CN105636781B - Thermal isolation film and its manufacture method - Google Patents
Thermal isolation film and its manufacture method Download PDFInfo
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- CN105636781B CN105636781B CN201480056121.6A CN201480056121A CN105636781B CN 105636781 B CN105636781 B CN 105636781B CN 201480056121 A CN201480056121 A CN 201480056121A CN 105636781 B CN105636781 B CN 105636781B
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- 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
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- 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
- B32B27/065—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 of foam
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- 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
- B32B27/08—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 of synthetic resin
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/022—Foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/026—Porous
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- B32B2607/00—Walls, panels
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
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- 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
- C08J2207/00—Foams characterised by their intended use
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- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
The problem of the present invention, which is to provide, a kind of has high thermal insulation and the thermal isolation film and its manufacture method of high transparency concurrently.The thermal isolation film of the present invention is with plastic foil and forms the polymeric layer with loose structure on the plastic foil.The manufacture method of the thermal isolation film of the present invention includes：(1) process for forming block copolymer layer on the plastic film, (2) process that micro phase separation structure is formed on the block copolymer layer, (3) part or all by a polymer phase of the block copolymer layer for foring micro phase separation structure removes, so as to form the process of the polymeric layer with loose structure.
Description
Technical field
The present invention relates to thermal isolation film and its manufacture method.
Background technology
All the time, in building field, automotive field etc., from reduction air-conditioning expense (energy-conservation) and ensure to include preventing from tying
From the viewpoint of living space comfortableness including dew etc., various methods are employed to effectively obtain thermal insulation.
However, for the position for requiring visual as window-glass, house is with the heat-insulated material used in wallpaper
Expect that normally transparent is relatively low, can not be used from the viewpoint of visuality.Therefore, as heat-insulated between window-glass inside and outside
Means, laminated glass, compound glass etc. are developed, but they are costly, in order to set these glass in slide window etc., need
Window frame construction is carried out, further increases cost.
In addition, as the method that enters of the hot-fluid from window is improved, the guarantor of metal film also by film forming on the plastic film
Cuticula is pasted onto the method on window, for this method, enters although can suppress hot-fluid, and the effect gone out to suppression hot-fluid is not
Foot.
Patent Document 1 discloses one kind to paste window, and it is at least made up of two panels resin film, and with two panels
The pad of air layer is formed between resin film, the patch window is to be pointed to the one side reality than the resin film of air layer more indoor
The insulation resin film of far infrared reflectance coating is applied.
Hollow silica nano-particle is used as heat-barrier material to have heat-insulated Patent Document 2 discloses one kind
Property and the transparency thermal isolation film.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-138659 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-102401 publications
The content of the invention
The invention problem to be solved
However, for the thermal isolation film of patent document 1,2, thermal insulation can not fully be had both by existing asks with transparent
Topic.
In view of the above problems, problem of the invention is to provide a kind of higher thermal insulation and higher transparent of having concurrently
Thermal isolation film and its manufacture method.
The method for solving problem
The result that the present inventor etc. have made intensive studies to solve above-mentioned problem is found, by setting on the plastic film
Put the low thermal conductivity block copolymer layer with loose structure, can obtain have concurrently higher thermal insulation and compared with high transparency every
Hotting mask, so as to complete the present invention.
That is, the present invention provides following [1]~[9].
[1] a kind of thermal isolation film, it has：Plastic foil and the gathering with loose structure formed on the plastic foil
Compound layer.
[2] thermal isolation film described in above-mentioned [1], wherein, the loose structure is derived from the microphase-separated knot of block copolymer
Structure and formed.
[3] thermal isolation film described in above-mentioned [1], wherein, the loose structure is micropore, and the average pore size of the micropore is 5
~1000nm.
[4] thermal isolation film described in above-mentioned [1], wherein, the thermal conductivity factor of thermal isolation film is below 0.1W/mK.
[5] thermal isolation film described in above-mentioned [2], wherein, the block copolymer forms the knot that is separated by self-organization
Structure, and be that any of A-B types, A-B-A types and the B-A-B types being made up of mutual exclusive unit (A) and unit (B) is embedding
Section copolymer, wherein, the unit (A) and the unit (B) be respectively be selected from styrenic polymer, poly- (methyl) acrylate,
At least one of polyvinylpyridine derivative, conjugated diolefine polymer, polyolefin.
