CN107406755A - Thermochromic film - Google Patents
Thermochromic film Download PDFInfo
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- CN107406755A CN107406755A CN201680017823.2A CN201680017823A CN107406755A CN 107406755 A CN107406755 A CN 107406755A CN 201680017823 A CN201680017823 A CN 201680017823A CN 107406755 A CN107406755 A CN 107406755A
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- line
- thermochromic film
- resin
- vanadium dioxide
- film
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Even if the present invention provides and is subjected to the thermochromic film that the lifting course of temperature displays that good thermal discoloration and inhibits total light transmittance to reduce repeatedly.The present invention is a kind of thermochromic film, wherein, contain vanadium dioxide line and resin；The average minor axis of above-mentioned vanadium dioxide line is 10~100nm, and the length-width ratio defined by average major diameter/average minor axis is 5~500；Above-mentioned resin is that linear expansion coefficient is 12 × 10‑5/ below K crystalline resin or linear expansion coefficient is 12 × 10‑5The amorphous resin that/below K and glass transition temperature are more than 85 DEG C.
Description
Technical field
The present invention relates to thermochromic film.
Background technology
Vanadium dioxide as vary with temperature and display thermotropic that the optical characteristics such as transmissivity, reflectivity reversibly changes
The material of color gets most of the attention.The crystal of rutile-type vanadium dioxide shows semiconductor phase when less than phase transition temperature, in phase transformation
To Metal Phase Transition when more than temperature.The phase transformation reversibly occurs at about 68 DEG C, the change of infrared transmitting rate, particularly near-infrared
The transmissivity significantly change in region.
Using such property, for example, in Japanese Unexamined Patent Publication 2004-4795 publications (equivalent to U.S. Patent Application Publication
No. 2003/0196454 specification) in, it is proposed that the multi-functional automatic tune of the light modulation film containing vanadium oxide has been coated to glass
Light heat-protecting glass.
In addition, in Japanese Unexamined Patent Publication 2014-73955 publications, it is proposed that use and contain the excellent oxidation of thermal discoloration
The laminated glass of the intermediate coat of vanadium (IV) particle and thermoplastic resin.In addition in Japanese Unexamined Patent Publication 2011-136873 publications,
Propose thermochromic film obtained from vanadium dioxide is mixed into resin and shaping.
The content of the invention
It will be appreciated, however, that described in Japanese Unexamined Patent Publication 2014-73955 publications and Japanese Unexamined Patent Publication 2011-136873 publications
Lifting course of the resin film containing vanadium dioxide due to being subjected to temperature repeatedly, reduced with preliminary phase than total light transmittance.
Therefore even if it is an object of the invention to provide the lifting course for being subjected to temperature repeatedly to display that good thermotropic
Color and the thermochromic film for inhibiting total light transmittance to reduce.
The present inventor etc. have made intensive studies to solve above-mentioned problem.Contain length-width ratio as a result, finding to utilize
It can be solved in the thermochromic film of the resin of particular range with vanadium dioxide line and linear expansion coefficient of the average grain diameter in particular range
Certainly above-mentioned problem, so as to complete the present invention.
That is, the present invention is a kind of thermochromic film, wherein, contain vanadium dioxide line and resin；Above-mentioned vanadium dioxide line
Average minor axis is 10~100nm, and the length-width ratio defined by average major diameter/average minor axis is 5~500；Above-mentioned resin is that line is swollen
Swollen coefficient is 12 × 10-5/ below K crystalline resin or linear expansion coefficient is 12 × 10-5/ below K and glass transition
Temperature is more than 85 DEG C of amorphous resin.
Embodiment
The present invention is a kind of thermochromic film, wherein, containing vanadium dioxide line and resin, above-mentioned vanadium dioxide line is averaged
Minor axis is 10~100nm, and the length-width ratio defined by average major diameter/average minor axis is 5~500, and above-mentioned resin is line expansion system
Number is 12 × 10-5/ below K crystalline resin or linear expansion coefficient is 12 × 10-5/ below K and glass transition temperature
For more than 85 DEG C amorphous resins.Even if the thermochromic film of the invention with such composition plays is subjected to temperature repeatedly
Lifting course display that good thermal discoloration and suppress total light transmittance and reduce this excellent effect.
Why the thermochromic film of the present invention plays the effect above, and its detailed reason is still not clear, it is believed that is discussed further below
Mechanism.It should illustrate, following mechanism is to speculate, the invention is not restricted to following mechanism.
In Japanese Unexamined Patent Publication 2014-73955 publications and Japanese Unexamined Patent Publication 2011-136873 publications, it is proposed that contain
Show the vanadium dioxide particle of thermal discoloration and the film of resin.However, it specify that in Japanese Unexamined Patent Publication 2014-73955 publications
In the technology recorded with Japanese Unexamined Patent Publication 2011-136873 publications, exist due to being subjected to the lifting course of temperature repeatedly and visible
Light transmission (total light transmittance) reduces this problem.The present inventor etc. thinks that this is relevant with following phenomenon, i.e., due to dioxy
The linear expansion coefficient of change vanadium particle and the linear expansion coefficient of resin are different greatly, so as to cause to go through in the lifting for being subjected to temperature repeatedly
Cheng Shi, space is produced at the interface of vanadium dioxide particle and resin, make transmission of visible light (total light transmittance) reduction.
For the discoveries such as such problem, the present inventor utilize containing average minor axis be 10~100nm and by average major diameter/
The vanadium dioxide line and linear expansion coefficient that the length-width ratio that average minor axis defines is 5~500 are 12 × 10-5/ below K crystallinity tree
Fat or linear expansion coefficient are 12 × 10-5The thermotropic for the amorphous resin that/below K and glass transition temperature are more than 85 DEG C
Color film can solve above-mentioned problem.By as such composition, even if being subjected to the lifting course of temperature repeatedly, can also suppress
The interface of vanadium dioxide line and resin produces space.As a result, even if the lifting course that can obtain being subjected to temperature repeatedly also shows
The thermochromic film shown good thermal discoloration and inhibit total light transmittance to reduce.
Hereinafter, the preferred embodiment of the present invention is illustrated.It should illustrate, the present invention is not limited only to following reality
Apply mode.Should illustrate, in this specification, represent scope " X~Y " refer to comprising X as lower limit, comprising Y as the upper limit
The scope of value.In addition, as long as no special records, then operation and the measure of physical property etc. are in room temperature (20~25 DEG C)/relative humidity
Determined under conditions of 40~50%RH.
[vanadium dioxide line]
The thermochromic film of the present invention contains average minor axis for 10~100nm and defined by average major diameter/average minor axis
Length-width ratio is 5~500 vanadium dioxide line.
The vanadium dioxide line contains vanadium dioxide.Various crystalline phases in vanadium dioxide be present, have single within specified temperatures
Oblique Jingjing body and tetragonal crystal (rutile-type) reversibly phase transformation and make the thermal discoloration of infrared transmitting rate significantly change.
The average minor axis of vanadium dioxide line of the present invention is 10~100nm.It is low that average minor axis can not substantially be synthesized
In 10nm vanadium dioxide line.On the other hand, when average minor axis is more than 100nm, total light at the initial stage of obtained thermochromic film
Line transmissivity is insufficient.The average minor axis is preferably 10~80nm, more preferably 10~50nm.It should illustrate, vanadium dioxide line
Average minor axis use the equal minor axis of number determined by the method described in embodiment.
Moreover, it relates to the length-width ratio defined by average major diameter/average minor axis of vanadium dioxide line be 5~500.
When length-width ratio is less than 5, it cannot suppress to be subjected to the effect of the line expansion of thermochromic film after the lifting course of temperature repeatedly, always
Light transmittance reduces.On the other hand, it is broken during the online synthesis of vanadium dioxide line more than 500, therefore substantial nothing
Method synthesizes.The length-width ratio is preferably 10~250, and more preferably 20~200.
