R in above-mentioned formula (1)1It is identical.In addition, above-mentioned R2It can such as quote in formula (1) R1Illustration.
As the specific example of the silicon compound precursor shown in above-mentioned formula (2), for example, it can include the following formula that X is 3 Compound shown in (2 ').In following formula (2 '), R1And R2It is identical with above-mentioned formula (2) respectively.Work as R1And R2It is above-mentioned during for methyl Silicon compound precursor is trimethoxy (methyl) silane (hereinafter also referred to " MTMS ").
The silicon compound of above-mentioned monomer is for example from the excellent aspect of low-refraction, preferably above-mentioned 3 functional silane.This Outside, the silicon compound of above-mentioned monomer is for example from the excellent aspect of intensity (such as marresistance), preferably above-mentioned 4 function silicon Alkane.In addition, one kind can be for example used only in the silicon compound of the above-mentioned monomer of the raw material as above-mentioned gel silicon compound, It can be used in combination two or more.As specific example, as the silicon compound of above-mentioned monomer, for example, it can only contain above-mentioned 3 official Can silane, can also only contain above-mentioned 4 functional silane, can also contain above-mentioned 3 functional silane and above-mentioned 4 functional silane this two Person, can also be further containing other silicon compounds.The silicon compound of above-mentioned monomer is used as using two or more silicon compounds When, its ratio is not particularly limited, and can suitably set.
The present invention extra-low refractive index layer for example can also contain be used for make above-mentioned formation fine voids structure one kind or The catalyst that a variety of Component units are chemically bonded each other.The containing ratio of above-mentioned catalyst is not particularly limited, relative to upper State the weight for the one or more Component units to form fine voids structure, for example, 0.01~20 weight %, 0.05~10 weight Measure % or 0.1~5 weight %.
It is used to make above-mentioned formation fine voids knot in addition, the extra-low refractive index layer of the present invention for example can also further contain One or more Component units of structure carry out the crosslinking auxiliary of indirect linkage each other.The containing ratio of above-mentioned crosslinking auxiliary does not have Be particularly limited to, for example relative to above-mentioned formation fine voids structure one or more Component units weight, be 0.01~20 Weight %, 0.05~15 weight % or 0.1~10 weight %.
The form of the extra-low refractive index layer of the present invention is not particularly limited, usually film shape.
The extra-low refractive index layer of the present invention is, for example, coiled material body.In addition, the extra-low refractive index layer such as above institute of the present invention State and further contain resin film, and above-mentioned extra-low refractive index layer can also be formed on the above-mentioned resin film of strip.Now, Another strip film can be laminated on the stacked film of the present invention or containing above-mentioned resin film and above-mentioned extra-low refractive index Another strip resin film (such as lining paper, mold release film, surface protection film) rolled afterwards is laminated on the stacked film of the invention of layer The form of material body.
The manufacture method of the stacking film coiled material of the present invention is not particularly limited, for example, can pass through the present invention as shown below Manufacture method manufacture.
[manufacture methods of 2. stacking film coiled materials]
The manufacture method of the stacking film coiled material of the present invention preferably comprises following processes as described above：Make containing micropore grain The process of the liquid of son；Aforesaid liquid is painted on to the process on resin film；And the process that the liquid of institute's application is dried, But do not limit.The above-mentioned liquid (hereinafter sometimes referred to " liquid of particle containing micropore ") containing micropore particle is not limited especially Determine, for example, the suspension containing above-mentioned micropore particle.In addition, it is following, it is mainly gel to above-mentioned micropore particle The crushed material of compound and above-mentioned extra-low refractive index layer for the crushed material containing gel-thickened compound porous body it is (preferably organic Silicon porous body) situation illustrate.But, even beyond above-mentioned micropore particle is the crushed material of gel-thickened compound Situation, the present invention can also similarly be implemented.In the manufacture method of the stacking film coiled material of the present invention, above-mentioned extra-low refractive index layer The porous body that for example, micropore particle is chemically bonded each other, and in above-mentioned extra-low refractive index layer formation process, example Above-mentioned micropore particle is such as set to be chemically bonded each other.Above-mentioned micropore particle is, for example, the micropore particle of silicon compound, Above-mentioned porous body is organosilicon porous body.The micropore particle of above-mentioned silicon compound is for example containing gelatinous silica compound Grinding bodies.In addition, as above-mentioned extra-low refractive index layer another form, have be made up of fibrous materials such as nanofibers and with The cambial void layer of form in the space wound mutually containing the fibrous material.With above-mentioned micropore in terms of manufacture method Particle is identical.In addition, other also comprising used hallow nanoparticles or nanoclay void layer, use hollow nano-sphere or The void layer of magnesium fluoride formation.In addition, these extra-low refractive index layer can be by single construct texture into void layer, also may be used With for by a variety of construct textures into void layer.The form of void layer can also be single above-mentioned form, or by The void layer of a variety of above-mentioned morphosises.The porous body being chemically bonded each other mainly for above-mentioned micropore particle below Void layer is illustrated.
Manufacturing method according to the invention, can form the extra-low refractive index layer for showing excellent low-refraction.Its reason For example it is presumed as follows, but the present invention is not limited by this supposition.
The above-mentioned crushed material used in the manufacture method of the present invention is due to being after above-mentioned gel silicon compound is crushed The three-dimensional structure of gel silicon compound before material, therefore above-mentioned crushing becomes to be separated into the state of three-dimensional basic structure.And And, in the manufacture method of the present invention, by the way that the crushed material of above-mentioned gel silicon compound is painted on above-mentioned base material, and shape Into the precursor of the cellular structure based on above-mentioned three-dimensional basic structure.That is, manufacturing method according to the invention, can be formed with it is upper That states that the different above-mentioned crushed materials by above-mentioned three-dimensional basic structure of three-dimensional structure of gel silicon compound are formed is novel porous Structure.Therefore, the above-mentioned extra-low refractive index layer finally obtained can produce for example with air layer to same extent function Low-refraction.In addition, in the manufacture method of the present invention, will in order to further make above-mentioned crushed material be chemically bonded each other Above-mentioned new structure immobilization.Therefore, although the above-mentioned extra-low refractive index layer finally obtained is the structure with space, Sufficient intensity and pliability can be maintained.Like this, by the present invention manufacture method obtain extra-low refractive index layer for example It is all useful in terms of low refrangible function aspects and intensity and pliability as the substitute of above-mentioned air layer.In addition, In the case of above-mentioned air layer, such as must by component and component between the two via sept gap be set and carried out Stacking, thus forms air layer between above-mentioned component.But, the extra-low refractive index layer example obtained by the manufacture method of the present invention As only configured on target site, the low refractiveness with above-mentioned air layer to same extent function can be played.Therefore, such as It is above-mentioned such, compared with forming above-mentioned air layer, it can be easier and easily such as optical component is assigned and above-mentioned air The low refractiveness of layer to same extent function.
The manufacture method of the present invention is as long as no special record, and the extra-low refractive index layer that can quote the invention described above is said It is bright.
In the manufacture method of the present invention, above-mentioned gel-thickened compound and its crushed material, above-mentioned monomeric compound and above-mentioned The precursor of monomeric compound can quote the explanation in the porous structure of the invention described above.
The manufacture method of the present invention has the process for making the liquid containing micropore particle as described above.Above-mentioned micropore When particle is the crushed material of gel-thickened compound, above-mentioned crushed material can for example be obtained by the way that above-mentioned gel-thickened compound is crushed .As described above, by crushing above-mentioned gel-thickened compound, the three-dimensional structure of above-mentioned gel-thickened compound is destroyed and is dispersed into Three-dimensional basic structure.
Hereinafter, for above-mentioned monomeric compound the generating of above-mentioned gel-thickened compound of utilization gelation, above-mentioned gel The modulation using the crushed material crushed of shape compound is illustrated, but the present invention is not restricted to following illustration.
The gelation of above-mentioned monomeric compound for example can be by making above-mentioned monomeric compound carry out hydrogen bonding each other or divide Power is bonded to carry out between son.
Above-mentioned monomeric compound can for example include the above-mentioned formula (1) described in the extra-low refractive index layer of the invention described above Shown silicon compound.
The silicon compound of above-mentioned formula (1) is due to for example can be via respective between hydroxyl, therefore the monomer of above-mentioned formula (1) Hydroxyl carry out hydrogen bonding or molecular separating force bonding.
In addition, above-mentioned silicon compound can also be the hydrolysate of above-mentioned silicon compound precursor as described above, for example can also The silicon compound precursor shown in above-mentioned formula (2) that will be described in the extra-low refractive index layer of the invention described above is hydrolyzed and given birth to Into.
The method for hydrolysis of above-mentioned monomeric compound precursor is not particularly limited, for example, can pass through the change in the presence of catalyst Learn reaction and carry out.As above-mentioned catalyst, acid etc. such as can include oxalic acid, acetic acid.Above-mentioned hydrolysis for example can be with By the way that the aqueous solution of oxalic acid is slowly added dropwise into the mixing mixed to above-mentioned silicon compound and dimethyl sulfoxide (DMSO) under room temperature environment After in liquid (such as suspension), 30 minutes or so are stirred in this case to carry out.During by above-mentioned silicon compound precursor hydrolysis, example Such as can be by by the alkoxy complete hydrolysis of above-mentioned silicon compound precursor, further can efficiently embody gel thereafter Change the heating immobilization after curing gap structure is formed.
The gelation of above-mentioned monomeric compound can for example be carried out by the dehydration condensation between above-mentioned monomer.It is above-mentioned Dehydration condensation is for example preferably carried out in the presence of a catalyst, as above-mentioned catalyst, can for example include hydrochloric acid, oxalic acid, The dehydrating condensation catalyst such as the base catalyst such as the acid catalysts such as sulfuric acid and ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide.On State the particularly preferred base catalyst of dehydrating condensation catalyst.In above-mentioned dehydration condensation, above-mentioned catalyst is relative to above-mentioned The addition of monomeric compound is not particularly limited, and relative to above-mentioned 1 mole of monomeric compound, catalyst is, for example, 0.1~10 Mole, 0.05~7 mole, 0.1~5 mole.