[6] thermal isolation film described in above-mentioned [1], it also has adhesive phase.
[7] thermal isolation film described in above-mentioned [1], the thermal isolation film are used as window with film.
[8] a kind of manufacture method of thermal isolation film, it is the manufacture method of the thermal isolation film described in above-mentioned [1], and this method includes：
(1) process for forming block copolymer layer on the plastic film,
(2) process that micro phase separation structure is formed on the block copolymer layer,
(3) part or all by a polymer phase of the block copolymer layer for foring micro phase separation structure is removed
Go, so as to form the process of the polymeric layer with loose structure.
[9] manufacture method of the thermal isolation film described in above-mentioned [8], wherein, the loose structure is micropore, and the micropore is flat
Equal aperture is 5~1000nm.
The effect of invention
According to the present invention, the micro- of the self-assem bed formation by block copolymer (BCP) is utilized by being formed on the plastic film
Phase separation structure and with loose structure polymeric layer, using the teaching of the invention it is possible to provide it is a kind of have concurrently higher thermal insulation and compared with high transparency every
Hotting mask.
Brief description of the drawings
Fig. 1 is the profile for an example for showing the thermal isolation film of the present invention.
Fig. 2 is for determining the temperature difference by the thermal isolation film of the present invention when adhesive phase is pasted on the glass substrate
The explanation figure of composition.
Fig. 3 is AFM photo (a) (measure of the block copolymer layer obtained in embodiments of the invention 1 after microphase-separated
Scope：11 μm of μ m) and ultraviolet-ozone processing after AFM photos (b) (measurement range：1μm×1μm).
Fig. 4 is AFM photo (a) (measure of the block copolymer layer obtained in embodiments of the invention 2 after microphase-separated
Scope：11 μm of μ m) and oxygen plasma etch after AFM photo (measurement ranges：1μm×1μm).
Fig. 5 is to show in embodiments of the invention 3 after microphase-separated the micropore obtained from the etching of ultraviolet irradiation
The SEM photograph (1 μm of 1 μ m of measurement range) on surface.
Symbol description
1：Thermal isolation film
2：Plastic foil
3a：Block copolymer layer
3b：Block copolymer layer with micro phase separation structure
3c：Polymeric layer with loose structure
4：Adhesive phase
5：Glass substrate
6：With the heat-insulated film surface of atmosphere
7：With the glass substrate face of atmosphere
Embodiment
[thermal isolation film]
The thermal isolation film of the present invention is to form the thermal isolation film of the polymeric layer with loose structure on the plastic film.
Fig. 1 is an example of the profile for showing the thermal isolation film of the present invention.As shown in figure 1, the feature of thermal isolation film 1 exists
In foring the polymeric layer 3c with loose structure on plastic foil 2.Here, " loose structure " refers to, has such as nanometer
The very fine emptying aperture of size, and according to given shape, interval, arrangement forms the fine emptying aperture independently of each other
Structure.By forming the loose structure for the micro phase separation structure for being derived from the block copolymer described below, energy on the plastic film
Enough obtain has higher thermal insulation and the thermal isolation film compared with high transparency concurrently.
＜ plastic foils ＞
As the resin for forming plastic foil, can enumerate：Thermosetting resin, thermoplastic resin, light-cured resin etc..Can
To enumerate for example：The polyolefin resins such as polyethylene, polypropylene；The styrene resins such as polystyrene；Poly-methyl methacrylate
The acrylic resins such as ester；Polyamide (nylon 6, nylon66 fiber etc.), poly, poly- paraphenylene terephthalamide are to benzene
The acid amides resinoid such as diamines；Polyethylene terephthalate, polybutylene terephthalate (PBT), poly- naphthalenedicarboxylic acid ethylene glycol
The polyester resins such as ester, polyarylate；Norbornene polymer, monocyclic cyclic olefin polymer, cyclic conjugated diene class
The cycloolefin polymers such as polymer, vinyl alicyclic hydrocarbon polymer and their hydride；Vinyl chloride；Polyimides；It is poly-
Amide imide；Polyphenylene oxide；Polyether-ketone；Polyether-ether-ketone；Makrolon；The polysulfones resinoid such as polysulfones, polyether sulfone；Polyphenylene sulfide；
And these two or more high molecular combinations；Etc..Wherein, from versatility and the transparency it is excellent from the viewpoint of, it is excellent
Select the polyesters such as polyethylene terephthalate, polybutylene terephthalate (PBT), PEN, polyarylate
Resin.
