CN107921751A - Functional sheet - Google Patents

Functional sheet Download PDF

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Publication number
CN107921751A
CN107921751A CN201680046687.XA CN201680046687A CN107921751A CN 107921751 A CN107921751 A CN 107921751A CN 201680046687 A CN201680046687 A CN 201680046687A CN 107921751 A CN107921751 A CN 107921751A
Authority
CN
China
Prior art keywords
layer
functional sheet
functional
mold release
release film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201680046687.XA
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Chinese (zh)
Inventor
西尾昌二
小山博和
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Konica Minolta Opto Inc
Original Assignee
Konica Minolta Opto Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Opto Inc filed Critical Konica Minolta Opto Inc
Publication of CN107921751A publication Critical patent/CN107921751A/en
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation

Abstract

The technical problems to be solved of the present invention are, a kind of functional sheet is provided, it is the functional sheet of the 3-dimensional shape in the exterior face that can easily fit in application face or the vehicles of building etc., built-in face etc., the functional sheet effectively shielding ultraviolet rays or infrared ray, not irregular, defect, the generation in crack, can maintain the shielding of the ultraviolet or infrared ray for a long time.The functional sheet of the present invention, it at least has electromagnetic wave shielding performance, wherein, adhesive layer and one or more layers the functional layer at least containing electromagnetic wave shielding are sandwiched between the first mold release film and the second mold release film different from the fissility of adjacent layer.

Description

Functional sheet
Technical field
The present invention relates to a kind of functional sheet.Specifically, the present invention relates to one kind can easily fit in building The functional sheet of the 3-dimensional shapes such as the exterior faces of the application face of thing or the vehicles etc., built-in face, the functional sheet have Effect ground shielding ultraviolet rays or infrared ray, and irregular, defect and crack will not be produced, the ultraviolet or red can be maintained for a long time The shielding of outside line.
Background technology
Always into the glass pane or plastics, the glass of automobile for being about to the film containing ultraviolet light screener and being formed at building On the surfaces such as glass, so as to suppress ultraviolet to indoor, in-car injection, thus prevent article sunburn, discoloration, protect human body from Harmful ultraviolet.In addition, the film containing infrared shield agent is formed always, so that suppressing infrared ray injects room It is interior, in-car, suppress indoor or the indoor temperature of car rising.
In order to form the film containing ultraviolet light screener or infrared shield agent, generally to being combined with ultraviolet light screener Or the coating liquid of infrared shield agent, adhesive ingredients, solvent etc., it is coated using hairbrush or is sprayed using spray gun. It is coated For example, Patent Document 1 discloses following coating liquids are applied or sprayed by hairbrush etc., the coating liquid is matched somebody with somebody Conjunction has ultraviolet light screener or an infrared shield agent, and the alkoxy silane containing epoxy group and active hydrogen are contained amino Alkoxy silane reaction product as adhesive ingredients.In addition, patent document 1 describe can profit computerized control Nozzle control valve, used the spray gun controlled the open hour of spray nozzle and off-period to carry out application.
But it is not general therefore, it is necessary to using special adhesive ingredients in the method described in patent document 1 's.In addition, in embodiment, the liquid for being impregnated in non-woven fabrics is coated although describing, curing at room temperature can be with shape Into irregular, uneven color the film of coating will not be produced, still, in the patent document 1, wide not with coating area per hour Spray-coating carry out coating example, and may carry out how degree improvement it is also unclear.
Therefore, the present inventor is studied using atomized spray painting machine, is as a result distinguished：With high pressure and reducing ejection Nozzle diameter and make masking liquid ultra micro granulation spray, formed film common application under the conditions of, spray volume reduce and adjust It is whole when being desired coating weight (coating thickness), it is necessary to which multiple repetition coating, therefore, is difficult to obtain the high film of intensity.Separately Distinguish outside：According to operating environment in this case, produce and be coated with irregular, uneven color, spot, albefaction are produced on film, is lacked The problem of peculiar in spray-coating as damage, crack.
Also, for this film, in the case of being preserved under hot and humid environment, there is the stripping that film occurs Or gaps and omissions, it is impossible to the problem of chronically continuously and effectively playing ultraviolet screener performance or infrared shield performance.
On the other hand, since black combination used in the application of the instrument board of automobile is the face such as carbon or ferroso-ferric oxide Material, therefore region of ultra-red, that is, hot line is absorbed, therefore, under burning sun when, can reach a high temperature.Although as long as will be used as prevents heat Material, that is, titanium oxide of the absorption of line etc. is used for pigment, but since titanium oxide pigments are not black, for the instrument During the material of disk, exist since the problem of diffusing reflection is deteriorated so as to the visual field in front occurs.Therefore, the visual field in front is being ensured On the basis of, it is necessary to the application formed by the composition of black, in this case, it is desirable to do not absorb the application of the part of hot line.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-64308 publications
The content of the invention
The technical problems to be solved by the invention
The present invention in view of the above problems, situation and complete, its solve technical problem be, there is provided one kind can be easy Ground fits in the functional sheet of the 3-dimensional shapes such as the exterior face of application face or the vehicles of building etc., built-in face, the function Property sheet material effectively shielding ultraviolet rays or infrared ray, will not produce irregular, defect or crack, can maintain the ultraviolet for a long time Or the shielding of infrared ray.
For solving the technical solution of technical problem
In order to solve the above-mentioned technical problem the present inventor, sends out during studying the reason for the above problem etc. It is existing：There is electricity by sandwich functional property layer and adhesive layer between different 2 mold release films of the fissility in adjacent layer The functional sheet of magnetic wave shielding, can easily fit in the exterior face, built-in of application face or the vehicles of building etc. The 3-dimensional shape in face etc., effectively shielding ultraviolet rays or infrared ray, and by that will not produce irregular, defect for a long time or split Seam, can obtain being able to maintain that the functional sheet of the shielding of the ultraviolet or infrared ray.