It should illustrate, the average major diameter of vanadium dioxide line uses the number determined by the method described in embodiment long
Footpath.The average major diameter is preferably 50~50000nm, more preferably 100~25000nm, more preferably 500~20000nm.
＜ is coated with ＞
It is preferred that at least a portion on the surface of vanadium dioxide line of the present invention is by inorganic coating agent and organic smears
At least one of coating.The surface of vanadium dioxide line is coated by using inorganic coating agent, titanium dioxide can be suppressed
The surface oxidation of vanadium line, even if the lifting course for being subjected to temperature repeatedly is also easier to maintain thermal discoloration.In addition, by using
Organic smears is coated to the surface of vanadium dioxide line so that organic group be present in vanadium dioxide line surface, so as to tree
The compatibility of fat improves, and is not susceptible to the mutual cohesion of line, therefore the total light transmittance at the initial stage of thermochromic film improves.
Especially by after the surface of vanadium dioxide line is coated with inorganic coating agent, further applied with organic smears
Cloth, even if being subjected to the lifting course of temperature repeatedly so as to obtain and being also easier to maintain thermal discoloration this effect, and also obtain
Obtain and the mutual cohesion of line is not susceptible to because being improved with the compatibility of resin so total light at the initial stage of thermochromic film transmits
Effect as rate raising.
《Inorganic coating agent》
As the example of inorganic coating agent, for example, inorganic oxide, inorganic nitride can be enumerated.
As inorganic oxide, for example, silica, titanium dioxide, aluminum oxide, tantalum oxide, niobium oxide, oxidation can be enumerated
Lanthanum, tin oxide, vanadium oxide, barium strontium, barium zirconium phthalate, lead zirconate titanate, load lanthanium titanate, strontium titanates, barium titanate, barium fluoride magnesium,
Bismuth titanates, strontium bismuth titanate, strontium bismuth tantalate, tantalum bismuth niobate, yittrium oxide etc..As inorganic nitride, for example, can enumerate silicon nitride,
Boron nitride, titanium nitride etc..
These inorganic coating agents can be used alone or combine two or more use.In these inorganic coating agents, from
From the viewpoint of the adaptation of vanadium dioxide line, preferred inorganic oxide is more preferably selected from silica, titanium dioxide and oxidation
It is at least one kind of in aluminium.
As the method on the surface that vanadium dioxide line is coated with inorganic coating agent, it is not particularly limited, can enumerate will be above-mentioned
Inorganic coating agent or its precursor are stirred in the presence of acid and/or alkali in a solvent with vanadium dioxide line, are dried thereafter
Method.
As the example of the precursor for the inorganic oxide for belonging to preferable inorganic coating agent, for example, orthosilicic acid four can be enumerated
Ethyl ester (TEOS), titanium sulfate, sodium aluminate, isopropanol tantalum, ethanol niobium, butanol lanthanum etc..These precursors can be used alone or group
Close two or more use.
Temperature and time when being stirred is different according to the species of the inorganic coating agent used or its precursor, it is impossible to one
In general, temperature is preferably 20~120 DEG C, and the time is preferably 1~72 hour.
《Organic smears》
As the example of organic smears, for example, silane coupler, saturated fatty acid can be enumerated, unrighted acid, contained
Nitrogen organic compound, organic compounds containing sulfur etc..Wherein, from from the viewpoint of the adaptation of vanadium dioxide line, preferred silane
Coupling agent.Silane coupler can use known silane coupler, for example, can enumerate the silane coupler containing alkoxy,
Silane coupler containing halogen, the silane coupler containing amino, the silane coupler containing sulfydryl, the silicon containing vinyl
Alkane coupling agent, the silane coupler containing epoxy radicals, the silane coupler containing acetoxyl group, the silane containing acryloxy
Coupling agent, silane coupler containing methacryloxy etc..The silane coupler can be the oligomer of partial condensates.
As the more specifically example of silane coupler, for example, dimethyldimethoxysil,ne, dimethyl diethyl can be enumerated
TMOS, dimethoxydiphenylsilane, diphenyl diethoxy silane, MTMS, methyl triethoxy
Silane, methyl tripropoxy silane, the butoxy silane of methyl three, ethyl trimethoxy silane, ethyl triethoxysilane, tetramethyl
TMOS, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, aminomethyl phenyl dimethoxysilane, trimethyl first
TMOS, trimethylethoxysilane, 2- cyano ethyls triethoxysilane, phenyltrimethoxysila,e, styryl second
Base trimethoxy silane, 4- ammobutyltriethoxysilanes (4- ア シ ノ Block チ Le ト リ エ ト キ シ シ ラ Application) etc. contain
The silane coupler of alkoxy；3- r-chloropropyl trimethoxyl silanes, 3- r-chloropropyl trimethoxyl silanes, 3- chloropropyl trichlorines
Silane, (to chloromethyl) phenyltrimethoxysila,e, 4- chlorphenyls trimethoxy silane, dimethyldichlorosilane, diphenyl two
The silane couplers containing halogen such as chlorosilane, trim,ethylchlorosilane, methyl trichlorosilane, trifluoro propyl trimethoxy silane；
P-aminophenyl trimethoxy silane, N- (2- amino-ethyls) -3- TSL 8330s, aminoethylamino
Methylphenethyl trimethoxy silane, 3- TSL 8330s, APTES, 4- ammonia
Base butyl triethoxysilane, N- (6- Aminohexyls) TSL 8330 etc. contain the silane coupled of amino
Agent；The silane couplers containing sulfydryl such as 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi methyl dimethoxysilanes；
Vinyltrimethoxy silane, VTES, vinyltriacetoxy silane, (the 2- methoxyl groups of vinyl three
Ethyoxyl) silane coupler containing vinyl such as silane, vinyl trichlorosilane；3- glycidoxypropyl group trimethoxies
Silane, 3- glycidoxypropyl groups triethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-
The silane couplers containing epoxy radicals such as (3,4- epoxycyclohexyls) ethyl triethoxysilane；Phenyl triacetoxysilane
Deng the silane coupler containing acetoxyl group；3- acryloxypropyls trimethoxy silane, 3- acryloxypropyls three
The silane coupler containing acryloxy such as Ethoxysilane；3- methacryloxypropyl trimethoxy silanes, 3-
Silane coupler containing methacryloxy such as methacryloxypropyl etc..These are silane coupled
Agent can be used alone or combine two or more use.
In above-mentioned silane coupler, the silane coupler containing amino is in polymethyl methacrylate (PMMA), three second
Dispersiveness in acid cellulose (TAC), polyamide 6 (PA6), polyamide 66 (PA66) etc. is particularly preferably.
Mercaptosilane coupling agents are in polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polysulfones
(PSF) dispersiveness, in polyether sulphone (PES) etc. is particularly preferred.
Silane coupler containing vinyl is in cyclic olefin polymer (COP), cyclic olefine copolymer (COC), polytetrafluoroethyl-ne
Dispersiveness in alkene (PTFE), Kynoar (PVDF) etc. is particularly preferably.
Silane coupler containing epoxy radicals polymethyl methacrylate (PMMA), polystyrene (PS), acrylonitrile-
Dispersiveness in SB (ABS) etc. is particularly preferably.
Silane coupler containing methacryloxy cyclic olefin polymer (COP), cyclic olefine copolymer (COC),
Polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid ethylene glycol
Dispersiveness in ester (PEN), polybutylene terephthalate (PBT) (PBT), PBN (PBN) is particularly preferably.
As the method on the surface that vanadium dioxide line is coated with silane coupler, it is not particularly limited, can enumerate will be above-mentioned
Silane coupler and vanadium dioxide line are stirred in a solvent, thereafter dry method.
Temperature and time when being stirred is different according to the species of the silane coupler used, it is impossible to lumps together,
Temperature is preferably 20~80 DEG C, and the time is preferably 0.5~6 hour.