The gelation of above-mentioned monomeric compound is for example preferably carried out in a solvent.Above-mentioned monomeric compound in above-mentioned solvent Ratio be not particularly limited.Above-mentioned solvent can for example include dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP), DMAC N,N' dimethyl acetamide (DMAc), dimethylformamide (DMF), gamma-butyrolacton (GBL), acetonitrile (MeCN), ethylene glycol ethyl Ether (EGEE) etc..Above-mentioned solvent can be for example a kind, can also be two kinds or more.The solvent that will be used in above-mentioned gelation Hereinafter also referred to " gelation solvent ".
The condition of above-mentioned gelation is not particularly limited.Relative to the processing of the above-mentioned solvent containing above-mentioned monomeric compound Temperature is, for example, 20~30 DEG C, 22~28 DEG C, 24~26 DEG C, processing time is, for example, 1~60 minute, 5~40 minutes, 10~30 Minute.When carrying out above-mentioned dehydration condensation, its treatment conditions is not particularly limited, and can quote these illustrations.By entering The above-mentioned gelation of row, for example, can make siloxanes key grow and form silica primary particle, further be entered by reaction Exhibition, makes above-mentioned primary particle be connected to each other to beads shape and generates the gel of three-dimensional structure.
The above-mentioned gel-thickened compound obtained by above-mentioned gelation preferably implements maturation process after gelation reaction.It is logical Above-mentioned maturation process is crossed, for example, makes the primary particle further growth of the gel with three-dimensional structure obtained by gelation, Can increase the size of particle itself, result be the neck that particle can be made to be in contact with each other contact condition from a contact amplification to Face is contacted.Having carried out the gel such as gel of the maturation process as described above intensity of itself can increase, and result is to improve The intensity of three-dimensional basic structure after being crushed.Thus, for example in the drying process after the above-mentioned crushed material of application, it can press down The pore size for making the gap structure of above-mentioned three-dimensional basic structure deposition is volatilized and shunk with the solvent of drying process.
Above-mentioned maturation process for example can by set point of temperature and above-mentioned gel-thickened compound is cultivated in the stipulated time and Carry out.Above-mentioned set point of temperature is not particularly limited, and its lower limit is, for example, more than 30 DEG C, more than 35 DEG C, more than 40 DEG C, its upper limit example It it is such as 80 DEG C below, 75 DEG C below, 70 DEG C below, its scope is, for example, 30~80 DEG C, 35~75 DEG C, 40~70 DEG C.Above-mentioned rule Fix time and be not particularly limited, its lower limit is, for example, more than 5 hours, more than 10 hours, more than 15 hours, and its upper limit is, for example, 50 It is hour following, less than 40 hours, less than 30 hours, its scope is, for example, 5~50 hours, 10~40 hours, 15~30 hours.Separately Outside, the optimum condition on curing, the main purpose of condition is for example the increasing for obtaining above-mentioned silica primary particle size The increase of big and neck contacts area.And then, it is considered preferred to the boiling point of the solvent used, it is molten if for example curing temperature is too high Agent will excessively volatilize, it is possible to produce because the concentration of coating liquid (coagulant liquid) concentration makes the pore of three-dimensional gap structure remain silent Unfavorable condition.On the other hand, for example when curing temperature is too low, do not simply fail to fully obtain the effect brought by above-mentioned curing, And batch production technique through when temperature inequality can also increase, it is possible to form ropy product.
Above-mentioned maturation process can for example be used handles identical solvent with above-mentioned gelation, specifically, in preferred pair State the reactant after Gel Treatment (that is, the above-mentioned solvent containing above-mentioned gel-thickened compound) directly implementation.Terminate after gelation Maturation process above-mentioned gel (above-mentioned gel-thickened compound, such as above-mentioned gel silicon compound) in contained residual silane The molal quantity of alcohol radical be, for example, the molal quantity for the alkoxy for setting added raw material (such as above-mentioned monomeric compound precursor) as The ratio of residual silanol groups when 100, its upper limit is, for example, less than 50%, less than 40%, less than 30%, and its lower limit is, for example, More than 1%, more than 3%, more than 5%, its scope is, for example, 1~50%, 3~40%, 5~30%.In order to improve the hard of gel Degree, the molal quantity of such as residual silanol groups is more low more preferred.If the molal quantity of silanol group is too high, being for example possible to can not Gap structure is remained to make organosilicon porous body precursor be crosslinked untill.On the other hand, if the molal quantity of silanol group It is too low, then for example it is possible in the process of the above-mentioned liquid of particle containing micropore (such as suspension) and/or process thereafter is made, It can become to make the crushed material of gel-thickened compound to be crosslinked and sufficient film-strength can not be assigned.In addition, above-mentioned is silanol The example of base, such as, can also be to each functional group when the silicon compound of monomer is modified with various reactive functional groups It is applicable identical phenomenon.
Make above-mentioned monomeric compound that after gelation, resulting gel-thickened compound be entered in above-mentioned gelation solvent Row is crushed.Above-mentioned crushing for example can directly implement pulverization process to the gel-thickened compound in above-mentioned gelation solvent, Above-mentioned gelation can be replaced as after other solvents with solvent, the gel-thickened compound in above-mentioned other solvents is implemented to crush Processing.In addition, for example, because catalyst and solvent used used in gelation reaction also can be residual after curing step Deposit, thus produce liquid through when gelation (working life), drying process when drying efficiency reduce when, be preferably replaced as it Its solvent.By above-mentioned other solvents hereinafter also referred to " crushing solvent ".
Above-mentioned crushing is not particularly limited with solvent, for example, can use organic solvent.Above-mentioned organic solvent can for example be enumerated It is less than 130 DEG C, the solvent that boiling point is less than 100 DEG C, boiling point is less than 85 DEG C to go out boiling point.As specific example, for example, it can arrange Enumerate isopropanol (IPA), ethanol, methanol, butanol, propylene glycol monomethyl ether (PGME), methyl cellosolve, acetone, dimethyl methyl Acid amides (DMF) etc..Above-mentioned crushing solvent for example can be a kind, or of more than two kinds to be used in combination.
Above-mentioned gelation is not particularly limited with solvent with above-mentioned crushing with the combination of solvent, can for example include DMSO with IPA combination, DMSO and ethanol combination, the combination of DMSO and methanol, combination of DMSO and butanol etc..Like this, by inciting somebody to action Above-mentioned gelation is replaced as above-mentioned crushing solvent with solvent, for example, painting evenly can be formed in film described later is formed Fill film.
The breaking method of above-mentioned gel-thickened compound is not particularly limited, for example, can pass through ultrasonic homogenizer, high speed Homogenizer, the reducing mechanism of other utilization cavitation or the reducing mechanism for making liquid impact each other angularly with high pressure etc. is rotated to come Carry out.The device of the progress medium crushing such as ball mill for example destroys the gap structure of gel for physically when crushing, with this Relatively, cavitation erosion mode reducing mechanism preferred in the present invention such as homogenizer is for example due to for without medium mode, it is possible to height The shearing force of speed peels off the weaker silicon dioxide granule composition surface of the bonding being enclosed in gel three-dimensional structure.By This, the colloidal sol three-dimensional structure of acquisition can for example keep the gap structure with a range of size distribution, can be by applying Fill deposition when drying and re-form gap structure.The condition of above-mentioned crushing is not particularly limited, for example, be preferably able to pass through Moment assigns the flowing of high speed, crushes gel in the case where not making solvent volatilize.For example, it is preferable to according to as described above The mode of crushed material of granularity uneven (such as volume average particle size or size distribution) crushed.Assuming that working as grinding time When the amount of work such as intensity are not enough, for example, it can not only remain coarse grain and the pore of densification can not be formed, and it is also possible to outward appearance lacks Point also increases, it is impossible to obtain high-quality.On the other hand, when amount of work is excessive, thus it is for example possible to can turn into than desired granularity The finer sol particles of distribution, makes the void size deposited after coating, drying become fine, and can not meet expectation Void content.