That is, above-mentioned technical problem of the invention is solved by the following method.
1. a kind of functional sheet, it at least has electromagnetic wave shielding performance, wherein, different from the fissility of adjacent layer The first mold release film and the second mold release film between sandwich adhesive layer and at least containing electromagnetic wave shielding one or more layers Functional layer.
2. the functional sheet as described in Section 1, wherein, by first mold release film from the adjacent functional layer Required peeling force is set to Pf during upper stripping1, and when second mold release film is peeled off from the adhesive layer, is required Peeling force is set to Pf2When, meet following formula (P).
Formula (P) Pf2＜ Pf1
3. the functional sheet as described in the 2nd, wherein, in the measure under 23 DEG C, 55%RH environment, the peeling force (Pf1) it is more than 2000mN/50mm, and the peeling force (Pf2) it is below 100mN/50mm.
4. such as the functional sheet any one of the 1st~the 3rd, wherein, the electromagnetic wave shielding contains electricity Magnetic wave shielding material or electromagnetic wave shielding performance particulate, and contain adhesive resin.
5. such as the functional sheet any one of the 1st~the 4th, wherein, the electromagnetic wave shielding is shielding The layer of ultraviolet or infrared ray.
6. such as the functional sheet any one of the 1st~the 5th, wherein, with first mold release film adjoining The functional layer is the electromagnetic wave shielding.
7. such as the functional sheet any one of the 1st~the 5th, wherein, with first mold release film adjoining The functional layer is hard conating or infrared-reflecting layers.
8. such as the functional sheet any one of the 1st~the 7th, wherein, the thickness of the adhesive layer 0.5~ 10.0 in the range of μm.
9. such as the functional sheet any one of the 1st~the 8th, wherein, in first mold release film and institute State functional layer connect side surface on there is substrate layer.
The effect of invention
By the present invention above-mentioned technical proposal, can provide a kind of application face that can easily fit in building or The functional sheet of the 3-dimensional shapes such as the exterior faces of the vehicles etc., built-in face, the functional sheet effectively shielding ultraviolet rays or Infrared ray, and irregular, defect, crack will not be produced, the shielding of the ultraviolet or infrared ray can be maintained for a long time.
Effect on the present invention shows mechanism and mechanism of action, indefinite, but is presumed as follows.
The functional sheet of the present invention is characterized in that, at least functional sheet with electromagnetic wave shielding performance, its structure To have sandwiched adhesive layer between first mold release film and second mold release film different from the fissility of adjacent layer and at least having contained One or more layers functional layer of electromagnetic wave shielding, the functional sheet can easily fit in the application of building The 3-dimensional shape in the exterior faces of face or the vehicles etc., built-in face etc..
As described above, contain ultraviolet light screener or infrared ray currently in order to being formed on object article (such as glass etc.) The film of screener, generally using hairbrush coating or spray gun to being combined with ultraviolet light screener or infrared shield agent, adhesive The coating liquid of component and solvent etc. carries out application, but when using spray-coating machine, in order to be adjusted to desired coating weight, Need to be repeated several times and be coated with, therefore, be difficult to obtain the high film of intensity, additionally, there are coating is produced according to operating environment not Even, uneven color, on film produce spot, albefaction, defect, crack the problem of.In addition, for this film, in high temperature In the case of being preserved under high humidity environment, there is the stripping that film occurs or gaps and omissions, it is impossible to which chronically continuous and effective plays ultraviolet The problem of line shielding properties or infrared shield performance.
As described above, the functional sheet of the present invention is characterized by the feature piece at least with electromagnetic wave shielding performance Material, it is characterised in that be the exterior face that can easily fit in application face or the vehicles of building etc., built-in face etc. 3 Tie up the functional sheet of shape.
The functional sheet of the present invention is due to in first mold release film different from the fissility of adjacent layer and second The structure of functional property layer and adhesive layer is sandwiched between mold release film, first, even in hot and humid lower preservation functional sheet In the case of, the application to the distortional stress of functional layer can be also relaxed by 2 films, so as to suppress the crack of functional layer Generation.
Also, since the first mold release film and the second mold release film are different from the fissility of adjacent layer, thus it is speculated that being：Can So that the film in preserving vertically is disperseed by the flexible stress produced, functional layer can be suppressed and produce crack.
In addition, when the functional sheet of the present invention is fitted in article, such as second by making to abut with adhesive layer The peeling force of mold release film is smaller, and the defect of adhesive layer can be prevented when peeling off the second mold release film and exposing adhesive layer, so as to Uniformly it is bonded.
In addition, thus it is speculated that due to supporting mass when stronger first mold release film of peeling force is as fitting compared with the second mold release film Play a role, and by functional layer across on the article that the adhesive layer fits in object, therefore the equal of functional layer can be made It is bonded evenly without producing gauffer, the stripping of part or crack.
It is speculated as：After the functional sheet of the present invention has been bonded as described above, first mold release film, Ke Yisuo are peeled off State the one or more functions layer containing electromagnetic wave shielding to be sufficiently formed in as needed on the article, therefore, no Need the repetition of above-mentioned masking liquid the operation such as to be coated with, can solve to produce the irregular coating, uneven color, spot, albefaction, lack The problem of damage, crack.
In addition, the stripping of film occurs in the case of film or lacks, but it is speculated as：Due to the functional sheet of the present invention Uniform functional layer can be formed on article, therefore, generating function layer is not easy under hot and humid environment Stripping or gaps and omissions, can chronically maintain ultraviolet screener performance or infrared shield performance.
Brief description of the drawings
Figure 1A is the sectional view of the functional sheet example of the present invention；
Figure 1B is the sectional view of the functional sheet example of the present invention；
Fig. 1 C are the sectional views of the functional sheet example of the present invention；
Fig. 1 D are the sectional views of the functional sheet example of the present invention；
Fig. 1 E are the sectional views of the functional sheet example of the present invention；
Fig. 2 is the schematic diagram of example when representing to fit in the functional sheet of the present invention into article.