＜ displaced atoms ＞
The a part of of the vanadium atom of above-mentioned vanadium dioxide line can be by selected from tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin
(Sn), rhenium (Re), iridium (Ir), osmium (Os), ruthenium (Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminium (Al), fluorine (F) and phosphorus
(P) at least one kind of atom substitution in.By that containing such displaced atom, the thermal discoloration of vanadium dioxide line can be made (special
It is not phase transition temperature) it is easier to control.The content of displaced atom during containing these displaced atoms is excellent relative to vanadium (V) atom
Elect 0.1~5 atom %, more preferably 1~3 atom % as.If the content of displaced atom more than 5 atom %, vanadium atom
Amount is relative to be reduced, and thermal discoloration reduces sometimes.The method containing these displaced atoms in vanadium dioxide line is described below.
The content of vanadium dioxide line in the thermochromic film of the present invention is preferably 1~50 matter relative to the gross mass of film
Measure %, more preferably more preferably 5~30 mass %, 7~15 mass %.If the scope, then thermic can be obtained
The excellent thermochromic film of the total light transmittance at discolouration and initial stage.
The manufacture method ＞ of ＜ vanadium dioxide lines
The manufacture method of vanadium dioxide line of the present invention is not particularly limited, and preferably enumerates the system for including following process
Make method：(A) using vfanadium compound as raw material, in oxidant and/or reducing agent and it is added as needed on former containing displacement
Hydro-thermal reaction, three vanadium hydrate (V of the oxidation of synthesis seven are carried out in the presence of the compound of son3O7·H2O process)；(B) will obtain
V3O7·H2O further carries out reduction reaction, obtains the process of vanadium dioxide line as raw material；(C) by above-mentioned (B) process
The process that obtained vanadium dioxide line is made annealing treatment.Here, hydro-thermal reaction refers to using high-temperature high pressure water, such as temperature
More than 180 DEG C, the reaction of more than pressure 1MPa hot water.
As the vfanadium compound used in (A) process, for example, vanadic anhydride (V can be enumerated2O5), ammonium vanadate
(NH4VO3), vanadyl oxalate hydrate (VOC2O4·nH2O), vanadic sulfate (VOSO4·nH2O), vanadium oxytrichloride (VOCl3), partially
Sodium vanadate (NaVO3) etc..These vfanadium compound can be used alone or combine two or more use.
In addition, as the Oxidizing and Reducing Agents used in (A) process, for example, oxalic acid, acetic acid, formic acid, the third two can be enumerated
Acid, propionic acid, butanedioic acid, citric acid, amino acid, ascorbic acid, butyric acid, valeric acid, benzoic acid, gallic acid, mellitic acid, breast
Acid, malic acid, maleic acid, aconitic acid, glutaric acid, methanol, phenol, ethylene glycol, cresols, ethanol, dimethylformaldehyde, acetonitrile, third
Ketone, ethyl acetate, propyl alcohol, butanol, hydrazine, hydrogen peroxide, peracetic acid, chloramines, dimethyl sulfoxide (DMSO), metachloroperbenzoic acid, nitric acid
Deng.These Oxidizing and Reducing Agents may be used singly or as a mixture of two or more.
(A) reaction temperature of the hydro-thermal reaction in process is not particularly limited, preferably 230~350 DEG C, more preferably
250~300 DEG C.In addition, the reaction time is it is not also specifically limited, preferably 1~120 hour, more preferably 6~72 hours.This
Outside, the addition of oxidant or reducing agent is preferably 5~50 mass % relative to the vfanadium compound as raw material, more preferably
10~30 mass %.
The average minor axis of vanadium dioxide line, average major diameter and length-width ratio can be somebody's turn to do the hydro-thermal reaction of (A) process by regulation
Reaction temperature, reaction time, the oxidant used and/or the species of reducing agent and addition etc. control.
When obtaining the vanadium dioxide line containing displaced atom, the chemical combination containing displaced atom is added preferably in hydro-thermal reaction
Thing.As the species of displaced atom, as described above, it is preferred to selected from tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium
(Re), in iridium (Ir), osmium (Os), ruthenium (Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminium (Al), fluorine (F) and phosphorus (P)
It is at least one kind of.Compound containing displaced atom can be used alone or combine two or more use.Change containing displaced atom
The addition of compound is suitably adjusted in a manner of as the preferred content of above-mentioned displaced atom.
The solvent used in reduction reaction as (B) process, for example, water can be enumerated；Methanol, ethanol, normal propyl alcohol, 2-
The alcoholic solvents such as propyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, phenmethylol, methyl cellosolve；The dihydric alcohols such as ethylene glycol, diethylene glycol are molten
Agent；The ketone solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Ethyl acetate, butyl acetate, carbitol acetic acid
The ester solvents such as ester, acetate of butyl carbitol；The ether solvents such as methyl cellosolve, ethyl cellosolve, butyl ether, tetrahydrofuran；Benzene, first
Aromatic solvents such as benzene, dimethylbenzene etc..These solvents may be used singly or as a mixture of two or more.(B) going back in process
The reaction temperature of original reaction is not particularly limited, preferably 150~350 DEG C, more preferably 200~300 DEG C.In addition, during reaction
Between it is not also specifically limited, preferably 12~120 hours, more preferably 24~96 hours.
After (B) process, for the purpose of obtained vanadium dioxide to be transformed into the R phases of display thermal discoloration, carry out (C)
Annealing.This is due to the vanadium dioxide obtained after (B) process by not showing the A phases of thermal discoloration and the mixture of B phases
Obtain, but by further implementing annealing at high temperature and to R phase in version.The atmosphere of annealing is not particularly limited,
It is preferred that under the rare gas atmosphere such as argon, under blanket of nitrogen, vacuum atmosphere it is inferior.In addition, the treatment temperature of annealing is preferably 300
~800 DEG C, processing time is preferably 0.5~24 hour.
Thus, it is possible to obtain vanadium dioxide line of the present invention.
[resin]
The resin used in the present invention is that linear expansion coefficient is 12 × 10-5/ below K crystalline resin or line expansion
Coefficient is 12 × 10-5The amorphous resin that/below K and glass transition temperature are more than 85 DEG C.It should illustrate, the line of resin is swollen
Swollen coefficient, glass transition temperature (Tg) and fusing point can be determined using the method described in embodiment.
＜ crystalline resins ＞
As the crystalline resin used in the present invention, as long as linear expansion coefficient is 12 × 10-5/ below K crystallinity
Resin does not just limit, for example, can enumerate polyethylene terephthalate (PET), PEN (PEN),
Polybutylene terephthalate (PBT) (PBT), PBN (PBT), polyformaldehyde (POM), polytetrafluoroethylene (PTFE)
(PTFE), Kynoar (PVDF), cellulose triacetate (TAC), polyamide 6 (PA6), polyamide 66 (PA66), polyamide
11 (PA11), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 612 (PA612) etc..These crystalline resins can
To be used singly or in combination of two or more thereof.In these crystalline resins, from the viewpoint of the transparency, it is preferably selected from
It is at least one kind of in polyethylene terephthalate, PEN and cellulose triacetate.
In the case of crystalline resin, it is believed that because the presence for crystallizing position makes its structure become firm, so thermally-induced
Volume Changes are so big unlike amorphous resin, and crystalline resin is influenceed small by glass transition temperature.However, crystallinity tree
The linear expansion coefficient of fat is more than 12 × 10-5In the case of/K, in the phase transformation of vanadium dioxide line, vanadium dioxide line and resin it
Between easily produce space, when being subjected to the lifting course of temperature repeatedly, total light transmittance reduce.The line expansion of the crystalline resin
Coefficient is preferably 10 × 10-5/ below K, more preferably 8 × 10-5/ below K.