According to the above-mentioned liquid (such as suspension) that can be made containing above-mentioned micropore particle.And then, it can make After liquid containing above-mentioned micropore particle or in manufacturing process, the above-mentioned micropore particle is set to be changed each other by addition Learn the catalyst of bonding and contain liquid containing above-mentioned micropore particle and above-mentioned catalyst to make.The addition of above-mentioned catalyst It is not particularly limited, relative to the weight of above-mentioned micropore particle (such as the crushed material of gel silicon compound), is, for example, 0.01~20 weight %, 0.05~10 weight % or 0.1~5 weight %., for example can be in bonding described later by the catalyst Above-mentioned micropore particle is set to be chemically bonded each other in process.Above-mentioned catalyst can also be for example to promote above-mentioned micropore grain The catalyst of the mutual crosslinking bonding of son.As the chemical reaction for making above-mentioned micropore particle be chemically bonded each other, preferably Utilize the dehydration condensation of residual silanol groups contained in silicon dioxide gel molecule.By promoting silicon with above-mentioned catalyst The mutual reaction of the hydroxyl of silane alcohol base, can realize the continuous film forming in a short time solidifying gap structure.Urged as above-mentioned Agent, for example, can include photoactive catalyst and thermal activities catalyst.According to above-mentioned photoactive catalyst, such as without heating Above-mentioned micropore particle can just be chemically bonded (such as crosslinking bonding) each other.Thus, for example due to being difficult because of heating And produce contraction, it is possible to maintain higher voidage.In addition, in addition to above-mentioned catalyst, or can also use can Replaced with producing the material (catalyst producing agent) of catalyst.For example, it is also possible to be：Above-mentioned catalyst is cross-linking reaction Accelerator, and above-mentioned catalyst producing agent is the material for producing above-mentioned crosslinking promoter.For example, except above-mentioned photolytic activity is urged Beyond agent, or it can also use by the material (photochemical catalyst producing agent) of light generation catalyst to replace；Except Beyond above-mentioned thermal activities catalyst, or it can also use by the material (thermocatalyst producing agent) of heat generation catalyst to take And instead of.As above-mentioned photochemical catalyst producing agent, it is not particularly limited, for example, can includes Photobase generator and (be produced by light irradiation The catalyst of raw base catalyst), photoacid generator (material that acidic catalyst is produced by light irradiation) etc., preferably light alkali Agent.As above-mentioned Photobase generator, for example, it can include：9- anthrylmethyls N, N- diethylamino formic acid esters (9- Anthrylmethyl N, N-diethylcarbamate, trade name WPBG-018), (E) -1- [3- (2- hydroxyphenyls) -2- propylene Acyl group] piperidines ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, trade name WPBG-027), 1- (anthraquinone -2- bases) ethyl imidazol(e) carboxylate (1- (anthraquinon-2-yl) ethyl imidazolecarboxylate, Trade name WPBG-140), 2- nitrobenzophenone methyl 4- methacryloxy piperidines -1- carboxylates (trade name WPBG-165), 1,2- diisopropyls -3- [double (dimethylamino) methylene] guanidine 2- (3- benzoyloxy phenyls) propionic esters (trade name WPBG- 266), 1,2- dicyclohexyls -4,4,5,5- tetramethyl biguanides normal-butyl triphenyl borine acid esters (trade name WPBG-300) and 2- (9- oxa- xanthene -2- bases) propionic acid 1,5,7- tri- azabicyclo [4.4.0] decyl- 5- alkene (Tokyo HuaCheng Industry Co., Ltd), contain Compound (the trade name HDPD-PB100 of 4- piperidine carbinols：Heraeus company systems) etc..In addition, the above-mentioned business containing " WPBG " The name of an article is the trade name of Wako Pure Chemical Industries, Ltd..As above-mentioned photoacid generator, for example, it can include aromatic series sulfonium salt (trade name SP-170：ADEKA companies), triarylsulfonium salt (trade name CPI101A：San-Apro companies), aromatic iodonium salts (trade name Irgacure250：Ciba Japan companies) etc..In addition, making what above-mentioned micropore particle was chemically bonded each other Catalyst is not limited to above-mentioned photoactive catalyst, for example, can also be thermal activities catalyst as urea.Make above-mentioned micropore The catalyst that particle is chemically bonded each other base catalysis such as can include potassium hydroxide, sodium hydroxide, ammonium hydroxide Acid catalysts such as agent, hydrochloric acid, acetic acid, oxalic acid etc..In them, preferably base catalyst.Above-mentioned micropore particle is set to enter each other The catalyst of row chemical bonding can be for example added to containing above-mentioned crushed material (micropore particle) before it will carry out application Used in sol particles liquid (such as suspension), or mixed liquor obtained from above-mentioned catalyst is mixed into solvent can be used as To use.Above-mentioned mixed liquor for example can be：Directly addition is dissolved in coating liquid obtained from above-mentioned sol particles liquid, made Solution obtained from stating catalyst dissolution in a solvent, make above-mentioned catalyst it is scattered in a solvent obtained from dispersion liquid.It is above-mentioned Solvent is not particularly limited, such as can include various organic solvents, water, buffer solution.
In addition, for example when above-mentioned micropore particle is to be closed by the silication at least containing the saturated bond functional group below 3 functions , can also be after the liquid containing above-mentioned micropore particle is made or in system during the crushed material for the gel silicon compound that thing is obtained Make further to add in process for making the crosslinking auxiliary of above-mentioned micropore particle indirect linkage each other.The crosslinking auxiliary leads to Cross between particle, particle is each interacted or is bonded with crosslinking auxiliary, can make slightly to separate apart from upper Particle be also bonded each other, can efficiently improve intensity.It is used as above-mentioned crosslinking auxiliary, preferably many cross-linking silane lists Body.Above-mentioned many cross-linking silane monomers specifically have the alkoxysilyl of such as more than 2 and less than 3, and alcoxyl Chain length between base silicyl can be carbon number more than 1 and less than 10, it is possible to contain the element in addition to carbon.It is used as above-mentioned friendship Join adjuvant, for example, can include：Double (trimethoxysilyl) ethane, double (triethoxysilyl) ethane, double (three Methoxysilyl) methane, double (triethoxysilyl) methane, double (triethoxysilyl) propane, double (front threes Epoxide silicyl) propane, double (triethoxysilyl) butane, double (trimethoxysilyl) butane, double (three ethoxies Base silicyl) pentane, double (trimethoxysilyl) pentanes, double (triethoxysilyl) hexanes, double (trimethoxies Silicyl) hexane, double (trimethoxysilyl)-N- butyl-N- propyl group-ethane -1,2- diamines, three-(3- trimethoxies Silylpropyl) isocyanuric acid ester, three-(3- triethoxysilylpropyltetrasulfides) isocyanuric acid esters etc..It is auxiliary as the crosslinking The addition of auxiliary agent, is not particularly limited, for example relative to above-mentioned silicon compound micropore particle weight, be 0.01~20 Weight %, 0.05~15 weight % or 0.1~10 weight %.
Then, manufacture method of the invention has the above-mentioned liquid of particle containing micropore (such as suspension) application as described above Process on resin film.Above-mentioned application can for example use various application modes described later, in addition, being not limited to these. In addition, by the way that the solvent containing above-mentioned crushed material is directly painted on above-mentioned base material, the precursor of above-mentioned porous body can be formed (coated film).The precursor of above-mentioned porous body is for example referred to as coating layer.In addition, above-mentioned porous body precursor is bonding described later The precursor of above-mentioned porous body before process is for example referred to as the precursor film of the extra-low refractive index layer relative to the invention described above (or precursor layer).By forming the precursor (coated film) of above-mentioned porous body, such as after being destroyed by above-mentioned three-dimensional structure Above-mentioned crushed material sedimentation deposition and construct new three-dimensional structure.
Above-mentioned solvent (hereinafter also referred to " application with solvent ") is not particularly limited, for example, can use organic solvent.It is above-mentioned Organic solvent can for example include the solvent that boiling point is less than 130 DEG C.As specific example, can for example include IPA, ethanol, Methanol, butanol etc., in addition it is possible to use with above-mentioned crushing solvent identical solvent.The present invention includes the above-mentioned gel of crushing During the process of compound, in the formation process of the precursor of above-mentioned porous body, for example, it can also directly use and contain above-mentioned gel The above-mentioned crushing solvent of the crushed material of shape compound.
In above-mentioned coating process, for example preferably by the above-mentioned crushed material of the colloidal sol shape being dispersed in above-mentioned solvent (with It is painted on above-mentioned base material down also referred to as " sol particles liquid ").The sol particles liquid of the present invention for example can be attached to base material in painting It is upper and after drying, by bond sequence is chemically crosslinked and the sky of film-strength that continuous film forming goes out more than with certain level Gap layer.In addition, " colloidal sol " in the present invention refers to, by the way that the three-dimensional structure of gel is crushed, make holding gap structure one The silica sol particles for the nanometer three-dimensional structure divided disperse in a solvent and show the state of mobility.
Concentration of the above-mentioned crushed material in above-mentioned solvent is not particularly limited, and for example, 0.3~50% (v/v), 0.5~ 30% (v/v), 1.0~10% (v/v).If the excessive concentration of above-mentioned crushed material, such as the mobility of above-mentioned sol particles liquid Condensation product application striped when being possible to significantly reduce and producing application.On the other hand, if the concentration mistake of above-mentioned crushed material Low, then for example not only the drying of the solvent of above-mentioned sol particles liquid needs to expend the suitable time, and due to just dried Residual solvent can also increase, thus be possible to void content reduction.
The physical property of above-mentioned colloidal sol is not particularly limited.The shear viscosity of above-mentioned colloidal sol is for example in 10001/s shear rate Under, it is below viscosity 100cPas, viscosity below 10cPas, below viscosity 1cPas.If shear viscosity is too high, for example A problem that being possible to produce application striped, and see the reduction of the transferring rate of intaglio plate application.On the contrary, in shear viscosity When too low, thus it is for example possible to wet thickness when can not thicken application and desired thickness can not be obtained after the drying.
Above-mentioned crushed material is not particularly limited relative to the painting loading amount of above-mentioned base material, for example can be many according to above-mentioned organosilicon Expectation thickness of hole body etc. and suitably set.It is many for 0.1~1000 μm of above-mentioned organosilicon forming thickness as specific example During hole body, above-mentioned crushed material relative to above-mentioned base material painting loading amount above-mentioned base material every 1m2Area is, for example, 0.01~60000 μ g, 0.1~5000 μ g, 1~50 μ g.The preferred painting loading amount of above-mentioned sol particles liquid is due to the concentration or application with such as liquid Mode etc. is relevant, so being difficult to make single definition, if considering productivity ratio, preferably carries out application as far as possible with thin layer.If coating Amount is excessive, then can for example be improved by dry possibility in drying oven before solvent volatilization.Thus, nanometer pulverization sol particles Sedimentation is deposited and formed before gap structure in a solvent, it is possible to the formation in space is hindered because of solvent seasoning, makes emptying aperture Rate is greatly reduced.On the other hand, if coating weight is excessively thin, because base material concavo-convex hydrophilic and hydrophobic it is unequal, produce application it is recessed Sunken risk is possible to uprise.