Description of symbols
1 first mold release film
2 functional layers
3 electromagnetic wave shieldings
3A infrared ray-absorbing layers
4 adhesive layers
5 second mold release films
6 glass
7 hard conatings
8 infrared-reflecting layers
9 resinous coats
10 functional sheets
Embodiment
The present invention functional sheet be at least have electromagnetic wave shielding performance functional sheet, it is characterised in that with Adhesive layer has been sandwiched between the fissility of adjacent layer different the first mold release film and the second mold release film and at least contains electromagnetic wave One or more layers functional layer of shielded layer.It is characterized in that the feature of the technology shared with the invention of each claim.
As embodiments of the present invention, from the viewpoint of the effect for showing the present invention, under hot and humid Preservation in can not also be produced irregular, defect, the functional layer in crack from the viewpoint of, by above-mentioned first mold release film from Required peeling force is set to Pf when being peeled off in adjacent above-mentioned functional layer1, and by above-mentioned second mold release film from above-mentioned bonding Required peeling force is set to Pf when being peeled off on layer2When, preferably Pf2＜ Pf1.In addition, will compared with the second mold release film peeling force compared with The first strong mold release film plays a role as supporting mass, and functional layer is fitted in the article of object across the adhesive layer On, therefore, being equably bonded without producing gauffer, the stripping of part or crack for functional layer can be made.
Above-mentioned peeling force (Pf1) it is more than 2000mN/50mm, and above-mentioned peeling force (Pf2) it is that below 100mN/50mm is excellent The scope of the peeling force of choosing.
In addition, go out from the viewpoint that ultraviolet-shielding type or infrared shield can be equably assigned to functional sheet Hair, above-mentioned electromagnetic wave shielding is shielding ultraviolet rays or the layer of infrared ray, and contains adhesive resin, and contains electromagnetic wave shielding Material or electromagnetic wave shielding performance particulate are preferred embodiments.
In addition, the sight from the traumatic resistance and infrared shield for improving the electromagnetic wave shielding that fitting is formed on article Point sets out, and preferably the above-mentioned functional layer with the adjoining of above-mentioned first mold release film is above-mentioned electromagnetic wave shielding, it is additionally preferred to the work( Energy property layer is hard conating or infrared-reflecting layers.
In addition, from can not produce irregular, defect when functional sheet is fitted in article, be bonded to crack Viewpoint is set out, and the thickness of above-mentioned adhesive layer is preferable mode in the range of 0.5~10.0 μm.
Also, from the concavo-convex smooth of the first demoulding film surface is made, formed from the viewpoint of uniform functional layer, preferably existed There is substrate layer on the surface of the side to connect with above-mentioned functional layer of above-mentioned first mold release film.
Hereinafter, to the present invention and its technical characteristic and for implementing the mode of the present invention, form is described in detail. It should be noted that in the application, "~" is used as lower limit and the meaning of upper limit value to contain in its front and rear described numerical value Use.
《The summary of the functional sheet of the present invention》
The present invention functional sheet be at least with electromagnetic wave shielding performance functional sheet, it is characterised in that with Adhesive layer has been sandwiched between the fissility of adjacent layer different the first mold release film and the second mold release film and at least contains electromagnetic wave One or more layers functional layer of shielded layer.
In the present invention described " electromagnetic wave shielding " refer to can by the reflection, absorption, multipath reflection of electromagnetic wave and Make the layer of electromagnetic wave attenuation.That is, make for that can be lost by reflection loss, absorption loss water or multipath reflection by the shielded layer Electromagnetic wave attenuation layer.
In the present invention, for electromagnetic wave shielding, UV-absorbing layer, ultraviolet reflecting layer, infrared ray-absorbing layer and Infrared-reflecting layers are preferable forms.
For the functional sheet of the present invention, when above-mentioned first mold release film is peeled off from adjacent above-mentioned functional layer Required peeling force is set to Pf1, and required peeling force is set when above-mentioned second mold release film is peeled off from above-mentioned adhesive layer For Pf2When, it is preferably Pf2＜ Pf1。
For the measure of the peeling force of the present invention, as performance evaluation (experiment) method of adhesive tape/sheet material, it can make With JIS Z0237：The 180 ° of stripping methods or 90 ° of stripping methods of defined in 2009.
An example ＞ of ＜ determination methods
For the pre-treatment of sample, as long as no specifying, then temperature be 23 ± 1 DEG C, relative humidity for (50 ± 5) more than when placement 24 is small in the atmosphere of the standard state of %.
The width adjustment of sample is 50mm, and length is set to 200mm.
Experimental rig uses cupping machine, uses the cupping machine or same drawing specified in JIS B 7721 Stretch testing machine.
The end of first stripping film or the second stripping film is peeled off and sandwiched from part of functions layer or adhesive layer In cupping machine, the required power peeled with draw speed 300m/min from the end peeled off along 180 ° of directions is carried out Measure.Unit is (mN/50mm).
For the present invention, in the measure under 23 DEG C, 55%RH environment, the functional layer of the first mold release film and adjoining Peeling force (Pf1) it is preferably more than 2000mN/50mm, the more preferably scope of 2000~5000mN/50mm.
Meanwhile second mold release film and adhesive layer peeling force (Pf2) it is preferably below 100mN/50mm, more preferably 30~ The scope of 100mN/50mm.
If above-mentioned peeling force (Pf1) it is more than 2000mN/50mm, and above-mentioned peeling force (Pf2) for 100mN/50mm with Under, then in hot and humid lower preservation functional sheet, the stress of the flexible generation in preservation by film can be made vertically to disperse, It can suppress the generation of the irregular of functional layer, defect, crack, in addition, when functional sheet is fitted in article, can not Produce the irregular of functional layer, defect, be bonded to crack.