＜ block copolymers ＞
As block copolymer, as long as by self-assem bed formation micro phase separation structure and by mutually mutual exclusive list
First (A) is bonded with unit (B) to be formed, and is not particularly limited.Block copolymer can enumerate A-B types, A-B-A types, B-A-B
The block copolymers such as type.In addition, block copolymer can also be A-B-C types containing other units, for example containing unit (C),
A-B-C-A types etc..Wherein, the difficulty from phase separation, from the viewpoint of the difficulty of micropore control, preferably A-B types, A-B-A
The block copolymer of the block copolymer of type, B-A-B types, more preferably A-B types.
As unit (A) and unit (B), can enumerate：It is styrene, poly- o-methyl styrene, poly- p-methylstyrene, poly-
The styrenic polymers such as propylstyrene, polymethoxy styrene and their derivative；Poly- (methyl) methyl acrylate, gather
(methyl) ethyl acrylate, poly- (methyl) tert-butyl acrylate, poly- (methyl) cyclohexyl acrylate, poly- (methyl) acrylic acid benzyl
Ester, the polymethyl containing polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane)
Poly- (methyl) acrylate such as acid esters and their derivative；The polyvinylpyridine such as polyvinylpyridine and their derivative
Derivative；Polyisoprene, polybutadiene, polyprene, poly- hexadiene, dicyclopentadiene, polycyclohexadiene, polycyclic heptan two
Alkene, polycyclic octadiene and their derivative equiconjugate diolefinic polymer；The polyolefin such as polyethylene；Etc..
As the specific example of block copolymer, can enumerate：Polystyrene-polyisoprene (PS-b-PI), polyphenyl second
Alkene-polybutadiene (PS-b-PBD), polystyrene-polyisoprene-polybutadienes-polystyrene (SIBS resins), polyethylene
Yl pyridines-polybutadiene (PVP-b-PBD), polyvinylpyridine-polyisoprene (PVP-b-PI), poly-methyl methacrylate
Ester-polyisoprene (PMMA-b-PI), polymethyl methacrylate-polystyrene (PMMA-b-PS), poly-methyl methacrylate
Ester-polybutadiene (PMMA-b-PB), polymethyl methacrylate-polymethyl containing polyhedral oligomeric silsesquioxane
Acid esters (PMMA-b-PMAPOSS) etc..Wherein, from heat resistance, weatherability, thermal conductivity factor, the difficulty being separated, micropore control
Difficulty from the viewpoint of, preferably polystyrene-polyisoprene (PS-b-PI), polymethyl methacrylate-polystyrene
(PMMA-b-PS), polymethyl methacrylate-polymethacrylates (PMMA-b- containing polyhedral oligomeric silsesquioxane
PMAPOSS), more preferably polymethyl methacrylate-polyisoprene (PMMA-b-PI).
It should be noted that above-mentioned block copolymer can use the product that polymerization obtains, commercially available product can also be used.It is poly-
Conjunction method is not particularly limited, and known method can be used, for example, can be by using work of the s-butyl lithium as initiator
Property anionic polymerisation is synthesized into.
Preferably comprise the glass of at least one of said units (A) and unit (B) of above-mentioned block copolymer by polymer
Change the monomer that transition temperature is preferably more than 50 DEG C, more preferably more than 80 DEG C, more preferably more than 90 DEG C to form.Glass
The upper limit for changing transition temperature is not particularly limited, usually less than 200 DEG C.Glass transition temperature is heat-resisting in above range
Property is excellent, can be preferably used as thermal isolation film.Glass transition temperature can use means of differential scanning calorimetry measure device (DSC) to carry out
Measure.