And then, manufacture method of the invention has the liquid of particle containing micropore after application (before porous body as described above Body (coated film)) process that is dried.By above-mentioned drying process, such as in the precursor that can not only remove above-mentioned porous body Above-mentioned solvent (in above-mentioned sol particles liquid contained solvent), purpose is more to settle sol particles in drying process Deposition, to form gap structure.The temperature of above-mentioned drying process is, for example, 50~250 DEG C, 60~150 DEG C, 70~130 DEG C, on The time for stating drying process is, for example, 0.1~30 minute, 0.2~10 minute, 0.3~3 minute.It is timely on drying process temperature Between, such as in continuous productivity ratio or embody under the association of high void content, preferably lower temperature and shorter time.If condition is excessively tight Lattice, then for example in the case where base material is resin film, because of the glass transition temperature close to above-mentioned base material, above-mentioned base material can be dry The shortcomings of being stretched in dry stove and be possible to crack in the gap structure formed after firm application.On the other hand, in bar When part is excessively loose, such as due to containing residual solvent at the time of drying oven is left, so in subsequent processing with roller friction When to be likely to occur scratch etc. apparent bad.
Above-mentioned drying process can be for example natural drying, or heat drying, can also be to be dried under reduced pressure.It is above-mentioned Drying means is not particularly limited, for example, can use general heating arrangements.Above-mentioned heating arrangements can for example include hot blast Device, heating roller, far infra-red heater etc..Wherein, in the case of premised on industrially continuous production, heating is preferably used Dry.In addition, on used solvent, shrinkage stress, the Yi Jiyou for volatilizing and producing with solvent during in order to suppress to dry The seminess of its void layer (above-mentioned organosilicon porous body) produced, the preferably low solvent of surface tension.As above-mentioned solvent, Such as can to include with isopropanol (IPA) be the lower alcohol of representative, hexane, perflexane, but it is not limited to these.
Above-mentioned drying process can be able to be for example heat drying, or be dried under reduced pressure to spontaneously dry.It is above-mentioned dry Drying method is not particularly limited, for example, can use general heating arrangements.Above-mentioned heating arrangements can for example include fan heater, Heating roller, far infra-red heater etc..Wherein, in the case of premised on industrially continuous production, heating is preferably used dry It is dry.In addition, on used solvent, the shrinkage stress that volatilizees and produce with solvent during in order to suppress to dry and by it During the seminess of the void layer (above-mentioned organosilicon porous body) of generation, the preferred low solvent of surface tension.As above-mentioned solvent, Such as can to include with isopropanol (IPA) be the lower alcohol of representative, hexane, perflexane, but it is not limited to these.This Outside, such as can also in above-mentioned IPA in add a small amount of full fluorine system surfactant or silicon systems surfactant and reduce table Face tension force.
The three-dimensional structure of above-mentioned crushed material in manufacturing method according to the invention, such as precursor of above-mentioned porous body is consolidated Fixedization.When carrying out immobilization using conventional sintering, for example, induce silanol by carrying out more than 200 DEG C of high-temperature process The dehydrating condensation of base, the formation of siloxanes key.In the present invention, by making the various additives of the above-mentioned dehydration condensation of catalysis Reacted, such as in the case where base material is resin film, damage will not be produced on above-mentioned base material, can be at 100 DEG C or so Relatively low drying temperature and be continuously formed gap structure in of short duration processing time less than several minutes and make its immobilization.
The above-mentioned method being chemically bonded is not particularly limited, for example can be according to the kind of above-mentioned gel silicon compound Class and suitably determine.As specific example, above-mentioned chemical bonding can for example pass through the mutual chemical crossbond of above-mentioned crushed material Close and carry out, in addition, in the case that inorganic particulate by titanium oxide etc. is added in above-mentioned crushed material, being additionally considered that can be with Above-mentioned inorganic particulate and above-mentioned crushed material is set to carry out chemical crosslinking bonding.In addition, in the case where supporting the biocatalysts such as enzyme, It is bonded it is also possible that the position different from catalyst activity point carries out chemical crosslinking with above-mentioned crushed material.It is therefore contemplated that this hair It is bright to be not only the example void layer that sol particles is formed each other as described above (organosilicon porous body), can also expanded application in organic It is inorganic to blend together void layer, host and guest (host-guest) void layer etc., but it is not limited to these.
Above-mentioned bonding for example can be according to the species of the crushed material of above-mentioned gel-thickened compound, by making above-mentioned crushed material Chemical reaction in the presence of the catalyst that (micropore particle) is chemically bonded each other is carried out.Above-mentioned catalyst can also be For example promote the catalyst of the mutual crosslinking bonding of micropore particle.As the chemical reaction in the present invention, preferably by dioxy The dehydration condensation of contained residual silanol groups in SiClx colloidal sol molecule.By promoting silanol group with above-mentioned catalyst The mutual reaction of hydroxyl, can enter to exercise the continuous film forming of gap structure solidification in a short time.As above-mentioned catalyst, for example Acid catalysts such as the base catalysts such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, hydrochloric acid, acetic acid, oxalic acid etc. can be included, but It is not limited to these.The particularly preferred base catalyst of catalyst of above-mentioned dehydration condensation.In addition it is also possible to preferably use Light production acid catalyst, light production base catalyst, photoacid generator, the light of catalyst activity are embodied by irradiation light (such as ultraviolet) Generated base alkaline agent etc..As light production acid catalyst, light production base catalyst, photoacid generator and Photobase generator, it is not particularly limited, for example such as It is upper described.Above-mentioned catalyst in the process for making the above-mentioned liquid of particle containing micropore for example as set forth above, it is possible to be added to above-mentioned In the liquid of particle containing micropore (for example, suspension of above-mentioned crushed material (micropore particle)).More specifically, for example preferably will be upper State catalyst and be added to the sol particles liquid containing above-mentioned crushed material (micropore particle) before it will carry out application and (for example suspend Liquid) in use, or used as mixed liquor obtained from above-mentioned catalyst is mixed into solvent.Above-mentioned mixed liquor for example may be used Think：Directly addition be dissolved in coating liquid obtained from above-mentioned sol particles liquid, make above-mentioned catalyst dissolution in a solvent and Obtained solution, make above-mentioned catalyst it is scattered in a solvent obtained from dispersion liquid.Above-mentioned solvent is not particularly limited, as above institute State such as can enumerate water outlet, buffer solution.
Chemical reaction in the presence of above-mentioned catalyst does not have in which of the manufacture method of present invention stage progress (causing) It is particularly limited to.Above-mentioned chemical reaction can be carried out by following manner, for example：To containing being added to above-mentioned sol particles in advance The above-mentioned coated film of above-mentioned catalyst in liquid (such as suspension) carries out light irradiation or heating；Or in above-mentioned coated film spray attachment State and light irradiation or heating are carried out after catalyst；Or light irradiation or heating are carried out while spray attachment above-mentioned catalyst.For example, when upper When stating catalyst for photoactive catalyst, by light irradiation above-mentioned micropore particle can be made to be chemically bonded and be formed each other Above-mentioned extra-low refractive index layer.In addition, when above-mentioned catalyst is thermal activities catalyst, above-mentioned micropore grain can be made by heating Son is chemically bonded and forms above-mentioned extra-low refractive index layer each other.Accumulated light in above-mentioned light irradiation is not particularly limited, It is, for example, 200~800mJ/cm in terms of@360nm conversions2, 250~600mJ/cm2Or 300~400mJ/cm2.From prevent irradiation Amount deficiency makes not being in progress using the decomposition of the light absorbs of catalyst producing agent and from the viewpoint of effect becomes insufficient, 200mJ/cm2Accumulated light above is preferable.In addition, sustaining damage and producing the sight of hot gauffer from the base material prevented under void layer Point sets out, 800mJ/cm2Following accumulated light is preferable.The condition of above-mentioned heating is not particularly limited, above-mentioned heating temperature Degree is, for example, 50~250 DEG C, 60~150 DEG C, 70~130 DEG C, and the above-mentioned heat time is, for example, 0.1~30 minute, 0.2~10 point Clock, 0.3~3 minute.Or, the process that the above-mentioned sol particles liquid (such as suspension) after application is dried can also be simultaneous Make the process chemically reacted in the presence of above-mentioned catalyst.That is, the above-mentioned sol particles liquid after by application (for example suspends Liquid) in the process that is dried, above-mentioned crushed material (micropore grain can also be made by the chemical reaction in the presence of above-mentioned catalyst Son) it is chemically bonded each other.In this case as well, it is possible to by the way that above-mentioned coated film is further added after above-mentioned drying process Heat, makes above-mentioned crushed material (micropore particle) further be bonded securely each other.And then, thus it is speculated that the change in the presence of above-mentioned catalyst Learning reaction sometimes also can be above-mentioned containing micropore grain in the process and application for making the above-mentioned liquid of particle containing micropore (such as suspension) Cause in the process of sub- liquid.However, the supposition is limited without any the present invention.In addition, on used solvent, being, for example, The shrinkage stress that volatilizees and produce with solvent when suppressing to dry, the preferably seminess for the void layer being generated by it, surface The low solvent of tension force.Such as can to include with isopropanol (IPA) be the lower alcohol of representative, hexane, perflexane, but do not limit Due to these.
According to it is above-mentioned can manufacture the present invention extra-low refractive index layer (stacking film coiled material), but the present invention manufacture method not It is limited by this.