The first stripping film and the second stripping film of the present invention are with the adjustment of the peeling force of adjacent layer preferably by following Method carries out.But the present invention is not limited to this.
a：Respectively to the formation functional layer on the first stripping film and the second stripping film or the aging condition after adhesive layer (temperature, humidity, time) is adjusted.
b：The face side of formation functional layer or adhesive layer to the first stripping film and the second stripping film is surface-treated. It is surface-treated as sided corona treatment, corona treatment, flame treatment, chemical conversion treatment etc..
c：The material of substrate layer to being formed on the first stripping film is suitably selected.
d：The material of adhesive layer is suitably selected.
The structure ＞ of the functional sheet of the ＜ present invention
In Fig. 1, the section view of the structure of the functional sheet of the present invention is illustrated in (A)~(E).(A)~(E) is an example Son, the present invention is not limited to this.
Fig. 1 (A) is the basic structure of the functional sheet of the present invention, and functional sheet 10 of the invention is by being adjacent to first The electromagnetic wave shielding 3 of mold release film 1 is used as functional layer 2, and adhesive layer 4 and second by being abutted with electromagnetic wave shielding 3 take off Mould film 5 is formed.The electromagnetic wave shielding 3 of the present invention is preferably UV-absorbing layer or infrared ray-absorbing layer described later.
Functional layer 2 containing one or more layers of electromagnetic wave shielding 3 by forming, as the multilayer, as an example, (in the case that (Fig. 1 (B), (D)) or electromagnetic wave shielding 3 are infrared ray-absorbing layer 3A, it can be enumerated as electricity in hard conating 7 The infrared-reflecting layers 8 (Fig. 1 (C), (D)) of one mode of magnetic wave shielded layer.
In addition, it can be set in adhesive layer for adjusting bonding force or adjusting the resinous coat 9 (Fig. 1 (E)) of peeling force.
Hereinafter, the technical characteristic of the present invention is described in detail.
[1] first mold release film and the second mold release film
As the first mold release film and the second mold release film of the functional sheet for being applicable to the present invention, from the viewpoint in operation Set out, be preferably transparent resin film.Described " transparent " refers in the present invention：On the basis of to JIS S3107 (2013) Method measure transmission of visible light, be more than 50%, be preferably more than 60%, more preferably more than 70%, particularly preferably For more than 80%.
The thickness of the first mold release film of the present invention is preferably more preferably 25~100 μm of model in the range of 20~200 μm In enclosing, in the range of more preferably 30~70 μm.If the thickness of transparent resin film is more than 20 μm, by feature Sheet material fits in the processing of the exterior face of application face or the vehicles of building etc., built-in face when above and is not likely to produce wrinkle Pleat etc., in addition, if thickness is less than 200 μm, then pair with the application face of the building or the exterior face of the vehicles etc., interior The tracing ability of curved surface when dress face paste is closed improves.As long as the thickness of the second mold release film is the model of the thickness same with the first mold release film Enclose, from the viewpoint of protectiveness and lightweight, in the range of preferably 25~100 μm.
As the first mold release film of the functional sheet for being applicable to the present invention, as long as it is transparent, without special Limitation, preferably using various resin films, such as can use polyolefin film (such as polyethylene, polypropylene etc.), polyester film (such as Polyethylene terephthalate, polyethylene naphthalate etc.), polycarbonate membrane, polyvinyl chloride, tri cellulose acetate membrane Deng, be preferably polyolefin film and polyester film, particularly preferably polyester film.
As the second mold release film, above-mentioned resin film can be similarly used, but especially because polyolefin film is light weight And also there is intensity, therefore it is preferred that.
The first mold release film of the present invention is preferably double axial orientated polyester film, but can also be used non-stretched or along at least one The polyester film that direction is stretched.Improved from intensity, from the aspect of thermal expansion suppression, preferably stretched film.It will particularly make And have the present invention functional sheet infrared shield sheet material be used for automobile front glass when, from have both curved surface tracing ability and From the viewpoint of intensity, more preferably stretched film.
For the first mold release film of the present invention, from functional sheet generation gauffer or electromagnetic wave shielding when preventing fitting From the viewpoint of producing crack, at 150 DEG C of temperature, in the range of preferably percent thermal shrinkage is 0.1~10.0%, more preferably In the range of 1.5~5.0%.
As the transparent resin film of the first mold release film and the second mold release film can by known general method come Manufacture.Such as melted as the resin of material using extruder, using annular die or T-shaped mould head extrude and rapid It is cold, it is possible thereby to manufacture the substantial unbodied non-stretched transparent resin film not being orientated.Furthermore it is possible to utilize single shaft Stretching, stenter formula is gradually biaxial stretch-formed, method edge known to stenter formula simultaneously biaxial drawing, tubular type simultaneously biaxial drawing etc. Flowing (longitudinal axis) direction of transparent resin film or flow direction (transverse axis) direction at a right angle with transparent resin film, to non-stretched Transparent resin film stretched and manufacture stretching transparent resin film.In this case draw ratio can be according to as transparent tree The resin of the raw material of adipose membrane suitably selects, but distinguishes preferably 2~10 times along y direction and along X direction.
In addition, for transparent resin film, in terms of the dimensional stability on can carry out relaxation processes, heat-treated offline. Relaxation processes preferably by above-mentioned polyester film after heat fixation has been carried out in stretching film making process until drawing stretching in the transverse direction The process of the winding carried out after being come out in width machine or from stenter carries out.Relaxation processes are 80~200 DEG C preferably in treatment temperature Lower progress, more preferably treatment temperature are 100~180 DEG C.Additionally, it is preferred that on longitudinal direction, width relaxation rate be 0.1 Carried out in the range of~10%.Base material after relaxed processing is improved by implementing heat-treated offline, heat resistance.