The fusing point of crystalline resin is not particularly limited, from the viewpoint of heat resistance and processability, preferably 150~
350 DEG C, more preferably 200~300 DEG C.
＜ amorphous resins ＞
As the amorphous resin used in the present invention, as long as linear expansion coefficient is 12 × 10-5/ below K and vitrifying
Transition temperature is that more than 85 DEG C of amorphous resin is just not particularly limited, for example, polymethyl methacrylate can be enumerated
(PMMA), polystyrene (PS), makrolon (PC), cyclic olefin polymer (COP), cyclic olefine copolymer (COC), polyphenylene oxide
(PPO), acrylonitrile-butadiene-styrene copolymer (ABS), polyacrylonitrile (PAN), SAN
(SAN), polysulfones (PSF), polyether sulfone (PES), PEI (PEI) etc..These amorphous resins can be used alone or
Combine two or more use.In these amorphous resins, from the viewpoint of the transparency, poly-methyl methacrylate is preferably selected from
It is at least one kind of in ester, polystyrene, makrolon, cyclic olefin polymer and cyclic olefine copolymer.
The linear expansion coefficient of amorphous resin is more than 12 × 10-5In the case of/K, in the phase transformation of vanadium dioxide line,
Space is easily produced between vanadium dioxide line and resin, when being subjected to the lifting course of temperature repeatedly, total light transmittance reduces.Should
The linear expansion coefficient of amorphous resin is preferably 10 × 10-5/ below K, more preferably 8 × 10-5/ below K.
Amorphous resin produces Volume Changes drastically in glass transition temperature or so.That is, amorphous resin is heating up
When if it exceeds glass transition temperature then volume dramatically increases, on the other hand, vanadium dioxide line has when exceeding phase transition temperature
The property of volume-diminished, so if the phase transition temperature of vanadium dioxide line is 68 DEG C of glass transition temperatures with amorphous resin
It is close, then space is easily produced between amorphous resin and vanadium dioxide line.Therefore, if the vitrifying of amorphous resin turns
Temperature is less than 85 DEG C, then when being subjected to the lifting course of temperature repeatedly, is produced between amorphous resin and vanadium dioxide line empty
Gap, total light transmittance reduce.The glass transition temperature of amorphous resin is preferably more than 100 DEG C, more preferably 120 DEG C with
On.
Above-mentioned resin can use commercially available product, can also use composite.As the example of commercially available product, for example, can enumerate
Vylopet (registration mark) series (Co. Ltd. system, polyethylene terephthalate spin in Japan), Teonex (registration mark)
Serial (Teijin Ltd's system, PEN), KC4UAW (Konica Minolta Opto Inc.'s system, triacetic acid
Cellulose), ACRYPET (registration mark) serial (Mitsubishi Rayon Co., Ltd's system, polymethyl methacrylate), HF77,679
(being above HS Amada Co., Ltd.s, polystyrene), Panlite (registration mark) series (Teijin Chemicals, Ltd.'s system, poly- carbon
Acid esters), ZEONOR (registration mark) serial (Japanese Zeon Co. Ltd. systems, cyclic olefin polymer), Apel (registration mark) system
Arrange (Mitsui Chemicals, Inc's system, cyclic olefine copolymer) etc..
[other compositions]
It is steady that the thermochromic film of the present invention can contain antioxidant, ultra-violet absorber, antistatic agent, light as needed
Determine the known additive all the time such as agent, antifoggant, plasticizer, lubricant, surfactant, dispersant, antiblocking agent.
[manufacture method of thermochromic film]
The manufacture method of the thermochromic film of the present invention is not particularly limited, for example, extrusion by melting can be enumerated, solution pours
Casting (solution casting method), rolling process, compression forming methods etc..In these methods, preferred molten extrusion molding, solution casting method
(solution casting method).
As extrusion by melting, it can enumerate by vanadium dioxide line, resin and other compositions as needed melt and mix
After refining, membranaceous method is shaped to by melting extrusion.The kneading machine used in mixing is not particularly limited, for example, can be with
Use the known kneading machine all the time such as the extruders such as single axle extruding machine, biaxial extruder, pressure kneader.In addition, conduct
Membranaceous extrusion by melting is shaped to, T-shaped mould head method, inflation method etc. can be enumerated.Forming temperature during melting extrusion is according to resin
Species and change, therefore cannot treat different things as the same, but preferably 200~300 DEG C., can be with T-shaped mould head method when being molded on film
Known single axle extruding machine, biaxial extruder leading section install T-shaped mould head, will be extruded as membranaceous film roll around and rolled up
The film of shape.At this time it is also possible to apply stretching by the temperature for suitably adjusting take-up roll and in extrusion direction to carry out single shaft drawing
Stretch process.Alternatively, it is also possible to be drawn by being applied to the process in extrusion direction and vertical direction stretched film to apply gradually twin shaft
Stretch, the process such as simultaneously biaxial drawing.In addition, in order that the optical isotropy of film, mechanical property stabilisation, can also stretched
It is heat-treated after processing (annealing) etc..
In addition, for solution casting method (solution casting method), can enumerate prepare containing vanadium dioxide line, resin and according to
After the solution or dispersion liquid (rubber cement) of the other compositions needed, method of (curtain coating) etc. of casting.
As the solvent used in solution casting method (solution casting method), be not particularly limited, for example, can enumerate chloroform,
The chlorine series solvent such as dichloromethane；The fragrant family solvents such as toluene, dimethylbenzene, benzene and their mixed solvent；Methanol, ethanol, just
Propyl alcohol, 2- propyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, 2,2,2 tfifluoroethyl alcohol, 2,2,3,3- hexafluoro -1- propyl alcohol, 1,
The fluoro- 2- propyl alcohol of 3- bis-, 1,1,1,3,3,3- hexafluoro -2- methyl-2-propanols, 1,1,1,3,3,3- hexafluoros -2- third
The alcohol series solvents such as the fluoro- 1- propyl alcohol of alcohol, 2,2,3,3,3- five；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl
Formamide, dimethyl sulfoxide (DMSO), 1,3- dioxolanes, 1,4- bis-Alkane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone
(MEK), methyl acetate, ethyl acetate, pentyl acetate, Anaesthetie Ether, nitroethane etc..These solvents can be used alone or
And use two or more.As the device for carrying out solution casting method (solution casting method), for example, stainless steel band, roller can be enumerated
Formula casting machine, band casting machine, spin coater etc..
In solution casting method (solution casting method), preferably by the work including rubber cement is cast on above-mentioned device
Sequence, the rubber cement of curtain coating dried into the process for basement membrane (ウ ェ Block), dry after process, stretching or the guarantor of basement membrane are peeled off from device
The method of the process and the process being further dried etc. of holding width carries out membranization.
The thickness of the thermochromic film of the invention obtained as described above is preferably 1~100 μm, more preferably 10~60 μ
m。
[purposes]
The thermochromic film of the present invention can be suitably used for being attached at the thermal isolation film of the window of building, automobile etc., decoration use
Display, sheet material, glass and the tent of agricultural, the clothing etc. in the outdoor goods of tarpaulin etc and field.
Embodiment
The effect of the present invention is illustrated using following embodiment and comparative example.But technical scope of the invention
It is not limited only to following embodiment.It should illustrate, vanadium dioxide line (following, also referred to as " VO2Line ") average major diameter peace
Equal minor axis is obtained as follows.That is, using transmission electron microscope (TEM), VO is observed under conditions of the voltage 100kV that pressurizes2Line,
Photo is shot under 4000 times.Obtained photo is put into image analyzer and obtains image, arbitrary 100 is selected and carries out figure
As handling, the major diameter and minor axis of a line are obtained.Then, the major diameter of 100 lines and the arithmetic mean of instantaneous value of minor axis are obtained, calculates number
The equal equal minor axis of major diameter (Ll) sum (Ls).In addition, length-width ratio is to utilize the equal minor axis of the equal major diameter of number obtained above (Ll) sum
(Ls) value, calculate the equal minor axis (Ls) of several equal major diameters (Ll)/number and try to achieve.