In addition it is also possible to carry out for example carrying out heating always to obtained extra-low refractive index layer (stacking film coiled material) of the invention The processing such as change improves process (below otherwise referred to as " aging process ") to improve the intensity of intensity.For example, on resin film upper strata In the case of the extra-low refractive index layer for being laminated with the present invention, process (aging process) is improved by above-mentioned intensity, can improve relative In the bonding peel strength of above-mentioned resin film., for example can also be by the present invention in above-mentioned intensity improves process (aging process) Extra-low refractive index layer heated.Temperature in above-mentioned aging process is, for example, 40~80 DEG C, 50~70 DEG C, 55~65 DEG C. The time of above-mentioned reaction is, for example, 5~30hr, 7~25hr or 10~20hr.In above-mentioned aging process, such as by that will heat Temperature is set to low temperature, can suppress to improve bonding peel strength while above-mentioned extra-low refractive index layer shrinks, can take into account height Both voidage and intensity.
Phenomenon and mechanism are unclear caused by above-mentioned intensity improves process (aging process), but it is considered that are due to For example by catalyst contained in the extra-low refractive index layer of the present invention, make the mutual chemical bonding (example of above-mentioned micropore particle Such as cross-linking reaction) further develop and intensity raising.It is used as specific example, it is believed that when above-mentioned micropore particle is silicon compound There is residual silane in micropore particle (such as the grinding bodies of gelatinous silica compound) and above-mentioned extra-low refractive index layer During alcohol radical (OH yls), above-mentioned residual silanol groups can be chemically bonded by cross-linking reaction each other.In addition, the present invention's is super Contained catalyst is not particularly limited in low-index layer, for example, can be the catalyst employed in above-mentioned bond sequence, The alkaline matter produced by light irradiation, above-mentioned bonding can also be passed through for the light production base catalyst employed in above-mentioned bond sequence Light production acid catalyst employed in process passes through acidic materials produced by light irradiation etc..But, the explanation does not limit to illustrate The fixed present invention.
In addition it is also possible to further form bonding adhesive linkage (bonding adhesive linkage shape on the extra-low refractive index layer of the present invention Into process).Specifically, coating (application) adhesive or bonding on the extra-low refractive index of present invention layer can also for example be passed through Agent and form above-mentioned bonding adhesive linkage.In addition it is also possible to pass through adhesive tape by above-mentioned bonding adhesive linkage is laminated with base material etc. Above-mentioned bonding adhesive linkage side conform to the present invention extra-low refractive index layer on, thus the present invention extra-low refractive index layer on shape Into above-mentioned bonding adhesive linkage.Now, the base material of above-mentioned adhesive tape etc. can keep the state directly fitted, and can also be glued from above-mentioned Adhesive linkage is closed to peel off.In the present invention, " adhesive " and " adhesive layer " for example refers to the agent premised on the peeling off again of clung body Or layer.In the present invention, " bonding agent " and " adhesive linkage " for example refers to the not agent premised on the peeling off again of clung body or layer.But It is that in the present invention, " adhesive " and " bonding agent " not can be distinguished clearly, and " adhesive layer " and " adhesive linkage " also not can be with bright Really difference.In the present invention, the adhesive or bonding agent for forming above-mentioned bonding adhesive linkage are not particularly limited, for example, can use General adhesive or bonding agent etc..As above-mentioned adhesive or bonding agent, for example, it can include acrylic acid series, vinyl alcohol The polymer bonding agents and rubber series bonding agent etc. such as system, silicon-type, Polyester, polyurethane series, polyethers system.In addition, also may be used Include by bonding agents constituted such as the water-soluble cross-linker of the vinyl alcohol based polymer such as glutaraldehyde, melamine, oxalic acid etc.. These adhesives and bonding agent can be used only a kind, can also will be a variety of and with (such as mixing, be laminated).Above-mentioned bonding is glued The thickness for connecing layer is not particularly limited, for example, 0.1~100 μm, 5~50 μm, 10~30 μm or 12~25 μm.
And then, the extra-low refractive index layer of the present invention can also be made to be reacted with above-mentioned bonding adhesive linkage and form configuration in this hair Bright extra-low refractive index layer and the intermediate layer (intermediate layer formation process) of the centre of above-mentioned bonding adhesive linkage.Pass through above-mentioned centre Layer, for example, can make the extra-low refractive index layer of the present invention be not easy to peel off with above-mentioned bonding adhesive linkage.Its reason (mechanism) is unclear Chu, but be presumably due to caused by anchoring properties (Anchoring Effect) in for example above-mentioned intermediate layer.Above-mentioned anchoring properties (Anchoring Effect) refers to Near interface in above-mentioned void layer Yu above-mentioned intermediate layer, above-mentioned intermediate layer forms the structure being interleaved to inside above-mentioned void layer, Thus make the phenomenon (effect) that above-mentioned interface is firmly fixed.But, the reasons why its reason (mechanism) is speculates (mechanism) One example, does not limit the present invention.The extra-low refractive index layer of the present invention is with the reaction of above-mentioned bonding adhesive linkage also without special Limit, for example, can also be the reaction using catalyst action.Above-mentioned catalyst can also be ultralow refraction of the invention Contained catalyst in rate layer.Specifically, can be for example the catalyst employed in above-mentioned bond sequence, or on State the light employed in bond sequence and produce base catalyst by being adopted in the alkaline matter produced by light irradiation, above-mentioned bond sequence Light production acid catalyst passes through acidic materials produced by light irradiation etc..In addition, the present invention extra-low refractive index layer with it is above-mentioned The reaction of bonding adhesive linkage for example can be that can generate the reaction (such as cross-linking reaction) of new chemical bond.The temperature of above-mentioned reaction Degree is, for example, 40~80 DEG C, 50~70 DEG C, 55~65 DEG C.The time of above-mentioned reaction be, for example, 5~30hr, 7~25hr or 10~ 20hr.In addition, the intermediate layer formation process can also double as being used to improve the above-mentioned strong of extra-low refractive index layer intensity of the invention Degree improves process (aging process).
It for example can further be laminated and make with other films (layer) according to extra-low refractive index layer of the invention obtained above Into the laminate structure containing above-mentioned porous structure.Now, in above-mentioned laminate structure, each inscape can for example be situated between It is laminated by adhesive or bonding agent.
From efficiency aspect, above-mentioned each inscape stacking for example can by using strip film continuous place Reason (so-called roll-to-roll (Roll to Roll) etc.) is laminated, when base material is shapes construction element etc., can also by through Those of batch processed are laminated.
Hereinafter, for the method for the extra-low refractive index layer that the invention described above is formed on base material, illustrated using Fig. 1~3 Bright continuous processing process.On Fig. 2, expression is film-made out above-mentioned organosilicon porous body (extra-low refractive index layer) and fits diaphragm afterwards simultaneously The process batched, when being laminated to another functional membrane, can use the above method, can also be in another work(of application Can property film and after being dried, the above-mentioned organosilicon porous body (extra-low refractive index after above-mentioned film forming of being fitted before will batching Layer).In addition, it is illustrated that film mode be only an example, be not limited to these.
In addition, above-mentioned base material can also be the resin film described in the explanation of the extra-low refractive index layer of the present invention.Now, lead to Cross and above-mentioned extra-low refractive index layer is formed on above-mentioned base material, the extra-low refractive index layer of the present invention can be obtained.In addition, above-mentioned The extra-low refractive index layer after above-mentioned extra-low refractive index layer by above-mentioned extra-low refractive index layer stackup in the present invention is formed on base material to say On resin film described in bright, it is also possible to obtain extra-low refractive index layer of the invention.
The work in the method that above-mentioned extra-low refractive index layer is formed on above-mentioned base material is schematically illustrated in Fig. 1 sectional view One example of sequence.In Fig. 1, the forming method of above-mentioned extra-low refractive index layer is included：Coating process (1), it is by above-mentioned gel The sol particles liquid 20 " of the crushed material of compound is painted on base material 10；Coated film formation process (drying process) (2), it makes The coated film 20 ' of the precursor layer as above-mentioned extra-low refractive index layer is dried and formed to sol particles liquid 20 "；And chemical treatment process (such as crosslinking Treatment process) (3), it is chemically treated (such as crosslinking Treatment) to coated film 20 ' and forms extra-low refractive index Layer 20.So extra-low refractive index layer 20 can be formed on base material 10 as shown.In addition, the formation of above-mentioned extra-low refractive index layer Method can suitably include or can not include the process in addition to above-mentioned operation (1)~(3).
In above-mentioned coating process (1), the coating process of sol particles liquid 20 " is not particularly limited, can be using general Coating process.As above-mentioned coating process, for example, it can include slit coventry type die head coventry (slot die) method, reverse intaglio plate coating Method, micro- intagliotype (micro-gravure coating process), infusion process (Dipcoat method), spin-coating method, spread coating, rolling method, flexible printing method, Wire rod rubbing method, spraying process, extrusion coated method, heavy curtain rubbing method, reverse rubbing method etc..In them, from productivity ratio, film The viewpoints such as flatness are set out, preferably extrusion coated method, heavy curtain rubbing method, rolling method, micro-gravure coating process etc..Above-mentioned colloidal sol grain The painting loading amount of sub- liquid 20 " is not particularly limited, for example, can be carried out in the way of so that extra-low refractive index layer 20 turns into suitable thickness Appropriate setting.The thickness of extra-low refractive index layer 20 is not particularly limited, for example can be as described above.
In above-mentioned drying process (2), sol particles liquid 20 " is dried and (that is, removed contained in sol particles liquid 20 " Decentralized medium) and form coated film (precursor layer) 20 '.The condition of drying process is not particularly limited, as described above.
And then, in above-mentioned chemical treatment process (3), to containing added before application above-mentioned catalyst (for example, light live Property the thermal activities such as catalyst or KOH catalyst) coated film 20 ' carry out light irradiation or heating, make the above-mentioned powder in coated film 20 ' Mince and be chemically bonded (be for example crosslinked) each other and form extra-low refractive index layer 20.In above-mentioned chemical treatment process (3) Light irradiation or heating condition be not particularly limited, as described above., for example can also be by using above-mentioned resin as base material 10 Film, is directly laminated extra-low refractive index layer 20 on above-mentioned resin film (base material 10).