The present invention functional sheet preferably on the first stripping film have substrate layer (also referred to as smooth layer, priming coat, easily Adhesive linkage).It is for the asperities of the film there are projection etc. of substrate layer to be planarized, or for utilizing film to set substrate layer Present on projection the bumps produced in functional layer or pin hole are filled and planarized.This substrate layer can be by any Material is formed, but preferably comprises carbon containing polymer, is more preferably made of carbon containing polymer., can as carbon containing polymer Enumerate：Polyester resin, acrylic acid modified polyester resin, polyurethane resin, acrylic resin, vinylite, inclined two chloroethene Olefine resin, polyethyleneimine vinylester resin, polyethylene imine resin, polyvinyl alcohol resin, modified polyvinylalcohol resin etc..
In addition, substrate layer preferably comprises curable resin.As curable resin, it is not particularly limited, can enumerates to work Property the irradiation ultraviolet isoreactivity energy line such as energy line curable material make its cure obtained from active energy ray-curable tree Fat；Or heat-curing resin etc. as obtained from heating thermoset materials and cured.Curable resin can individually make With can also combine two or more and use.
As the active energy ray-curable material for forming substrate layer, specifically, JSR Corp. can be used Compound hard material OPSTAR (registration mark) series that applies of UV curing type organic/inorganics of manufacture (is bonded on a silica particle The compound that organic compound with polymerism unsaturated group forms).In addition, as thermoset materials, specifically, It can enumerate：Coat plants of the Tutto prom serial (organopolysilazane) of Clariant Co., Ltd. manufacture, Ceramic formula meetings The SP COAT heat-resisting transparent coatings of society's manufacture, the nano combined polysiloxanes of ADEKA societies manufacture, Dainippon Ink Chemicals manufacture UNIDIC (registration mark) V-8000 series, EPICLON (registration mark) EXA-4710 (superelevation heat-resistance epoxy resin), SHIN-ETSU HANTOTAI The polyorganosiloxane resin X-12-2400 (trade name) of chemical industry Co., Ltd. manufacture, the nothing of Nitto Boseki Co. Ltd's manufacture Machine/organic nanocomposite SSG coatings, the Thermocurable polyurethane formed by acrylic polyol and isocyanate prepolymer Resin, phenolic resin, urea melamine, epoxy resin, unsaturated polyester resin, polyorganosiloxane resin, daiamid- Epichlorohydrin resins etc..
The flatness of substrate layer is with JIS B 0601:The value that surface roughness as defined in 2001 shows, maximum section are high In the range of degree Rt (p) is preferably 10~30nm.
For surface roughness, by using atomic force microscope (Atomic Force Microscope：AFM), And calculated by the concavo-convex section curve that the detector using the contact pilotage with minimum tip radius is continuously measured, and Above-mentioned surface roughness is repeatedly to be measured in tens of μm of section to measure direction using the contact pilotage of minimum tip radius, is The roughness related with fine concavo-convex amplitude.
Known additive can be added in substrate layer.Moreover, above-mentioned substrate layer can pass through roller coat, intaglio plate Method known to coating, cutter painting, dip-coating, spraying etc. is coated.As the coating weight of above-mentioned substrate layer, be preferably 0.01~ 2g/m2(drying regime) left and right.
As the thickness of substrate layer, it is not particularly limited, but in the range of preferably 0.1~10 μm.
[2] functional layer
The functional layer of the present invention refer to using electromagnetic wave shielding as necessary structure one or more layers.
Electromagnetic wave shielding is preferably following layer：Containing electromagnetic shielding material or electromagnetic wave shielding performance particulate, and contain There is adhesive resin, so as to have the function of to absorb or reflect ultraviolet or infrared ray and shielded, particularly preferably absorb Infrared ray and the infrared ray-absorbing layer shielded.
The present invention electromagnetic wave shielding performance layer it is preferably transparent, if transparent, then above-mentioned automobile black instrument When being bonded the electromagnetic wave shielding performance layer of the present invention on disk, do not hinder to become black, instrument board can be suppressed and absorb hot line.
" transparent " refers to：Electromagnetic wave shielding performance layer as on the basis of JIS S3107 (2013) method measure can It is more than 50% to see light transmission, is preferably more than 60%, more preferably more than 70%, particularly preferably more than 80%.
In addition, as the functional layer beyond electromagnetic wave shielding, can enumerate：Hard conating, resinous coat, conductive layer, Antistatic backing, gas barrier layer, stain-proofing layer, smelly eliminating layer, stream drop layer, slippery layer, abrasion resistence layer, protective layer, separating layer, printing layer, Luminescent layer, holographic layer etc., wherein, from the viewpoint of the protective layer as functional layer works, preferably hard conating is matched somebody with somebody It is placed in the face side of electromagnetic wave shielding.
[2.1] ultraviolet screener layer
For the ultraviolet screener layer (also referred to as UV-absorbing layer) of the present invention, preferably can be used for it is described later In the adhesive resin of infrared ray shielding layer, to being dispersed or dissolved as the ultra-violet absorber of electromagnetic shielding material and The layer contained, it is the feature for having the function of that the light of optical wavelength 200~350nm scopes is absorbed and shielded Layer.
As ultra-violet absorber, as inorganic UV absorber, can enumerate：Titanium oxide, zinc oxide, cerium oxide, Iron oxide etc..In addition, as organic ultra-violet absorber, can enumerate：Benzophenone, benzotriazole, phenyl salicylate Class and triazine-based ultraviolet absorbent etc..
In the present invention, from the viewpoint of long-term ultraviolet shielding effect is obtained, preferably using will not ooze out and The inorganic UV absorber that will not be distilled during shaping.
It is high from being assigned to functional sheet preferably using titanium oxide or zinc oxide as inorganic UV absorber From the viewpoint of transmissivity, particulate titanium dioxide or particulate zinc oxide in the range of being 5~50nm preferably using average grain diameter.
As above-mentioned particulate titanium dioxide or particulate zinc oxide, as the example of commercially available product, can enumerate：Stone originates in industry strain formula meeting The particulate titanium dioxide TTO serial (TTO-51 series, TTO-55 series, TTO-F series, TTO-W-5 etc.) and C.I.ization of society's manufacture Ultraviolet screener master batch of the ZnO containing ultra micron into Co., Ltd.'s manufacture etc..