＜ has the polymeric layer ＞ of loose structure
Polymeric layer with loose structure can be formed micro- by using the self-organization of above-mentioned block copolymer
Phase separation structure obtains.
For block copolymer, in the feelings that different blocks is not mutually mixed and is separated
Under condition, the domain structure with the feature to graded is taken.Micro phase separation structure is referred to as, for example, taking composition block
The two kinds of polymer of copolymer is with the size of molecular chain length degree, the structure that i.e. the tens nanometer order of magnitude is separated.
Above-mentioned micro phase separation structure changes according to the composition of above-mentioned block copolymer, can be categorized as layer structure, circle
Rod structure, spherical structure, helical structure etc..More specifically, micro phase separation structure according to form block copolymer monomeric species,
Combinations thereof, volume fraction and used in film forming be used for dissolve variety classes polymer solvent species without
Together.In above-mentioned various micro phase separation structures, the block copolymer that the present invention uses is formd for example by conjugated diene Type of Collective
Cylinder (cylinder) structure (phase) that thing unit is formed is present in the matrix (phase) being made up of styrenic polymer unit so
The micro phase separation structure with cylindrical structure.
Specifically, the polymeric layer with loose structure can be formed in the following manner：The shape on above-mentioned plastic foil
Into block copolymer layer, the block copolymer layer is brought it about into microfacies point for example, by being annealed in solvent atmosphere
From, and part or all by a polymer phase of the block copolymer layer after microphase-separated removes.
Above-mentioned loose structure preferably has the micropore that average pore size is 5~1000nm, more preferably 10~300nm, enters one
Step is preferably 30~150nm.Average pore size can obtain thermal insulation and transparent excellent thermal isolation film in above range.
Here, average pore size is the value calculated in the following way：With the table of AFM (AFM) observation block copolymer layer
Face, the output image (measurement range of image procossing is being carried out to observation result：11 μm of μ m) on select 50 micropores at random,
The maximum diameter in the aperture of each micropore, most path are read, the central value in each aperture in independent hole is obtained, then, to measure
All data carry out arithmetic average.
The shape of micropore is not particularly limited, and can enumerate for example：The columns such as cylindric, prism-shaped；Inverted cone, inverted pyramid
Deng inverted cone shape；The back taper mesa-shaped such as chamfered edge platform, inverted round stage；The combination of channel form etc. or these shapes.
In addition, the thickness of block copolymer layer is preferably 0.01~500 μm, it is more preferably 0.01~100 μm, further excellent
Elect 0.02~10 μm as.Thickness can obtain thermal insulation and transparent excellent thermal isolation film in the scope.
The present invention thermal isolation film thermal conductivity factor be preferably 0.1 (W/mK) below, more preferably 0.07 (W/mK) with
Under, particularly preferably 0.05 (W/mK) is below.Thermal conductivity factor can obtain high thermal insulation in the scope.
The mist degree of the thermal isolation film of the present invention is preferably less than 2%, and mist degree is more preferably less than 1.5%.Mist degree is in the scope
When, high transparency can be kept.
＜ adhesive phases ＞
The thermal isolation film of the present invention preferably also has adhesive phase.Using the adhesive phase, such as can be easy by thermal isolation film
Ground is pasted onto on window-glass etc..
As the adhesive for forming adhesive phase, it is not particularly limited, can enumerates for example：Acrylic adhesives, rubber
Glue class adhesive, polyurethane binding, polysiloxane-based adhesive etc..
Specifically, can as shown in Figure 1, in above-mentioned plastic foil 2 with foring with above-mentioned loose structure
Adhesive phase 4 is formed on the face of the polymeric layer 3c opposite side in face, can also foring with above-mentioned more in above-mentioned plastic foil 2
Adhesive phase 4 is formed on the polymeric layer 3c of pore structure face.
In above-mentioned adhesive, it is contemplated that thermal insulation, heat resistance, environment resistant, cost aspect, the transparency, more preferably third
Alkene acrylic binder.
It should be noted that above-mentioned adhesive may be used alone, can also be used in combination it is two or more.