Then, the painting device of slit coventry type die head coventry method is showed schematically in fig. 2 and has used its above-mentioned ultralow refraction One example of the forming method of rate layer.Although in addition, Fig. 2 is sectional view, pattern filling is eliminated in order to easily see.
As illustrated, each operation in the method for the device has been used and is while by roller by base material 10 towards a side To conveyance while carrying out.Conveyance speed is not particularly limited, for example, 1~100m/ minutes, 3~50m/ minutes, 5~30m/ points Clock.
First, transported while releasing base material 10 from outlet roller 101, while being carried out on coating roller 102 in base material 10 The coating process (1) of upper application sol particles liquid 20 ", then, in the internal migration of baking oven area 110 to drying process (2).Fig. 2's It is to carry out predrying process before drying process (2) after coating process (1) in painting device.Predry drying process can be without Heating is crossed, is carried out at room temperature.Heating arrangements 111 are used in drying process (2).As heating arrangements 111, as described above, Fan heater, heating roller, far infra-red heater etc. can suitably be used.In addition, for example drying process (2) can also be divided into many Individual process, makes drying temperature with follow-up drying process more and more higher.
After drying process (2), chemical treatment process (3) is carried out in chemical treatment area 120.In chemical treatment process (3) in, such as when dried coated film 20 ' contains photoactive catalyst, to configure the lamp (light irradiation in base material about 10 Mechanism) 121 progress light irradiations.Or, such as when coated film 20 ' after the drying contains thermal activities catalyst, use fan heater (heating arrangements) replace lamp (light irradiation device) 121, with configuring the fan heater 121 in base material about 10 heated base material 10. By the crosslinking Treatment, the mutual chemical bonding of the above-mentioned crushed material in coated film 20 ', extra-low refractive index 20 quilt of layer can be caused Solidification reinforcing.In addition, in this example, chemical treatment process (3) is carried out afterwards in drying process (2), but as described above, in the present invention Which of manufacture method in stage cause the mutual chemical bonding of above-mentioned crushed material to be not particularly limited.For example as described above, dry Drying process (2) can also double as chemical treatment process (3).Even in addition, producing above-mentioned chemical bonding in drying process (2) In the case of, chemical treatment process (3) can also be further carried out, makes the mutual chemical bonding of above-mentioned crushed material more firm. In addition it is also possible to drying process (2) previous process (for example predry drying process, coating process (1), make coating liquid (for example Suspension) process etc.) in cause the mutual chemical bonding of above-mentioned crushed material.Then, by base material after chemical treatment process (3) The layered product that extra-low refractive index layer 20 is formed with 10 is batched by takers-in 105., for example can also be by making as base material 10 Above-mentioned resin film is used, extra-low refractive index layer 20 is directly laminated on above-mentioned resin film (base material 10).In addition, in fig. 2, will be above-mentioned The extra-low refractive index layer 20 of layered product is coated to and protected with the screening glass released from roller 106.Here, can also make by strip Other layers of film formation are laminated on extra-low refractive index layer 20 replacing above-mentioned screening glass.
The painting device of micro- intagliotype (micro-gravure coating process) is showed schematically in figure 3 and has used the above-mentioned ultralow of its One example of the forming method of index layer.Although in addition, the figure is sectional view, in order to easily see that eliminating pattern fills out Fill.
As illustrated, each operation in the method for the device has been used and is in the same manner as Fig. 2 while by roller by base Material 10 is transported while carrying out in one direction.Conveyance speed is not particularly limited, for example, 1~100m/ minutes, 3~50m/ points Clock, 5~30m/ minute.
First, transported while releasing base material 10 from outlet roller 201, while carrying out the application sol particles on base material 10 The coating process (1) of liquid 20 ".The application of sol particles liquid 20 " as illustrated, utilizes reservoir 202, scraper (doctor Knife) 203 and nick version 204 carry out.Specifically, the sol particles liquid 20 " for making storage stay in reservoir 202 is attached to 204 surfaces of nick version, then defined thickness is controlled into scraper 203, while being painted on the surface of base material 10 with nick version 204.Separately Outside, nick version 204 is not limited by this to illustrate, and can also use other any applying mechanisms.
Followed by drying process (2).Specifically, as illustrated, application is transported in baking oven area 210 molten The base material 10 of the sub- liquid 20 " of micelle, and heated by the heating arrangements 211 in baking oven area 210 and dry sol particles liquid 20 ". Heating arrangements 211 for example can also be identical with Fig. 2.In addition, can also for example be made by the way that baking oven area 210 is divided into multiple blocks Drying process (2) is divided into multiple processes, makes drying temperature with follow-up drying process more and more higher.After drying process (2), Chemical treatment process (3) is carried out in chemical treatment area 220.In chemical treatment process (3), such as when dried coated film 20 ' when containing photoactive catalyst, and light irradiation is carried out in lamp (light irradiating means) 221 of the base material about 10 to configure.Or, example Such as when dried coated film 20 ' contains thermal activities catalyst, lamp is replaced using fan heater (heating arrangements), and (light irradiation is filled Put) 221, base material 10 is heated with configuring the fan heater (heating arrangements) 221 below base material 10., can by the crosslinking Treatment To cause the mutual chemical bonding of the above-mentioned crushed material in coated film 20 ', extra-low refractive index layer 20 is formed.
Then, the layered product that porous structure 20 is formed with base material 10 is passed through into volume after chemical treatment process (3) Roller 251 is taken to batch., for example can also be straight on above-mentioned resin film (base material 10) by using above-mentioned resin film as base material 10 Connect stacking extra-low refractive index layer 20.Thereafter, for example other layers can also be laminated on above-mentioned layered product.In addition, by above-mentioned stacking Before body is batched by takers-in 251, for example other layers can also be laminated on above-mentioned layered product.
In addition, representing to be formed the another of the continuous processing process in the method for the extra-low refractive index layer of the present invention in Fig. 4~6 One example.As shown in Fig. 4 sectional view, this method is to form the chemical treatment process of extra-low refractive index layer 20 (such as crosslinking Treatment process) (3) carry out intensity and improve process (aging process) (4) afterwards, in addition with being represented in Fig. 1~3 Method is identical.As shown in Figure 4, in intensity improves process (aging process) (4), the strong of extra-low refractive index layer 20 is made Degree is improved, and the extra-low refractive index layer 21 of intensity raising is made.Intensity improves process (aging process) (4) and is not particularly limited, example As discussed.
Fig. 5 is to represent the painting device of the slit coventry type die head coventry method different from Fig. 2 and used its above-mentioned extra-low refractive index The schematic diagram of another example of the forming method of layer.As illustrated, the painting device is carrying out chemical treatment process (3) Chemical treatment area 120 after and then have carry out intensity improve process (aging process) (4) intensity improve area (aging area) 130, it is identical with Fig. 2 device in addition.That is, improve to enter in area (aging area) 130 in intensity after chemical treatment process (3) Row intensity improves process (aging process) (4), improves bonding peel strength of the extra-low refractive index layer 20 relative to resin film 10, and Form the extra-low refractive index layer 21 that bonding peel strength is improved.Intensity, which improves process (aging process) (4), can also for example pass through Fan heater (heating arrangements) 131 using configuration in base material about 10, in the above described manner enters the heating of extra-low refractive index layer 20 OK.Heating-up temperature, time etc. are not particularly limited, for example as described above.Thereafter, it will be formed in the same manner as Fig. 3 on base material 10 The stacked film for having extra-low refractive index layer 21 is batched by takers-in 105.
Fig. 6 is to represent the painting device of the micro- intagliotype (micro-gravure coating process) different from Fig. 3 and used the above-mentioned of its The schematic diagram of another example of the forming method of porous structure.As illustrated, the painting device is being carried out at chemistry And then have behind the chemical treatment area 220 of science and engineering sequence (3) and carry out the intensity raising area that intensity improves process (aging process) (4) (aging area) 230, it is identical with Fig. 3 device in addition.That is, area's (aging is improved after chemical treatment process (3) in intensity Area) 230 interior progress intensity raising processes (aging process) (4), improve bonding of the extra-low refractive index layer 20 relative to resin film 10 Peel strength, and form the extra-low refractive index layer 21 that bonding peel strength is improved.Intensity improves process (aging process) (4) for example Can also be by using the fan heater (heating arrangements) 231 configured in base material about 10, in the above described manner by extra-low refractive index layer 20 heat to carry out.Heating-up temperature, time etc. are not particularly limited, for example as described above.Thereafter, will be in base in the same manner as Fig. 3 The stacked film that extra-low refractive index layer 21 is formed with material 10 is batched by takers-in 251.
In addition, representing to be formed the another of the continuous processing process in the method for the extra-low refractive index layer of the present invention in Fig. 7~9 One example.As shown in Fig. 7 sectional view, this method is forming the chemical treatment process of extra-low refractive index layer 20 (such as crosslinking Treatment process) (3) are included afterwards：The bonding adhesive linkage of application bonding adhesive linkage 30 is applied on extra-low refractive index layer 20 Fill process (bonding adhesive linkage formation process) (4) and extra-low refractive index layer 20 is reacted with bonding adhesive linkage 30 and is formed centre The intermediate layer formation process (5) of layer 22.In addition, the method for Fig. 7~9 is identical with the method shown in Fig. 4~6.In addition, In the figure 7, intermediate layer formation process (5) doubles as improving the process (intensity raising process) of the intensity of extra-low refractive index layer 20, Extra-low refractive index layer 20 becomes the extra-low refractive index layer 21 for turning to intensity raising to intermediate layer formation process (5) later.But, the present invention It is not limited by this, for example in intermediate layer formation process (5), extra-low refractive index layer 20 can also not change afterwards.Adhesive linkage is bonded to apply Dress process (bonding adhesive linkage formation process) (4) and intermediate layer formation process (5) are not particularly limited, for example as described above.