As organic ultra-violet absorber, that is, benzophenone ultraviolet absorbent, can enumerate for example：2,4- dihydroxy- Benzophenone, 2-Hydroxy-4-methoxy-benzophenone, 2- hydroxyls -4- n-octyloxies-benzophenone, 2- hydroxyl -4- dodecanes Epoxide-benzophenone, 2- hydroxyls -4- octadecane epoxides-benzophenone, 2,2 '-dihydroxy -4- methoxy-benzophenones, 2, 2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2,2 ', 4,4 '-tetrahydroxy-benzophenone etc..
As Benzotriazole Ultraviolet Stabilizer, can enumerate for example：2- (2 '-hydroxy-5-methyl base phenyl) benzotriazole, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl phenyl) benzotriazole, 2- (2 '-hydroxyl -3 '-tert-butyl group -5 '-aminomethyl phenyl) benzo Triazole etc..
As phenyl salicylate class ultra-violet absorber, can enumerate for example：Phenyl salicylate, 2-4- di-t-butyls phenyl- 3,5- di-t-butyl -4-HBA esters etc..As hindered amines ultra-violet absorber, double (2,2,6,6- tetramethyls can be enumerated Phenylpiperidines -4- bases) sebacate etc..
As triazine-based ultraviolet absorbent, can enumerate for example：2,4- diphenyl -6- (2- hydroxyl -4- methoxyphenyls) - 1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- ethoxyl phenenyls) -1,3,5- triazines, 2,4- diphenyl-(2- hydroxyls - 4- propoxyphenyls) -1,3,5- triazines, 2,4- diphenyl-(2- hydroxyl -4- butoxy phenyls) -1,3,5- triazines, 2,4- hexichol Base -6- (2- hydroxyl -4- butoxy phenyls) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- Hexyloxy-phenyls) -1,3, 5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- octyloxyphenyls) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyls -4- Dodecyloxy phenyl) -1,3,5- triazines, 2,4- diphenyl -6- (2- hydroxyl -4- benzyloxy-phenyls) -1,3,5- triazines etc..
The usage amount of ultra-violet absorber relative to ultraviolet screener layer gross mass 0.1~20 mass % scope It is interior, it is preferably in the range of 1~15 mass %, is more preferably in the range of 3~10 mass %.By the way that usage amount is set to these In the range of, the adaptation with other structures layer can be kept well, improve weatherability.
As the wet coating mode of the formation for ultraviolet screener layer, it is not particularly limited, such as can suitably makes With No. 2761419 rolling method, stick coating method, air knife coating process, spray application method, sliding-type curtain coating method or U.S. Patent No. explanations Sliding hopper rubbing method, extrusion coating method described in No. 2761791 book, U.S. Patent No. specifications etc. etc..
The dried thickness of ultraviolet screener layer is preferably set to the thickness same degree with infrared ray shielding layer described later.
[2.2] infrared ray shielding layer
The infrared ray shielding layer of the present invention preferably mainly has the near infrared ray to the scope of 700~2500nm of optical wavelength The light functional layer of function that is absorbed and shielded.
The infrared ray shielding layer is preferably the infrared ray-absorbing layer containing infrared ray-absorbable particulate and adhesive resin, is made For above-mentioned infrared ray-absorbable particulate, preferably using ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide) and tungsten oxide Deng, from infrared shield, the transparency from the viewpoint of, more preferably use the infrared ray-absorbable particulate as tungsten oxide.
In addition, the preferred luminous ray transmissivity of infrared ray shielding layer of the present invention is more than 70% and infrared shield rate For more than 70% infrared ray shielding layer.
[infrared ray-absorbable particulate]
Infrared ray-absorbable particulate is with absorption, special with optical absorption near infrared ray~IR wavelength domain The compound particles of property, it is however generally that, the metal oxide particle such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide) is It is well-known.
As the infrared ray-absorbable particulate for the present invention, from luminous ray transmissivity, near infrared ray absorbing, setting The viewpoints such as the scattered adaptive in fat are set out, and are preferably metal oxide particle, can be enumerated for example：Tin oxide, zinc oxide, oxidation Titanium, tungsten oxide and indium oxide etc..As the concrete example of hot line absorbing particle, aluminium doped stannum oxide particle, indium doping are preferably comprised Tin oxide particles, antimony-doped tin oxide (ATO) particle, Ga-doped zinc oxide (GZO) particle, indium doping zinc oxide (IZO) particle, Aluminium-doped zinc oxide (AZO) particle, niobium adulterated TiOx particle, tin-doped indium oxide (ITO) particle, tin mixed with zinc oxide grain Son, silicon doped zinc oxide particles, formula MxWyOz(wherein, M be selected from H, He, alkali metal, alkaline-earth metal, rare earth element, Mg, Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、 F, more than a kind of element in P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W are tungsten, and O is oxygen, 0.001≤x/y≤1,2.2 ＜ z/y≤3.0) represent compound tungsten oxide particulate and general formula X B6(wherein, element X is choosing From at least one or more in La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr or Ca) represent 6 boron The particulate of compound.
Wherein, preferably tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), the tungsten oxide (Cs containing caesium0.33WO3) etc.. These materials can be used alone or combine two or more and use.
Alternatively, it is also possible to using the infrared absorbing material of organic matter, enumerate at the same time：Polymethine class, phthalocyanines, naphthalene cyanines Class, metal complex species, aluminium class, imines, diimine class, Anthraquinones, dithiol metal complex class, naphthoquinones class, indoles Phenol, azo, the compound etc. of triallyl methane class.Particularly preferably using metal complex species compound, aluminium class Compound (aluminium derivative), phthalocyanine-like compound (phthalocyanine derivates), naphthalene cyanine compound (naphthalene cyanines derivative), diimine class Compound (diimine derivative), Si Kualin classes compound (Si Kualin derivatives) etc..