Within the scope without prejudice to the object of the present invention, such as tackifier, plasticizer, light can be added in above-mentioned adhesive to gather
Other compositions such as conjunction property compound, light trigger, foaming agent, polymerization inhibitor, age resistor, filler, coupling agent, antistatic agent.
The thickness of adhesive phase is preferably 1~200 μm, more preferably 10~100 μm.The thickness of adhesive phase is in the scope
When, it can be ensured that with the dhering strength of glass material etc. and not damaging thermal insulation, the transparency.
The thermal isolation film of the present invention, which is pasted onto in building field, automotive field etc. on window-glass etc., to be used, thus, it is possible to
Realize and cut down air-conditioning expense, while indoor or in-car condensation etc. can be suppressed, the comfortableness of living space can be improved.
[manufacture method of thermal isolation film]
The present invention thermal isolation film manufacture method be form on the plastic film the polymeric layer with loose structure every
The manufacture method of hotting mask, this method include：
(1) process for forming block copolymer layer on the plastic film,
(2) process that micro phase separation structure is formed on the block copolymer layer,
(3) part or all by a polymer phase of the block copolymer layer for foring the micro phase separation structure is removed
Go, the process for forming the polymeric layer with loose structure.
The manufacture method of the present invention is illustrated with Fig. 1.
(1) block copolymer layer formation process
Block copolymer layer formation process is by above-mentioned block copolymer, is for example dissolved in the block copolymer of organic solvent
Solution coating is in the process on Fig. 1 plastic foil 2, forming block copolymer layer 3a.As the forming method of block copolymer layer,
Be able to will be made with known method above-mentioned block copolymer be dissolved in organic solvent obtained from solution coating on the plastic film, root
According to needing to be dried, so as to form block copolymer layer.As thickness desired by coating, such as preferred thickness of the present invention
0.01~500 μm of scope coating method, can enumerate for example：Spin coating, roller coat, dip-coating, die coating, gravure coating etc., do not have
There is special limitation.It should be noted that Zone Full is formed uniformly the block copolymer of tens of nm orders of magnitude in real estate
In the case of layer, particularly preferably it is coated with using spin coating, die coating, gravure.
From obtaining from the viewpoint of there is the micro phase separation structure of cylindrical structure, as the dissolving block used in the present invention
The solvent of copolymer, it can enumerate：Cyclopentanone, toluene, ethyl acetate, chloroform, THF, benzene, cyclohexanone, particularly from evaporation speed
From the viewpoint of degree, preferred cyclopentanone.
In addition, from the viewpoint of the block copolymer layer of the tens of nm orders of magnitude of thickness is formed uniformly, above-mentioned block is total to
The concentration of block copolymer in copolymer solution is preferably 0.1~10 mass %, more preferably 0.2~5 mass %.
(2) micro phase separation structure formation process
Micro phase separation structure formation process is the block copolymer layer 3a obtained in above-mentioned block copolymer layer formation process
The upper process for forming micro phase separation structure 3b.As the method for forming micro phase separation structure, it is not particularly limited, preferably by block
Copolymer layer keeps the method (solvent anneal method) of certain time under solvent vapour atmosphere.By using solvent anneal method, hold
The self-organization of block copolymer is carried out easily on film thickness direction, so as to be effectively formed on block copolymer layer to depth
The micro phase separation structure that degree, average diameter and shape etc. are controlled., can be with as the solvent used in above-mentioned solvent anneal
Enumerate for example：Toluene, the mixed solvent of toluene and hexane, carbon disulfide, benzene, THF etc.., can be by appropriate in the process
Selection or adjustment solvent species, annealing conditions form desired micro phase separation structure.
(3) loose structure formation process
Loose structure formation process is to form microphase-separated knot by what is obtained in above-mentioned micro phase separation structure formation process
Part or all of removing of one polymer phase of the block copolymer layer of structure, so as to form the polymer with loose structure
Layer 3b process.
Part or all of method removed of one phase of block copolymer layer is not particularly limited, example can be enumerated
Such as：Handled by ozone, the method that the processing of UV ozone, oxygen plasma processing, ultraviolet treatment with irradiation etc. are etched.At this
In process, by engraving method and etching condition suitably select or adjust, desired loose structure can be formed.And then
It is preferred that cleaned and rinsed to remove wall and etch residue by etching the loose structure formed.As cleaning fluid,
It can suitably be selected, can be enumerated for example according to plastic substrate material, etch residue：Hexane, acetic acid, alcohols (methanol, IPA
Deng) etc..