Fig. 8 is the forming method for the above-mentioned extra-low refractive index layer for representing the painting device of slit coventry type die head coventry method and having used it Again another example schematic diagram.As illustrated, the painting device is carrying out the chemical treatment of chemical treatment process (3) And then there is the bonding adhesive linkage coating area 130a for carrying out bonding adhesive linkage coating process (4), in addition with figure behind area 120 5 device is identical.In the figure, the intermediate layer formation area (aging area) and then configured after bonding adhesive linkage coating area 130a 130 can be carried out improving area's (aging with Fig. 5 intensity by configuring the fan heater (heating arrangements) 131 in base material about 10 Area) 130 same heating.That is, in Fig. 8 device, carry out bonding adhesive linkage application work afterwards in chemical treatment process (3) Sequence (bonding adhesive linkage formation process) (4), i.e. by bonding adhesive linkage applying mechanism in bonding adhesive linkage coating area 130a 131a is coated with (application) adhesive or bonding agent on extra-low refractive index layer 20 and forms bonding adhesive linkage 30.In addition, as above institute State, can also be with the laminating (attaching) of the adhesive tape with bonding adhesive linkage 30 etc., to replace the coating of adhesive or bonding agent (application).And then, intermediate layer formation process (aging process) (5) is carried out in intermediate layer formation area (aging area) 130, is made ultralow Index layer 20 reacts with bonding adhesive linkage 30 and forms intermediate layer 22.In addition, as described above, in the process extra-low refractive index The extra-low refractive index layer 21 that the intensity that layer 20 turns into is improved.Heating-up temperature, time using fan heater (heating arrangements) 131 etc. do not have It is particularly limited to, for example as described above.
Fig. 9 is the painting device for representing micro- intagliotype (micro-gravure coating process) and the above-mentioned porous structure for having used it The schematic diagram of another example again of forming method.As illustrated, the painting device is carrying out chemical treatment process (3) And then be chemically treated has the bonding adhesive linkage coating area 230a for carrying out bonding adhesive linkage coating process (4) behind area 220, except this It is identical with Fig. 6 device in addition.In the figure, the intermediate layer formation area and then configured after bonding adhesive linkage coating area 230a (aging area) 230 by configuring the fan heater (heating arrangements) 231 in base material about 10 can improve with Fig. 6 intensity The same heating in area (aging area) 230.I.e., in the apparatus of fig. 9, bonding bonding is carried out afterwards in chemical treatment process (3) Layer coating process (bonding adhesive linkage formation process) (4), i.e. applied in bonding adhesive linkage coating area 230a by bonding adhesive linkage Mounting mechanism 231a is coated with (application) adhesive or bonding agent on extra-low refractive index layer 20 and forms bonding adhesive linkage 30.In addition, As described above, can also be with the laminating (attaching) of the adhesive tape with bonding adhesive linkage 30 etc., to replace adhesive or bonding agent Coating (application).And then, intermediate layer formation process (aging process) (5) is carried out in intermediate layer formation area (aging area) 230, Extra-low refractive index layer 20 is set to react with bonding adhesive linkage 30 and form intermediate layer 22.In addition, as described above, ultralow in the process The extra-low refractive index layer 21 that the intensity that index layer 20 turns into is improved.Utilize the heating-up temperature of fan heater (heating arrangements) 231, time Etc. being not particularly limited, for example as described above.
[3. optical component]
As described above, the optical component of the present invention is characterised by the extra-low refractive index layer containing the present invention.The present invention's Optical component is characterised by the extra-low refractive index layer containing the present invention, and other compositions are then unrestricted.The light of the present invention Component is learned for example in addition to the extra-low refractive index layer of the invention described above, can also further contain other layers.
In addition, as described above, the optical component of the present invention is characterised by the extra-low refractive index layer containing the invention described above It is used as low reflection layer.The present invention optical component be characterised by containing the present invention low reflection layer, other compositions then not by times What is limited.The optical component of the present invention for example in addition to the extra-low refractive index layer of the invention described above, can also further contain Other layers.The optical component of the present invention is, for example, web-like.
Embodiment
Next, being illustrated for embodiments of the invention.But, the present invention is not limited by following examples.
(embodiment 1)
In the present embodiment, the extra-low refractive index layer of the present invention is manufactured as follows.
(1) gelation of silicon compound
The precursor that silicon compound is dissolved in DMSO 2.2g is MTMS 0.95g.Added in above-mentioned mixed liquor 0.01mol/L oxalic acid aqueous solution 0.5g, makes MTMS hydrolyze and three (hydroxyl) methyl of generation for 30 minutes by being stirred at room temperature Silane.
After ammoniacal liquor 0.38g and pure water 0.2g that 28% concentration is added in DMSO 5.5g, then it is additional insert it is above-mentioned through hydrolysis The above-mentioned mixed liquor of processing, is stirred at room temperature 15 minutes, carries out the gelation of three (hydroxyl) methyl-monosilanes and obtains gel Silicon compound.
(2) maturation process
The above-mentioned mixed liquor handled through gelation is directly cultivated 20 hours at 40 DEG C, maturation process is carried out.
(3) pulverization process
Then, the above-mentioned gel silicon compound through maturation process is ground into of several mm~number cm sizes using scraper It is granular.IPA 40g are added thereto, stand 6 hours after being gently mixed at room temperature, the solvent being decanted off in gel and catalysis Agent.Same decantation processing repeats after 3 times, completes solvent displacement.Then to the above-mentioned gel silicon in above-mentioned mixed liquor Compound carries out pulverization process (high pressure is crushed without medium).Above-mentioned pulverization process (high pressure is crushed without medium) is to use homogenizer (trade name UH-50, SMT company system), in 5cc spiral bottle after weighing gel 1.18g and IPA1.14g, in 50W, 20kHz Under conditions of carry out the crushing of 2 minutes.
The above-mentioned gel silicon compound in above-mentioned mixed liquor is crushed by above-mentioned pulverization process, thus above-mentioned mixed liquor Sol solutionses as above-mentioned crushed material.In terms of dynamic light scattering formula Nanotrac grain size analyses (day machine dress company system, UPA- EX150 types) confirm to represent the uneven volume average particle size of the granularity of above-mentioned crushed material contained in above-mentioned mixed liquor, as a result for 0.50~0.70.And then, prepare the 0.3 weight % KOH aqueous solution, 0.02g KOH is added in above-mentioned sol solutionses 0.5g, adjust Make coating liquid.
(4) form coated film and form organosilicon porous body coiled material
Then, above-mentioned coating liquid is coated on by polyethylene terephthalate (PET) resin film processed (length by stick coating method On surface 100m), coated film is formed.Above-mentioned coating set is the surface of above-mentioned base material per 1mm2For 6 μ L above-mentioned sol solutionses. Above-mentioned coated film is handled 1 minute at 100 DEG C of temperature, in the film forming and above-mentioned precursor that complete the precursor of organosilicon porous body The above-mentioned mutual cross-linking reaction of crushed material, obtains coiled material body in coiling process.Thus, above-mentioned crushing is formed on above-mentioned base material Thing carries out the organosilicon porous body coiled material for 1 μm of thickness being chemically bonded each other.
(5) characteristic of extra-low refractive index layer is confirmed
By above-mentioned method, refractive index, mist degree, intensity, which (pass through, to be confirmed to the porous body being formed on above-mentioned base material The marresistance that Bemcot (registration mark) is obtained), the void size in hole.
(embodiment 2)
In the gelation as the silicon compound precursor MTMS of raw material, it is by condition mitigation：The ammonia of catalyst will be used as The addition of water reduces into 0.09g and is changed into the culture of above-mentioned curing step at 40 DEG C 20 hours and 2 hours at room temperature, except this In addition, organosilicon porous body is formed by method similarly to Example 1 and confirms various characteristics.
(comparative example 1)
In addition to not adding KOH for above-mentioned coating liquid, by forming porous body and true with the same method of comparative example 1 Recognize various characteristics.
These results are shown in table 1 below.
Table 1
Confirm as shown in above-mentioned table 1, the extra-low refractive index layer of the embodiment 1 of 1 μm of the thickness of acquisition is with being compared Example is different, and refractive index is less than 1.3 and is the refractive index equal with air layer.By further carrying out bonding processing, it can press down Scratch when system batches coiled material body is produced, and obtains the good strip film of coiled material outward appearance.In addition, having further acknowledged above-mentioned ultralow refraction Although rate layer further has sufficient intensity and the transparency concurrently with the space produced by loose structure.
(embodiment 3)
In the present embodiment, the extra-low refractive index layer of the present invention is manufactured as follows.
First, above-mentioned " gelation of (1) silicon compound " is carried out in the way of similarly to Example 1 and " at (2) curing Reason ".Then, 1.5 weight % light production base catalyst (Wako Pure Chemical Industries, Ltd. is added in above-mentioned sol particles liquid： Trade name WPBG266) IPA (isopropanol) solution replace the 0.3 weight % KOH aqueous solution, in addition, with embodiment 1 same mode carries out above-mentioned " (3) pulverization process ", modulates coating liquid.It is above-mentioned relative to above-mentioned sol particles liquid 0.75g The addition of the IPA solution of light production base catalyst is set as 0.031g.Thereafter, carried out in the way of similarly to Example 1 above-mentioned " (4) form coated film and form organosilicon porous body coiled material ".To irradiating UV according to dried porous body obtained above.On It is the light that illumination wavelength is 360nm to state UV irradiations, and light irradiation amount (energy) is set as 500mJ.And then, after irradiation UV, At 60 DEG C carry out heat ageing 22hr and formed the present embodiment extra-low refractive index layer (organosilicon porous body coiled material).
(embodiment 4)
In addition to not carrying out heat ageing after irradiation UV, operation similarly to Example 2 is carried out, the present embodiment is formed Extra-low refractive index layer.