Infrared ray shielding layer as functional layer preferably comprises the metal oxide and gold with infrared ray absorbing What is belonged to is at least one kind of, and the transparent layer containing adhesive resin.As having the function of the material of infrared ray absorbing, it is known that There is compound system of above-mentioned ITO or ATO, aluminium-doped zinc oxide or zinc oxide/silver/zinc oxide etc..In general, with ITO or ATO Based on oxide semiconductor material there is the property that is reflected of light for contrasting certain wavelength length.Certain wavelength is referred to as Gas ions vibration number, illustrates as follows.That is, in the case of there are the electric conductor of free electron, the material of electroneutral is kept Cause the change of charge density due to incident light and vibrated back to generation during neutrality, thus, low vibration number, that is, long wavelength The light of side can not be invaded to be reflected in material, only the light projection of short wavelength side.But just conventional ITO or ATO powder and Speech, it is 2 μm or so to cause the wavelength that the plasma vibrates, and can not reflect the near infrared region close to visible range in this region The light in domain is closer to visible range, it is necessary to make reflectivity rise (shielding wavelength).Remember in Japanese Unexamined Patent Publication 7-70363 publications The raising of electron density for carrying out block itself or the stabilisation of particle surface are loaded with, makes shielding wavelength and conventional ito powder phase Ito powder than being transferred to more than 1 μm visible range side (it is less than 1 μm to shield wavelength) is scattered in the visible range in organic resin Transmissivity be more than 80%, and the example of the film of near infrared ray can be effectively shielded, in the present invention it is also preferred that making With the ito powder.For ITO the or ATO powder used in the present invention, examined in terms of infrared ray absorbing function, the transparency Consider, preferably averagely 1 particle diameter is the material of below 200nm, and shields the material that wavelength is below 1000nm.
As scattered adhesive resins such as above-mentioned ITO or ATO powder, can enumerate：Acrylic resin, polyester tree Fat, acrylic acid modified polyester resin, polycarbonate resin, polyurethane resin, melmac, alkyd resin, epoxy resin, Vinyl chloride resin, polyvinyl alcohol resin, modified polyvinylalcohol resin, polyvinyl acetal-based resin, polyvinyl butyral resin tree Fat or the hard paint of ultraviolet curing etc., can use the one or more of these materials.Also, these can also be used Resin beyond material.
In addition, within the scope of the effect of the invention, it can make as needed in adhesive resin containing addition Agent etc..For example, dispersant, plasticizer, ultra-violet stabilizer, surfactant, antioxidant, fire retardant, anti-corrosion can be contained Agent, antioxidant, heat stabilizer, lubricant, filler, photoinitiator, photosensitizing agent, thermal polymerization, tackifier, coupling The additive such as agent, antistatic agent, levelling agent, bonding regulator, modifying agent or dyestuff or pigment for assigning arbitrary tone. These a kind of materials can be used, can also combine two or more and use.
The ratio of containing ratio or ITO or ATO powder and adhesive resin with regard to ITO the or ATO powder in infrared ray shielding layer It is more from the ratio relative to adhesive resin, these metal oxides for rate, then examined in terms of the more rise of hot line rejection effect Consider, the containing ratio of ITO or ATO powder is preferably the scope of 50~90 mass % or 60~80 mass %, ITO or ATO powder and The ratio of adhesive resin is preferably 1/1~9/1 or 6/4~8/2 scope by quality ratio.
In the present invention, in addition to above-mentioned ITO or ATO, preferably using LaB6(lanthanum hexaboride), CWO (composite tungstens containing caesium Oxide), wherein, the tungsten oxide absorbed preferably using the wide width to infrared spectral range, particularly more than wavelength 1000nm Or at least one of compound tungsten oxide.
In tungsten oxide, since effective free electron being not present in tungstic acid, tungstic acid is near red The absorption reflection characteristic in outside line region is few, is not effective as infrared ray-absorbable particulate.On the other hand, it is known to The so-called wolframic acid alkali metal salt of positive element added with Na etc. in the tungstic acid or tungstic acid of oxygen defect is electric conductivity Material, and be the material with free electron, implied by the analysis of the single crystals of these materials etc. to infrared spectral range The response of the free electron of light.Moreover, exist in the specific part of compositing range in the compound of tungsten and oxygen as infrared The particularly effective scope of line absorption particulate, it was found that be transparent in visible region and have near infrared range Tungsten oxide particle, the composite tungsten oxide particle of absorption, can be by the tungsten oxide particle or/and composite tungsten oxide particle As infrared ray-absorbable particulate.
Above-mentioned tungsten oxide can be enumerated with general formula WyOz(wherein, W is tungsten, and O is oxygen, 2.2≤z/y≤2.999) statement Compound, above-mentioned compound tungsten oxide, which can be enumerated, uses formula MxWyOz(wherein, M be selected from H, He, alkali metal, alkaline-earth metal, Rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, More than a kind of element in Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, and O is oxygen, 0.001≤x/y≤1,2.2≤z/y≤3)) compound of statement.
Above-mentioned compound tungsten oxide formula MxWyOzRepresent, due in the crystallization with hexagonal crystal, regular crystal, cubic crystal Excellent in te pins of durability in the case of structure, it is therefore preferable that containing selected from one or more of the hexagonal crystal, regular crystal, cubic crystal Crystalline texture.Wherein, hexagonal crystal due to the absorption of visible region it is minimum, particularly preferably.For example, being used as has hexagonal crystal Crystalline texture combined oxidation tungsten, can enumerate as preferable M element, containing selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, The compound tungsten oxide of more than a kind of element in each element of Sr, Fe, Sn.In the present invention, as combined oxidation tungsten, from The viewpoint such as infrared shield characteristic and weatherability is set out, the compound tungsten oxide preferably containing caesium.
The value of the x/y for the additive amount for representing element M is illustrated.