＜ VO2Line W1 synthesis ＞
1.V3O7·H2O synthesis
Vanadic anhydride (V) (V is added in pure water 16mL2O5, superfine, Wako Pure Chemical Industries, Ltd.'s system) 0.3g and
Oxalic acid dihydrate ((COOH)2·2H2O, superfine, Wako Pure Chemical Industries, Ltd.'s system) 0.075g is stirred, prepares water-soluble
Liquid.
Next, by the aqueous solution be put into high pressure with reaction decomposition container i.e. static HU 50ml cylinders (セ ッ ト) (pressure-resistant not
Become rusty steel outer barrel, PTFE sample containers HUTc-50：Three possess a fondness for science Co. Ltd. system), during with 290 DEG C of reaction temperature, reaction
Between 6 hours carry out hydro-thermal reaction.
The precipitated product obtained after reaction is terminated is filtered, and is cleaned with water and acetone, obtains seven oxidations three of wire
Vanadium hydrate (V3O7·H2O)。
2.VO2The synthesis of line
Next, with reaction decomposition container it is static HU 50ml cylinders (pressure-resistant stainless steel outer barrel, PTFE systems to high pressure
Sample container HUTc-50：Three possess a fondness for science Co. Ltd. system) in add pure water 8mL, 2- propyl alcohol (superfine, and Wako Pure Chemical Industries strain
Formula commercial firm system) 8mL and above-mentioned 1. obtain seven oxidation three vanadium hydrate (V3O7·H2O) 0.3g, carried out at 210 DEG C 72 hours
Reaction.
The precipitated product obtained after reaction is terminated is filtered, and is cleaned with water and acetone, is obtained the vanadium dioxide of wire
(VO2)。
Next, vanadium dioxide (the VO by obtained wire2) kept for 1 hour and moved back at 475 DEG C under an argon
Fire processing.Thus, vanadium dioxide line W1 is obtained.The obtained vanadium dioxide line W1 equal major diameter of number is 50nm, and the equal minor axis of number is
10nm, length-width ratio (the equal equal minor axis of major diameter/number of number) is 5.
＜ VO2Line W2~W12 synthesis ＞
By above-mentioned 1.V3O7·H2Reaction temperature and reaction time in O synthesis change according to table 1 below, in addition,
With ＜ VO2Line W1 synthesis ＞ is similarly carried out, synthesis vanadium dioxide line W2~W12.
[table 1]
＜ is to VO2Organic smears processing ＞ of line
《VO2Line S1 synthesis》
Prepare 5 matter of silane coupler (Shin-Etsu Chemial Co., Ltd's system, KBM-13, MTMS)
The % aqueous solution is measured, by VO obtained above2Line W7 is put into the aqueous solution, is stirred at 25 DEG C 1 hour, is used silane coupler
Handle the surface of line.Thereafter, recovery product, drying process in 1 hour is carried out at 110 DEG C.Thus, obtain having and implement silane idol
Join the VO on the surface of agent processing2Line S1.
《VO2Line S2 synthesis》
As silane coupler, KBM-903 (Shin-Etsu Chemial Co., Ltd's system, 3- aminopropyl trimethoxies are used
Base silane), it is in addition, and above-mentioned《VO2Line S1 synthesis》Similarly carry out, obtain VO2Line S2.
《VO2Line S3 synthesis》
As silane coupler, KBM-403 (Shin-Etsu Chemial Co., Ltd's system, 3- glycidoxypropyl groups are used
Triethoxysilane), it is in addition, and above-mentioned《VO2Line S1 synthesis》Similarly carry out, obtain VO2Line S3.
《VO2Line S4 synthesis》
As silane coupler, KBM-503 (Shin-Etsu Chemial Co., Ltd's system, 3- methacryloxies are used
Propyl trimethoxy silicane), it is in addition, and above-mentioned《VO2Line S1 synthesis》Similarly carry out, obtain VO2Line S4.
＜ is to VO2The inorganic coating agent processing ＞ of line
《VO2Line T1 synthesis》
Added in the solution that ethanol (superfine, Wako Pure Chemical Industries, Ltd.'s system) 20ml and pure water 5ml is mixed
Ammoniacal liquor (the mass % of concentration 28, superfine, Wako Pure Chemical Industries, Ltd.'s system), prepares the solution that pH value is 11.8.In the solution
Middle addition 1.0g VO obtained above2Line W7 and 0.3g tetraethyl orthosilicate ((C2H5O)4Si, it is superfine, and Wako Pure Chemical Industries strain formula
Commercial firm's system), it is stirred at 25 DEG C 4 hours.Next, the product for being filtered from obtained suspension, cleaning and reclaiming is existed
110 DEG C of progress drying process in 1 hour.Thus, the VO with the surface that coating is implemented using silica is obtained2Line T1.
《VO2Line T2 synthesis》
By VO obtained above2Line W7 is added in pure water 10ml and is stirred, and is heated to 60 DEG C, is maintained at the temperature.
Disposably 30 mass % titanium sulfates (IV) solution 0.30g of addition, and add 1N sodium hydrate aqueous solution and make into the solution
The solution that standby pH value is 8.After being stirred 1 hour under the state, by by filtering, cleaning the product that reclaims, to carry out 1 at 110 DEG C small
When drying process.Thus, the VO with the surface that coating is implemented using titanium dioxide is obtained2Line T2.
《VO2Line T3 synthesis》
To VO obtained above2Added parallel with Al simultaneously in a manner of pH value is maintained at 7.5 or so in line W72O3Conversion
The sulfuric acid of sodium aluminate aqueous solution and 1N equivalent to 2 mass % is neutralized, and is stirred 1 hour.Thereafter, pH is adjusted to 6
~8 scope, filtered, cleaned, the product of recovery is subjected to drying process in 15 hours at 120 DEG C.Thus, obtain that there is profit
The VO on the surface of coating is implemented with aluminum oxide2Line T3.
＜ is to VO2The inorganic coating agent processing of line and organic smears processing ＞
《VO2Line T1S1 synthesis》
It is above-mentioned in progress《VO2Line T1 synthesis》Afterwards, with it is above-mentioned《VO2Line S1 synthesis》Similarly carry out silane coupled
Agent is handled, and obtains VO2Line T1S1.
《VO2Line T1S2 synthesis》
It is above-mentioned in progress《VO2Line T1 synthesis》Afterwards, with it is above-mentioned《VO2Line S2 synthesis》Similarly carry out silane coupled
Agent is handled, and obtains VO2Line T1S2.
＜ tungsten replaces VO2Line W13 synthesis ＞
1.V3O7·H2O preparation
Vanadic anhydride (V) (V is added in pure water 16mL2O5, superfine, Wako Pure Chemical Industries, Ltd.'s system) and 0.3g, partially
Ammonium tungstate pentahydrate ((NH4)10W12O4·5H2O, Wako Pure Chemical Industries, Ltd.'s system) 0.01g and oxalic acid dihydrate
((COOH)2·2H2O, superfine, Wako Pure Chemical Industries, Ltd.'s system) 0.075g is stirred, prepare the aqueous solution.
Next, the aqueous solution is put into high pressure with reaction decomposition container i.e. static HU 50ml cylinders (pressure-resistant stainless steel
Outer barrel, PTFE sample containers HUTc-50：Three possess a fondness for science Co. Ltd. system), carry out 30 hours hydro-thermal reactions at 260 DEG C.