(embodiment 5)
After the IPA solution for adding light production base catalyst, and then relative to above-mentioned sol solutionses 0.75g additions 0.018g 5 weights % double (trimethoxy) silane are measured to adjust coating liquid, in addition, operation similarly to Example 2 is carried out, forms this reality Apply the extra-low refractive index layer of example.
(embodiment 6)
Addition relative to the IPA solution that above-mentioned sol solutionses 0.75g produces light base catalyst is set as 0.054g, except this In addition, operation similarly to Example 2 is carried out, the extra-low refractive index layer of the present embodiment is formed.
(embodiment 7)
Dried porous body is irradiated after UV in the way of similarly to Example 2, before heat ageing, at room temperature will After the above-mentioned adhesive side that coated on one side has the PET film of adhesive (bonding adhesive linkage) is attached on above-mentioned porous body, at 60 DEG C Lower heat ageing 22hr.In addition, operation similarly to Example 2 is carried out, the extra-low refractive index layer of the present embodiment is formed.
(embodiment 8)
Except in addition to heat ageing is not carried out after attaching PET film, carrying out operation similarly to Example 6, forming this reality Apply the extra-low refractive index layer of example.
(embodiment 9)
After the IPA solution for adding light production base catalyst, and then relative to above-mentioned sol solutionses 0.75g additions 0.018g 5 weights % double (trimethoxy) silane are measured to adjust coating liquid, in addition, operation similarly to Example 6 is carried out, forms this reality Apply the extra-low refractive index layer of example.
(embodiment 10)
Addition relative to the IPA solution that above-mentioned sol solutionses 0.75g produces light base catalyst is set as 0.054g, except this In addition, operation similarly to Example 6 is carried out, the extra-low refractive index layer of the present embodiment is formed.
For the extra-low refractive index layer of embodiment 3~10, refractive index, bonding peel strength and mist are determined by the above method Degree, and measurement result is shown in table 2 below and 3.But, in the bonding peel strength of embodiment 7~10 is determined, due to this A little stacking film coiled materials are the states for being fitted with PET film and adhesive layer, so eliminating the patch of PET film and acryloid cement It is attached.
Table 2
Table 3
As shown in above-mentioned table 2 and 3, the refraction of the extra-low refractive index layer of the embodiment 3~10 of 1 μm of obtained thickness Rate is extremely low and is 1.14~1.16.Further, since the haze value of these extra-low refractive index layer displays that 0.4 so extremely low number Value, so confirming that the transparency is also high.And then, the extra-low refractive index layer of embodiment 3~10 is due to bonding peel strength height, institute To confirm that coiled material body is made also with the high intensity for being difficult the other layers of stripping from stacking film coiled material even if batching.And then, Also the excellent scratch resistance of the extra-low refractive index layer of embodiment 3~10, pole not subject to damage are confirmed.In addition, embodiment 3~10 It is also unconfirmed to change due to carrying out visually observation after coating liquid is preserved 1 week, so also confirming the preservation of coating liquid Stability is also excellent, can efficiently manufacture the stacking film coiled material of stable quality.
Industrial applicability
As described above, extra-low refractive index layer of the invention is by showing characteristic as described above, so as to Easily realize the low-refraction for the substitute that can for example turn into air layer.Therefore, pass through without in order to obtain low-refraction Multiple components are configured at a certain distance to set air layer, by the way that the extra-low refractive index layer of the present invention was configured in the phase The position of prestige, can assign low refractiveness.Therefore, extra-low refractive index of the invention layer is for example for needing the optics of low-refraction Component etc. is useful.
Symbol description
10 base materials
20 extra-low refractive index layer
20 ' coated films (precursor layer)
20 " sol particles liquid
The extra-low refractive index layer that 21 intensity are improved
101 outlet rollers
102 coating rollers
110 baking oven areas
111 fan heaters (heating arrangements)
120 chemical treatment areas
121 lamps (light irradiating means) or fan heater (heating arrangements)
130a bonding adhesive linkages coating area
130 intermediates formation area
131a bonds adhesive linkage applying mechanism
131 fan heaters (heating arrangements)
105 takers-ins
106 rollers
201 outlet rollers
202 reservoirs
203 scrapers (doctor knife)
204 nicks version
210 baking oven areas
211 heating arrangements
220 chemical treatment areas
221 lamps (light irradiating means) or fan heater (heating arrangements)
230a bonding adhesive linkages coating area
230 intermediates formation area
231a bonds adhesive linkage applying mechanism
231 fan heaters (heating arrangements)
251 takers-ins

Claims (31)

1. a kind of stacking film coiled material of strip, it is characterised in that it is that refractive index is folded on resin film upper strata is less than 1.20 Extra-low refractive index layer.
2. stacking film coiled material according to claim 1, wherein, for extra-low refractive index layer, represent the logical of film-strength It is 60~100% to cross the marresistance that Bemcot obtains, and the Bemcot is registration mark, represents being tried by MIT for pliability It is more than 100 times to test obtained folding number.
3. stacking film coiled material according to claim 1 or 2, wherein, in extra-low refractive index layer, form fine voids One or more Component units of structure are chemically bonded each other.
4. stacking film coiled material according to claim 3, wherein, the Component units contain Direct Bonding each other.
5. the stacking film coiled material according to claim 3 or 4, wherein, the Component units contain indirect linkage each other.
6. the stacking film coiled material according to any one of claim 3~5, wherein, the mutual bonding of Component units contains There are hydrogen bond or covalent bond.
7. the stacking film coiled material according to any one of claim 3~6, wherein, the Component units are to select free particle The Component units of at least one of the group that shape, threadiness and tabular are constituted shape.
8. stacking film coiled material according to claim 7, wherein, the particle shape and flat Component units are by inorganic matter Constitute.
9. the stacking film coiled material according to claim 7 or 8, wherein, the constitution element of the particle shape Component units contains Selected from by least one of Si, Mg, Al, Ti, Zn and Zr group constituted element.
10. the stacking film coiled material according to any one of claim 3~9, wherein, the extra-low refractive index layer further contains Have for making one or more Component units of the formation fine voids structure carry out the crosslinking auxiliary of indirect linkage each other.
11. stacking film coiled material according to claim 10, wherein, relative to the formation fine voids structure one kind or The weight of a variety of Component units, the containing ratio of the crosslinking auxiliary is 0.01~20 weight %.
12. the stacking film coiled material according to any one of claim 1~11, wherein, the extra-low refractive index layer be containing The porous body of micropore particle.
13. the stacking film coiled material according to any one of claim 1~12, wherein, the void size in hole is 2~200nm.
14. the stacking film coiled material according to any one of claim 1~13, wherein, the space of the extra-low refractive index layer Rate is more than 40%.
15. the stacking film coiled material according to any one of claim 1~14, wherein, the thickness of the extra-low refractive index layer For 0.01~100 μm.
16. the stacking film coiled material according to any one of claim 1~15, wherein, the expression of the extra-low refractive index layer The mist degree of the transparency is less than 5%.
17. the stacking film coiled material of the strip according to any one of claim 1~16, wherein, the extra-low refractive index Acid of the layer containing the effect that the intensity for improving the extra-low refractive index layer is played by least one of light irradiation and heating Or alkali.
18. the manufacture method of the stacking film coiled material of a kind of strip, it is characterised in that it is to fold refractive index on resin film upper strata to be The manufacture method of the stacking film coiled material of the strip of less than 1.20 extra-low refractive index layer, it includes following processes：
The process for making the liquid containing the one or more Component units for forming fine voids structure；
The liquid is painted on to the process on resin film；And
The process that the liquid of institute's application is dried.
19. the manufacture method of stacking film coiled material according to claim 18, wherein, make one or more Component units It is chemically bonded each other and forms the extra-low refractive index layer.
20. the manufacture method of the stacking film coiled material according to claim 18 or 19, wherein, in the process of the making liquid In be further contained in the process that the catalyst for making the Component units be chemically bonded each other is added in the liquid.
21. the manufacture method of stacking film coiled material according to claim 20, wherein, the catalyst is to promote described constitute The catalyst of the mutual crosslinking bonding of unit.
22. the manufacture method of the stacking film coiled material according to any one of claim 18~21, wherein, make the composition single Member is bonded and forms the extra-low refractive index layer directly with one another.
23. the manufacture method of the stacking film coiled material according to any one of claim 18~22, wherein, make the composition single Member each other indirect linkage and form extra-low refractive index layer.
24. the manufacture method of stacking film coiled material according to claim 23, wherein, it is further contained in the liquid and adds Plus for making the process of the Component units crosslinking auxiliary of indirect linkage each other.
25. the manufacture method of stacking film coiled material according to claim 24, wherein, relative to the weight of the Component units Amount, the addition of the crosslinking auxiliary is 0.01~20 weight %.
26. the manufacture method of the stacking film coiled material according to any one of claim 18~25, wherein, constituted according to described Mutual mode of the bonding containing hydrogen bond or covalent bond of unit forms the extra-low refractive index layer.
27. the manufacture method of the stacking film coiled material according to any one of claim 18~26, wherein, the Component units It is the Component units selected from least one of the group being made up of particle shape, threadiness and tabular shape.
28. the manufacture method of stacking film coiled material according to claim 27, wherein, the particle shape and flat composition Unit is made up of inorganic matter.
29. the manufacture method of the stacking film coiled material according to claim 27 or 28, wherein, the particle shape Component units Constitution element contains selected from by least one of Si, Mg, Al, Ti, Zn and Zr group constituted element.
30. the manufacture method of the stacking film coiled material according to any one of claim 18~29, wherein, the Component units For micropore particle.
31. a kind of optical component, it is characterised in that containing in the stacking film coiled material any one of claim 1~17 Extra-low refractive index layer.
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