Above-mentioned loose structure is micropore, and the average pore size of the micropore is 5~1000nm.Average pore size is in above range
When, thermal insulation and transparent excellent thermal isolation film can be obtained.
Manufacturing method according to the invention, it can obtain that there is high thermal insulation and the thermal isolation film of high transparency.
Embodiment
Then, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these examples.
The measure of the thermal conductivity factor of the block copolymer layer of the thermal isolation film obtained in embodiment and comparative example, using thermal isolation film
The thermal insulation evaluation of the thermal insulation sample for evaluation of making is implemented in accordance with the following methods.
(a) Measured Results of Thermal Conductivity
For the polymeric layer of the thermal isolation film obtained in embodiment and comparative example, using 3 ω methods (with reference to Japanese Unexamined Patent Publication
2013-183088 specifications [0034] section etc.) calculate thermal conductivity factor.
(b) thermal insulation is evaluated
As shown in Fig. 2 by the (thickness of adhesive phase 4：20 μm) thermal isolation film 1 made in embodiment and comparative example is stacked on,
And it is pasted onto (the thickness of glass substrate 5：700 μm) on, make thermal insulation sample for evaluation.Then, will be connect with hot plate with air
The tactile side of heat-insulated film surface 6 is heated and is held in 100 DEG C, the temperature of the side of glass substrate face 7 of measure and atmosphere after 1h
Degree.
(c) mist degree determines
According to the standards of JIS K 7136, using haze meter, (electricity Se Industrial Co., Ltd of Japan system makes, ProductName " NDH-
2000 ") haze value of the thermal isolation film obtained in embodiment and comparative example is determined.
(embodiment 1)
As block copolymer, by polystyrene units (molecular weight 72000) and polyisoprene units, (molecular weight is
13000) block copolymer (Polymer source companies manufacture, P4014-PIp) that bonding forms is dissolved in cyclopentanone (Tokyo
Chemical conversion industry Co., Ltd. manufactures), it is prepared for the mass % of solution concentration 1 solution.The solution coating of preparation is existed with spin-coating method
Polyethylene terephthalate film (thickness：100 μm) on, formation thickness 150nm block copolymer layer.Then, using first
The volume % of benzene hexane=70/30 solution, the solvent anneal processing of 30 minutes is carried out under solvent vapour atmosphere, thus embedding
Micro phase separation structure is formd on section copolymer layer.The surface of the block copolymer layer with micro phase separation structure is entered with AFM
Observation is gone.Fig. 3 (a) shows AFM photo (measurement ranges：1μm×1μm).
Then, carried out 30 seconds using ozone irradiation unit (Samco companies manufacture, UV-Ozone dry stripper)
UV ozone irradiates, and carries out selective etch to a part for the isoprene unit of block copolymer layer, is cleaned with hexane solvent,
The polymeric layer with the loose structure being made up of micropore is obtained, has thus made thermal isolation film.With AFM to obtained thermal isolation film
Observed on the surface of polymeric layer.Fig. 3 (b) shows AFM photo (measurement ranges：1μm×1μm).
In the opposite side in the face with foring the polymeric layer with above-mentioned loose structure of the plastic foil of obtained thermal isolation film
The adhesive phase (thickness that is formed by acrylic adhesives of face superimposed layer：20 μm), make heat-insulated with adhesive phase
Film.
By the average pore size of the micropore of the polymeric layer of thermal isolation film, thermal conductivity factor, the haze value of thermal isolation film and with bonding
The thermal insulation evaluation result (temperature of glass substrate) of the thermal isolation film of oxidant layer is shown in table 1.