The precipitated product obtained after reaction is terminated is filtered, and is cleaned with water and acetone, is obtained the line containing a small amount of tungsten
Seven three vanadium hydrate (V of oxidation of shape3O7·H2O)。
2.VO2The synthesis of line
Next, with reaction decomposition container it is static HU 50ml cylinders (pressure-resistant stainless steel outer barrel, PTFE systems to high pressure
Sample container HUTc-50：Three possess a fondness for science Co. Ltd. system) in add pure water 8mL, 2- propyl alcohol (superfine, and Wako Pure Chemical Industries strain
Formula commercial firm system) 8mL, obtain containing tungsten seven oxidation three vanadium hydrate (V3O7·H2O) 0.3g, carried out at 210 DEG C 72 hours
Reaction.
Obtained precipitated product after terminating will be reacted to be filtered, cleaned with water and acetone, obtain wire containing tungsten
Vanadium dioxide (VO2)。
Next, vanadium dioxide (the VO containing tungsten by obtained wire2) kept for 1 hour at 475 DEG C in argon gas stream,
Made annealing treatment.Thus, the VO containing tungsten is obtained2Line W13.The obtained VO containing tungsten2The line W13 equal major diameter of number (Ll) is
10000nm, the equal minor axis (Ls) of number are 50nm, length-width ratio 200.In addition, use x-ray photoelectron spectroscopy (Co., Ltd. island
Tianjin makes made, model KRATOS Nova) result of elementary analysis that carries out is that the ratio of tungsten (W) atom and vanadium (V) atom is
1.5 atom % or so.
＜ tungsten replaces VO2Line W14 synthesis ＞
By ammonium metatungstate pentahydrate ((NH4)10W12O4·5H2O, Wako Pure Chemical Industries, Ltd.'s system) addition quantitative change
More 0.02g, in addition, VO is replaced with above-mentioned ＜ tungsten2Line W13 synthesis ＞ is similarly carried out, and obtains tungsten displacement VO2Line
W14。
The result of the elementary analysis carried out using x-ray photoelectron spectroscopy is the ratio of tungsten (W) atom and vanadium (V) atom
For 3.0 atom %.
＜ tungsten replaces VO2Line W15 synthesis ＞
By ammonium metatungstate pentahydrate ((NH4)10W12O4·5H2O, Wako Pure Chemical Industries, Ltd.'s system) addition quantitative change
More 0.03g, in addition, VO is replaced with above-mentioned ＜ tungsten2Line W13 synthesis ＞ is similarly carried out, and obtains tungsten displacement VO2Line
W15。
The result of the elementary analysis carried out using x-ray photoelectron spectroscopy is the ratio of tungsten (W) atom and vanadium (V) atom
For 5.0 atom %.
By VO2Line S1~S4, T1~T3, T1S1~T1S2 and W13~W15 each physical property are shown in table 2 below.
[table 2]
(embodiment 1：The making of thermochromic film 1)
To polymethyl methacrylate (PMMA) resin particle (ACRYPET (registration mark) VH001, the beautiful positive strain formula of Mitsubishi
Commercial firm's system) in addition VO2Line W1 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, in barrel
It is kneaded at 240~280 DEG C of temperature.Then, extruded from the T-shaped mould head of 200mm width, while turning into 40 μm of side with the thickness of film
Formula regularization condition, while being cooled down with chill roll, thus make thermochromic film 1.
(embodiment 2：The making of thermochromic film 2)
Use VO2Line W2 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 2.
(embodiment 3：The making of thermochromic film 3)
Use VO2Line W10 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 3.
(embodiment 4：The making of thermochromic film 4)
Use VO2Line W11 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 4.
(embodiment 5：The making of thermochromic film 5)
Use VO2Line W3 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 5.
(embodiment 6：The making of thermochromic film 6)
Use VO2Line W7 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 6.
(embodiment 7：The making of thermochromic film 7)
Use VO2Line W9 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 7.
(embodiment 8：The making of thermochromic film 8)
Use VO2Line W6 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 8.
(embodiment 9：The making of thermochromic film 9)
Use VO2Line W8 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 9.
(embodiment 10：The making of thermochromic film 10)
Make VO2Line W7 addition is 0.8 mass %, in addition, is carried out similarly to Example 6, makes thermotropic
Color film 10.
(embodiment 11：The making of thermochromic film 11)
Make VO2Line W7 addition is 1 mass %, in addition, is carried out similarly to Example 6, makes thermochromism
Film 11.
(embodiment 12：The making of thermochromic film 12)
Make VO2Line W7 addition is 5 mass %, in addition, is carried out similarly to Example 6, makes thermochromism
Film 12.
(embodiment 13：The making of thermochromic film 13)
Make VO2Line W7 addition is 30 mass %, in addition, is carried out similarly to Example 6, makes thermochromism
Film 13.
(embodiment 14：The making of thermochromic film 14)
Make VO2Line W7 addition is 50 mass %, in addition, is carried out similarly to Example 6, makes thermochromism
Film 14.
(embodiment 15：The making of thermochromic film 15)
Make VO2Line W7 addition is 52 mass %, in addition, is carried out similarly to Example 6, makes thermochromism
Film 15.
(embodiment 16：The making of thermochromic film 16)
Use VO2Line S1 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 16.
(embodiment 17：The making of thermochromic film 17)
Use VO2Line S2 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 17.
(embodiment 18：The making of thermochromic film 18)
Use VO2Line S3 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 18.
(embodiment 19：The making of thermochromic film 19)
Use VO2Line S4 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 19.
(embodiment 20：The making of thermochromic film 20)
Use VO2Line T1 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 20.
(embodiment 21：The making of thermochromic film 21)
Use VO2Line T2 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 21.
(embodiment 22：The making of thermochromic film 22)
Use VO2Line T3 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 22.
(embodiment 23：The making of thermochromic film 23)
Use VO2Line T1S1 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film
23。
(embodiment 24：The making of thermochromic film 24)
Use VO2Line T1S2 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film
24。
(embodiment 25：The making of thermochromic film 25)
The addition VO into polystyrene (PS) resin particle (HF77, PS Japan Corp.'s system)2Line W7 make its content into
For 10 mass %, using screw diameter 40mm single axle extruding machine, it is kneaded at 220~260 DEG C of barrel temperature.Then, from
The T-shaped mould head extrusion of 200mm width, the regularization condition in a manner of the thickness of film turns into 40 μm, and meanwhile cooled down with chill roll,
Thus thermochromic film 25 is made.
(embodiment 26：The making of thermochromic film 26)
Polystyrene (PS) resin is replaced using polystyrene (PS) resin particle (679, PS Japan Corp.'s system)
Grain (HF77, PS Japan Corp.'s system), in addition, is carried out similarly to Example 25, makes thermochromic film 26.
(embodiment 27：The making of thermochromic film 27)
Into makrolon (PC) resin particle (Panlite (registration mark) L-1250, Teijin Chemicals, Ltd.'s system)
Add VO2Line W7 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, barrel temperature 260~
It is kneaded at 280 DEG C.Then, extruded from the T-shaped mould head of 200mm width, while adjusting bar in a manner of the thickness of film turns into 40 μm
Part, while being cooled down with chill roll, thus make thermochromic film 27.
(embodiment 28：The making of thermochromic film 28)
To cyclic olefin polymer (COP) resin particle (ZEONOR (registration mark) 1020R, Japanese Zeon Co. Ltd. systems)
Middle addition VO2Line W7 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, in barrel temperature 240
It is kneaded at~260 DEG C.Then, extruded from the T-shaped mould head of 200mm width, while being adjusted in a manner of the thickness of film turns into 40 μm
Condition, while being cooled down with chill roll, thus make thermochromic film 28.
(embodiment 29：The making of thermochromic film 29)
To cyclic olefine copolymer (COC) resin particle (Apel (registration mark) 5014DP, Mitsui Chemicals, Inc's system)
Middle addition VO2Line W7 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, in barrel temperature 260
It is kneaded at~280 DEG C.Then, extruded from the T-shaped mould head of 200mm width, while being adjusted in a manner of the thickness of film turns into 40 μm
Condition, while being cooled down with chill roll, thus make thermochromic film 29.
(embodiment 30：The making of thermochromic film 30)
To polyethylene terephthalate (PET) resin particle, (strain is spun by Vylopet (registration mark) EMC500, Japan
Formula commercial firm system) in addition VO2Line W7 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, is expecting
It is kneaded at 260~280 DEG C of temperature of cylinder.Then, extruded from the T-shaped mould head of 200mm width, while with the thickness of film as 40 μm
Mode regularization condition, while being cooled down with chill roll, thus make thermochromic film 30.
(embodiment 31：The making of thermochromic film 31)
To PEN (PEN) resin particle (Teonex (registration mark) TN-8065S, Teijin
Dupont Films Co. Ltd. systems) in addition VO2Line W7 makes its content turn into 10 mass %, uses screw diameter 40mm list
Axle extruder, it is kneaded at 270~290 DEG C of barrel temperature.Then, extruded from the T-shaped mould head of 200mm width, while with film
Thickness turns into 40 μm of mode regularization condition, while being cooled down with chill roll, thus makes thermochromic film 31.
(embodiment 32：The making of thermochromic film 32)
430 are added into cellulose triacetate (TAC) film (KC4UAW, Konica Minolta Opto Inc.'s system) 90 mass parts
Parts by mass Methylene chloride, 90 mass parts Methanols and 10 mass parts VO2Line W7, is put into closed container, under elevated pressure 80
DEG C insulation, being stirred is completely dissolved it and obtains composition.Next filtering said composition, is maintained at 33 DEG C after cooling,
Uniformly it is cast, when solvent is evaporated to and can peeled off, is peeled off from stainless steel band, what is conveyed with multiple rollers on stainless steel band
Terminate drying simultaneously, make the thermochromic film 32 of 40 μm of thickness.
(embodiment 33：The making of thermochromic film 33)
Use VO2Line W13 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 33.
(embodiment 34：The making of thermochromic film 34)
Use VO2Line W14 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 34.
(embodiment 35：The making of thermochromic film 35)
Use VO2Line W15 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 35.
(comparative example 1：The making of thermochromic film 36)
Use VO2Line W4 replaces VO2 line W1, in addition, carries out similarly to Example 1, makes thermochromic film 36.
(comparative example 2：The making of thermochromic film 37)
Use VO2Line W12 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 37.
(comparative example 3：The making of thermochromic film 38)
Use VO2Line W5 replaces VO2Line W1, in addition, carry out similarly to Example 1, make thermochromic film 38.
(comparative example 4：The making of thermochromic film 39)
To polyvinyl butyral resin (PVB) resin particle (S-LEC (registration mark) BL-2, ponding chemical industry strain formula meeting
Society's system) in addition VO2Line W7 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, in barrel temperature
It is kneaded at 120~140 DEG C of degree.Then, extruded from the T-shaped mould head of 200mm width, while in a manner of the thickness of film turns into 40 μm
Regularization condition, while being cooled down with chill roll, thus make thermochromic film 39.
(comparative example 5：The making of thermochromic film 40)
To ethylene-vinyl acetate copolymer resin particle (NOVATEC EVA LV1511, Japanese polyethylene strain formula meeting
Society's system) in addition VO2Line W7 makes its content turn into 10 mass %, using screw diameter 40mm single axle extruding machine, in barrel temperature
It is kneaded at 120~140 DEG C of degree.Then, extruded from the T-shaped mould head of 200mm width, while in a manner of the thickness of film turns into 40 μm
Regularization condition, while being cooled down with chill roll, thus make thermochromic film 40.
(evaluation)
＜ glass transition temperatures (Tg) and fusing point ＞
The glass transition temperature and fusing point of each resin determine (DSC) by means of differential scanning calorimetry and obtained.From particle or film
Middle weighing about 10mg is put into aluminum pot, using differential scanning calorimeter (TA Instruments Co., Ltd. " DSC Q100 "),
Under nitrogen atmosphere, it is measured with the condition of 25~300 DEG C of temperature range, 10 DEG C/min of warming temperature.Schemed by obtained DSC
Calculate glass transition temperature (Tg) and fusing point (unit：℃).
The linear expansion coefficient ＞ of ＜ resins
Using each resin used in embodiment and comparative example, VO is not added2Line, it is same with above-described embodiment and comparative example
Ground carries out and makes the film of 40 μm of thickness, determines linear expansion coefficient.In addition, for TAC film, by what is used in embodiment 32
KC4UAW (Konica Minolta Opto Inc.'s system) is directly used in measure.The measure of linear expansion coefficient is to use Seiko
What Instruments Co. Ltd. systems TMA120C was carried out.
Sample uses width 3mm, the length 10mm film cut from film, is heated up with 10 DEG C loading 3g, programming rate/min
It is measured to 10~100 DEG C.Linear expansion coefficient in 25 DEG C~80 DEG C of resin is obtained by obtained figure.As TE1.
The linear expansion coefficient and line expansion suppression ＞ of ＜ thermochromisms
To the thermochromic film made in embodiment 1~32 and comparative example 1~5, carry out as described above, it is swollen to obtain line
Swollen coefficient.It is set to TE2.
In addition, calculate addition VO using following formula2Line expansion suppression TEc caused by line, according to following bases
Quasi- evaluation.It can then be actually used if △~◎.
Line expansion suppression TEc (%)=[(TE1-TE2)/TE1] × 100
◎：More than 30%
○：15% less than 30%
△：5% less than 15%
×：Less than 5%.
＜ total light transmittances ＞
Based on JIS K 7136：The total light transmittance for the thermochromic film that 2000 measure make.Measure uses light splitting light
Degree meter V-670 (Japan Spectroscopy Corporation's system) is carried out, and determination of the environment is set to 25 DEG C/50%RH.Judge according to following benchmark
As a result.If △~◎, then can actually use.
◎：More than 92%
○：87% less than 92%
△：80% less than 87%
×：Less than 80%.
[thermal discoloration]
As the evaluation of the thermal discoloration of the thermochromic film of making, determine in 25 DEG C/50%RH and 85 DEG C/50%RH
Under wavelength 1300nm the light transmittance (measured value under 25 DEG C/50%RH：T1 (%), the measure under 85 DEG C/50%RH
Value：T2 (%)), and the transmission rate variance (Δ T=T1-T2 (%)) calculated according to the evaluation of following metewands.Measure is to be divided
Temperature control unit (Japan Spectroscopy Corporation's system) is installed on photometer V-670 (Japan Spectroscopy Corporation's system) and carried out
's.It can then be actually used if △~◎.
◎：More than 20%
○：10% less than 20%
△：5% less than 10%
×：Less than 5%.
[thermal cycling test]
Between the thermochromic film of making is clipped in into 2 transparent glass plates, the glass plate is put into thermal cycling test machine
(ESPEC Co. Ltd. systems, model TSA-72ES), implement thermal cycling test.In thermal cycling test, by each sample-
40 DEG C preserve 30 minutes after, 80 DEG C preserve 30 minutes processes as 1 circulation, is carried out 1000 circulate.Tied in experiment
Shu Houcong glass plates remove thermochromic film, evaluate total light transmittance and thermal discoloration.
＜ total light transmittance sustainment rate Tr ＞
Total light transmittance before thermal cycling test is set to T1, the total light transmittance after thermal cycling test is set to T2
When, the total light transmittance sustainment rate Tr that judges to be calculated by following formula according to following benchmark.Then can be actual if △~◎
Use.
Total light transmittance sustainment rate Tr (%)=(T2/T1) × 100
◎：Tr >=95%
〇：87%≤Tr ＜ 95%
△：75%≤Tr ＜ 87%
×：Tr ＜ 75%.
＜ thermal discoloration sustainment rate Cr ＞
The thermal discoloration of film before thermal cycling test is set to C1, the thermal discoloration of the film after thermal cycling test is set
For C2 when, the thermal discoloration sustainment rate for judging to be calculated by following formula according to following benchmark evaluates Cr.If △~◎ then
It can actually use.