(embodiment 2)
As block copolymer, by polymethyl methacrylate unit and the poly- first containing polyhedral oligomeric silsesquioxane
Block copolymer (wound and the manufacture of science Co., Ltd., the trade name P9701- that the bonding of base acrylic ester unit forms
MMAPOSSMA) it is dissolved in cyclopentanone (Tokyo HuaCheng Industry Co., Ltd's manufacture), is prepared for the mass %'s of solution concentration 0.5
Solution.With spin-coating method by the solution coating of preparation in polyethylene terephthalate film (thickness：100 μm) on, form thickness
30nm block copolymer layer.Then, carried out using carbon disulfide solvent, under solvent vapour atmosphere at 20 minutes solvent anneals
Reason, thus forms micro phase separation structure on block copolymer layer.With AFM to the block copolymer with micro phase separation structure
Observed on the surface of layer.Fig. 4 (a) shows AFM photo (measurement ranges：1μm×1μm).
Then, using reactive ion etching device (Samco companies manufacture, UV-Ozone dry stripper), defeated
Go out under conditions of power 100W, vacuum pressure 5Pa, oxygen flow 10ccm and carry out 10 seconds oxygen plasma etch, to block copolymerization
A part for the polymethyl methacrylate unit of nitride layer carries out selective etch, is cleaned with hexane solvent, obtains having by micro-
The polymeric layer for the loose structure that hole is formed, has thus made thermal isolation film.With AFM to the polymer layer surface of obtained thermal isolation film
Observed.Fig. 4 (b) shows AFM photo (measurement ranges：1μm×1μm).
In the opposite side in the face with foring the polymeric layer with above-mentioned loose structure of the plastic foil of obtained thermal isolation film
The adhesive phase (thickness that is formed by acrylic adhesives of face superimposed layer：20 μm), make heat-insulated with adhesive phase
Film.
By the average pore size of the micropore of the polymeric layer of thermal isolation film, thermal conductivity factor, the haze value of thermal isolation film and with bonding
The thermal insulation evaluation result (temperature of glass substrate) of the thermal isolation film of oxidant layer is shown in table 1.
(embodiment 3)
As block copolymer, polymethyl methacrylate unit (PMMA units) is bonded with polystyrene units and formed
Block copolymer (wound and science Co., Ltd. manufacture, P2400-SMMA) be dissolved in toluene, be prepared for the matter of solution concentration 1
Measure % solution.With spin-coating method by the solution coating of preparation in polyethylene terephthalate film (thickness：100 μm) on, shape
Into thickness 150nm block copolymer layer.Then, 10 points are carried out with more than glass transition temperature 120 DEG C on hot plate
Clock is heat-treated, and micro phase separation structure is formd on block copolymer layer.
Then, by block copolymer layer with illumination 10mW/cm22 minutes ultraviolet lights are irradiated, to block copolymer layer
A part for PMMA units carries out selective etch, is cleaned with acetic acid solvent, obtains with the loose structure being made up of micropore
Polymeric layer, thermal isolation film is thus made.The surface of the polymeric layer of obtained thermal isolation film is observed with SEM.Fig. 5 shows
SEM photograph (measurement range is gone out：1μm×1μm).
In the opposite side in the face with foring the polymeric layer with above-mentioned loose structure of the plastic foil of obtained thermal isolation film
The adhesive phase (thickness that is formed by acrylic adhesives of face superimposed layer：20 μm), make heat-insulated with adhesive phase
Film.
By the average pore size of the micropore of the polymeric layer of thermal isolation film, thermal conductivity factor, the haze value of thermal isolation film and with bonding
The thermal insulation evaluation result (temperature of glass substrate) of the thermal isolation film of oxidant layer is shown in table 1.
(comparative example 1)
In addition to only forming block copolymer layer in embodiment 1 and not forming loose structure, similarly to Example 1
Thermal isolation film is made.In the face with foring the block copolymer layer for not having loose structure of the plastic foil of obtained thermal isolation film
Opposite side the adhesive phase (thickness that is made up of acrylic adhesives of face superimposed layer：20 μm), make and carried adhesive
The comparison thermal isolation film of layer.
By the thermal conductivity factor of the block copolymer layer of the thermal isolation film compared, the thermal isolation film compared haze value and carry
The comparison of adhesive phase is shown in table 1 with the thermal insulation evaluation result (temperature of glass substrate) of thermal isolation film.
For embodiment 1~3, compared with comparative example 1, thermal conductivity factor is low, from pasting on the glass substrate heat-insulated
The temperature in the face of film side and the temperature in the face of glass substrate side are understood, can be raised temperature and be controlled very low.In addition we know,
Haze value is substantially achieved holding, and the transparency is high.
[table 1]
Industrial applicibility
The present invention thermal isolation film excellent in heat insulating performance and there is high transparency, it can thus be assumed that building field, automobile neck
Window thermal isolation film can be applied in domain etc..
Claims (7)
1. a kind of thermal isolation film, it has：
Plastic foil and
The polymeric layer with loose structure on the plastic foil is formed,
Wherein, the loose structure is derived from the micro phase separation structure of block copolymer and formed,
The block copolymer forms phase separation structure by self-organization, and is by mutual exclusive unit A and unit B
Any of A-B types, A-B-A types and the B-A-B types of composition block copolymer, wherein, unit A and the unit B are respectively
Selected from styrenic polymer, poly- (methyl) acrylate, polyvinylpyridine derivative, conjugated diolefine polymer, polyene
At least one of hydrocarbon.
2. thermal isolation film according to claim 1, wherein, the loose structure is micropore, and the average pore size of the micropore is 5
~1000nm.
3. thermal isolation film according to claim 1, wherein, the thermal conductivity factor of thermal isolation film is below 0.1W/mK.
4. thermal isolation film according to claim 1, it also has adhesive phase.
5. thermal isolation film according to claim 1, the thermal isolation film is used as window with film.
6. a kind of manufacture method of thermal isolation film, it is the manufacture method of the thermal isolation film described in claim 1, and this method includes：
(1) process for forming block copolymer layer on the plastic film,
(2) process that micro phase separation structure is formed on the block copolymer layer,
(3) part or all by a polymer phase of the block copolymer layer for foring micro phase separation structure removes,
So as to form the process of the polymeric layer with loose structure.
7. the manufacture method of thermal isolation film according to claim 6, wherein, the loose structure is micropore, and the micropore
Average pore size is 5~1000nm.
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| PCT/JP2014/077236 WO2015056650A1 (en) | 2013-10-17 | 2014-10-10 | Insulating film and production method therefor |
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| TWI663198B (en) | 2018-02-21 | 2019-06-21 | 國立清華大學 | Method for fabricating nanoporous polymer thin film and method for fabricating nanoporous thin film |
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| CN101583657A (en) * | 2007-01-11 | 2009-11-18 | 日东电工株式会社 | Process for producing microporous polymeric object, microporous polymeric object, and separation membrane |
| CN101688047A (en) * | 2007-03-28 | 2010-03-31 | 日东电工株式会社 | Method for producing polymer article having micro-phase separation structure and polymer article having micro-phase separation structure |
| CN101855258A (en) * | 2007-09-03 | 2010-10-06 | 国立大学法人东京工业大学 | Microphase separated structure film and process for producing the microphase separated structure film |
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| JP4055507B2 (en) * | 2002-08-06 | 2008-03-05 | 王子製紙株式会社 | Transparent insulation sheet |
| JP2010138659A (en) | 2008-12-15 | 2010-06-24 | Toray Ind Inc | Window covering sheet |
| JP5176123B2 (en) | 2011-02-01 | 2013-04-03 | 国立大学法人 名古屋工業大学 | Thermal insulation film using nano hollow particles made of silica shell |
| JP6082726B2 (en) * | 2012-02-24 | 2017-02-15 | 国立大学法人九州工業大学 | Thermoelectric conversion material |
| JP2013173851A (en) * | 2012-02-24 | 2013-09-05 | Lintec Corp | Method of producing porous structure |
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| CN101583657A (en) * | 2007-01-11 | 2009-11-18 | 日东电工株式会社 | Process for producing microporous polymeric object, microporous polymeric object, and separation membrane |
| CN101688047A (en) * | 2007-03-28 | 2010-03-31 | 日东电工株式会社 | Method for producing polymer article having micro-phase separation structure and polymer article having micro-phase separation structure |
| CN101855258A (en) * | 2007-09-03 | 2010-10-06 | 国立大学法人东京工业大学 | Microphase separated structure film and process for producing the microphase separated structure film |
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