Thermal discoloration sustainment rate Cr (%)=(C2/C1) × 100
◎：Cr >=95%
〇：87%≤Cr ＜ 95%
△：75%≤Cr ＜ 87%
×：Cr ＜ 75%.
The composition and evaluation result of each embodiment and comparative example are shown in Table 3 below.
[table 3-1]
[table 3-2]
From the result of above-mentioned table 3, the maintenance of the total light transmittance after the thermal cycle of the thermochromic film of embodiment
The sustainment rate of rate and thermal discoloration is excellent.On the other hand, it is known that the heat of the thermochromic film of comparative example 1 and comparative example 3~5 is followed
The sustainment rate of total light transmittance after ring is low.In addition, understand the total light transmittance at the initial stage of the thermochromic film of comparative example 2
It is very low, it can not actually use.
It should illustrate, the application is based on Japanese patent application filed in 24 days March in 2015 the 2015-060877th, ginseng
According to and integrally quote the disclosure of which.
Claims (8)
1. a kind of thermochromic film, wherein, containing vanadium dioxide line and resin,
The average minor axis of the vanadium dioxide line is 10~100nm, and the length-width ratio defined by average major diameter/average minor axis is 5
~500,
The resin is that linear expansion coefficient is 12 × 10-5/ below K crystalline resin or linear expansion coefficient is 12 × 10-5/K
Below and glass transition temperature is more than 85 DEG C of amorphous resin.
2. thermochromic film according to claim 1, wherein, the content of the vanadium dioxide line relative to film gross mass
For 1~50 mass %.
3. thermochromic film according to claim 1 or 2, wherein, the crystalline resin is to be selected from poly terephthalic acid
It is at least one kind of in glycol ester, PEN and cellulose triacetate.
4. thermochromic film according to claim 1 or 2, wherein, the amorphous resin is to be selected from polymethylacrylic acid
It is at least one kind of in methyl esters, polystyrene, makrolon, cyclic olefin polymer and cyclic olefine copolymer.
5. according to thermochromic film according to any one of claims 1 to 4, wherein, utilize inorganic coating agent and organic coating
At least one of agent is coated with least a portion on the surface of the vanadium dioxide line.
6. thermochromic film according to claim 5, wherein, the inorganic coating agent is selected from silica, titanium dioxide
It is at least one kind of in titanium and aluminum oxide.
7. the thermochromic film according to claim 5 or 6, wherein, organic smears is silane coupler.
8. according to thermochromic film according to any one of claims 1 to 7, wherein, the vanadium atom in the vanadium dioxide line
A part by least one kind of atom in tungsten, molybdenum, niobium, tantalum, tin, rhenium, iridium, osmium, ruthenium, germanium, chromium, iron, gallium, aluminium, fluorine and phosphorus
Displacement.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-060877 | 2015-03-24 | ||
| JP2015060877 | 2015-03-24 | ||
| PCT/JP2016/059056 WO2016152879A1 (en) | 2015-03-24 | 2016-03-22 | Thermochromic film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107406755A true CN107406755A (en) | 2017-11-28 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680017823.2A Pending CN107406755A (en) | 2015-03-24 | 2016-03-22 | Thermochromic film |
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| Country | Link |
|---|---|
| JP (1) | JPWO2016152879A1 (en) |
| CN (1) | CN107406755A (en) |
| WO (1) | WO2016152879A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735084A (en) * | 2018-12-29 | 2019-05-10 | 上海锦湖日丽塑料有限公司 | A kind of polycarbonate compositions of temperature-controllable and preparation method thereof |
| CN116100888A (en) * | 2022-11-09 | 2023-05-12 | 慈溪市兰星塑胶实业有限公司 | Color-changing film and preparation method thereof |
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|---|---|---|---|---|
| JP2020012011A (en) * | 2016-11-16 | 2020-01-23 | コニカミノルタ株式会社 | Thermochromic composition and thermochromic film |
| WO2018105238A1 (en) * | 2016-12-06 | 2018-06-14 | コニカミノルタ株式会社 | Vanadium-dioxide-containing particles, thermochromic film, and method for producing vanadium-dioxide-containing particles |
| FR3068981B1 (en) * | 2017-07-11 | 2020-07-17 | Seb S.A. | TEMPERATURE INDICATOR FOR CULINARY ARTICLE |
| CN111499957A (en) * | 2020-06-12 | 2020-08-07 | 济南大学 | Composite film with heat insulation effect and preparation method |
| CN113462112B (en) * | 2021-07-19 | 2023-11-10 | 江苏润泽节能科技有限公司 | Temperature-sensing photosensitive composition for intelligent window |
| CN116444910A (en) * | 2023-04-28 | 2023-07-18 | 安徽江淮汽车集团股份有限公司 | PS composite material with good antibacterial property and VOC (volatile organic compound) property and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011136873A (en) * | 2009-12-28 | 2011-07-14 | Tsurumi Soda Co Ltd | Vanadium dioxide fine particles, manufacturing method and thermo-chromic film |
| US20110284809A1 (en) * | 2009-02-09 | 2011-11-24 | National Institute Of Advanced Industrial Science And Technology | Particles, method of producing particles, and coating material, film, and ink including particles |
| JP2012250879A (en) * | 2011-06-03 | 2012-12-20 | Sekisui Chem Co Ltd | Thermochromic film, interlayer for laminated glass, laminated glass and pasting film |
| WO2015030206A1 (en) * | 2013-08-30 | 2015-03-05 | 積水化学工業株式会社 | Intermediate film for laminated glass, and laminated glass |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004346260A (en) * | 2003-05-26 | 2004-12-09 | Toagosei Co Ltd | Thermochromic film and thermochromic glass |
| JP5476581B2 (en) * | 2008-06-30 | 2014-04-23 | 独立行政法人産業技術総合研究所 | Thermochromic fine particles, dispersion thereof, production method thereof, and light control paint, light control film and light control ink |
| JP2014073955A (en) * | 2012-09-12 | 2014-04-24 | Sekisui Chem Co Ltd | Vanadium oxide composition, vanadium oxide particle, dispersion containing vanadium oxide particle, interlayer for laminated glass and laminated glass |
-
2016
- 2016-03-22 JP JP2017508371A patent/JPWO2016152879A1/en active Pending
- 2016-03-22 WO PCT/JP2016/059056 patent/WO2016152879A1/en active Application Filing
- 2016-03-22 CN CN201680017823.2A patent/CN107406755A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110284809A1 (en) * | 2009-02-09 | 2011-11-24 | National Institute Of Advanced Industrial Science And Technology | Particles, method of producing particles, and coating material, film, and ink including particles |
| JP2011136873A (en) * | 2009-12-28 | 2011-07-14 | Tsurumi Soda Co Ltd | Vanadium dioxide fine particles, manufacturing method and thermo-chromic film |
| JP2012250879A (en) * | 2011-06-03 | 2012-12-20 | Sekisui Chem Co Ltd | Thermochromic film, interlayer for laminated glass, laminated glass and pasting film |
| WO2015030206A1 (en) * | 2013-08-30 | 2015-03-05 | 積水化学工業株式会社 | Intermediate film for laminated glass, and laminated glass |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735084A (en) * | 2018-12-29 | 2019-05-10 | 上海锦湖日丽塑料有限公司 | A kind of polycarbonate compositions of temperature-controllable and preparation method thereof |
| CN109735084B (en) * | 2018-12-29 | 2021-02-23 | 上海锦湖日丽塑料有限公司 | Temperature-controllable polycarbonate composition and preparation method thereof |
| CN116100888A (en) * | 2022-11-09 | 2023-05-12 | 慈溪市兰星塑胶实业有限公司 | Color-changing film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| WO2016152879A1 (en) | 2016-09-29 |
| JPWO2016152879A1 (en) | 2018-01-25 |
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