If the value of x/y is more than 0.001, an adequate amount of free electron can be generated and obtain infrared ray as a purpose Shield effectiveness.Moreover, the additive amount of element M is more, the quantity delivered of free electron more increases, and infrared shield efficiency also rises, But the value of x/y is 1 or so, the effect saturation.In addition, if the value of x/y is less than 1, then can be to avoid in the infrared ray-absorbable Impurities phase is generated in particulate, therefore preferably.
In the following, the value of z/y of the control to representing oxygen amount illustrates.
On the value of z/y, with MxWyOzIn the infrared ray-absorbable particulate of statement, and with above-mentioned WyOzThat states is infrared The same mechanism of line absorption particulate works, in addition, in z/y=3.0, due to there is the addition based on above-mentioned element M The supply of the free electron of amount, is more preferably 2.45≤z/y≤3.0 it is therefore preferable that being 2.2≤z/y≤3.0.
The particle diameter of above-mentioned infrared ray-absorbable particulate can each be selected according to its application target.It should be noted that The measure of average grain diameter is shot using infiltration type electron microscope, is randomly extracted such as 50 particles out and is measured the grain Footpath, carries out it value of average gained.In addition, in the case where the shape of particle is not spherical, it is defined as measure major diameter and calculates The value gone out.
First, in the case of the application for maintaining the transparency, the particle diameter preferably with below 800nm.This be because For the particle less than 800nm will not shield light completely due to scattering, can keep the visuality of visible ray regions, together When effectively keep the transparency.Particularly in the case where paying attention to the transparency of visible region, particle is further preferably considered Caused scattering.When paying attention to the reduction of scattering caused by the particle, particle diameter is below 200nm, preferably below 100nm.Should Reason is because particle diameter is smaller, due to geometry scattering or the luminous ray area of 400~780nm of wavelength of Michaelis diffusing scattering The scattering of the light in domain is reduced, as a result, can to avoid the light caused by particle scattering and infrared ray shielding layer becomes frosted glass, So as to which the transparent phenomenon of distinctness can not be obtained.That is, this is because, when particle diameter is below 200nm, the scattering of above-mentioned geometry or Michaelis diffusing scattering is reduced, and becomes Rayleigh scattering region.In Rayleigh scattering region, 6 powers for scattering light and particle diameter are inversely proportional And reduce, therefore, reduction is scattered with the reduction of particle diameter, the transparency improves.Also, when preferable particle size becomes below 100nm, dissipate Light is penetrated to tail off very much.From the viewpoint of the scattering for avoiding light, preferable particle size is small, but if particle diameter is more than 1nm, then industry is made Make easily.
By by above-mentioned below particle diameter selected as 800nm, making infrared ray-absorbable particulate be scattered in the media such as resin The haze value of infrared ray shielding layer can be adjusted to mist degree below 30% in transmission of visible light below 85%.Here, mist degree is During value more than 30%, become frosted glass, the transparency of distinctness can not be obtained.
In the present invention, as infrared ray-absorbable particulate, a kind of above-mentioned tungsten oxide or above-mentioned composite tungsten can be used Oxide, can also combine two or more and use.Furthermore, it is possible to titanium oxide, cerium oxide, indium oxide, zinc sulphide, oxidation Zinc, ATO and ITO etc. have the compound particles combination of optical absorption characteristic and use.
From the viewpoint of weatherability or dispersiveness, the surface of preferably infrared ray-absorbable particulate is overall or a part by containing The oxide for having more than a kind of Si, Ti, Zr, Al of metal is coated.Method for coating is not particularly limited, but by point The alkoxide that above-mentioned metal is added in the solution for having the infrared ray-absorbable particulate is dissipated, can be to the surface of infrared ray-absorbable particulate Coated.
Additionally, it is preferred that suppress the infrared shield characteristic of infrared ray shielding layer through reduction after a while, improve Metal salt is added under the purpose of weatherability.
Be suitable for the invention metal salt be by selected from alkali metal, alkaline-earth metal, nickel, manganese, cerium, zinc, copper, cobalt, zirconium, iron, The metal organic salt or metal inorganic salt that metallic element in tin and aluminium is formed, can use these a kind of materials, can also group Close two or more and use.
In the present invention, for the content of metal salt contained in infrared ray shielding layer, from compatibility, dispersiveness, mist From the viewpoint of degree, relative to 100 mass parts of infrared ray-absorbable particulate, in the range of being preferably 5~60 mass parts, further In the range of preferably 10~40 mass parts.If it is more than 5 mass parts, infrared shield characteristic can be adequately suppressed Through reduction after a while, within 60 mass parts, then moldable resin or excellent in compatibility with solvent, production The raising of raw dispersiveness and the reduction of mist degree.
, can be without special for solvent in the case that the infrared ray-absorbable particulate of the present invention is set to dispersion liquid Limit ground and use known organic solvent.
Specifically, can enumerate：Methanol (MA), ethanol (EA), 1- propyl alcohol (NPA), isopropanol (IPA), butanol, penta The alcohols solvents such as alcohol, benzylalcohol, diacetone alcohol；Acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methylisobutylketone (MIBK), The ketones solvents such as cyclohexanone, isophorone；The esters solvents such as 3- methyl-methoxy-propionic acid ester (MMP)；Glycol monoethyl ether (MCS), ethylene glycol monoethyl ether (ECS), ethylene glycol isopropyl ether (IPC), methyl proxitol (PGM), propylene glycol ethylether (PE), the diol, derivatives such as propylene glycol methylether acetate (PGMEA), propylene glycol ethyl ether acetic acid esters (PEAC)；Formamide (FA), the acid amides such as N-METHYLFORMAMIDE, dimethylformamide (DMF), dimethylacetylamide, n-methyl-2-pyrrolidone (NMP) Class；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Halogenated hydrocarbons such as ethlyene dichloride, chlorobenzene etc..Wherein, preferred low organic molten of polarity Agent, the particularly more preferably glycol ethers second such as aromatic hydrocarbon, PGMEA, PE-AC such as the ketone such as MIBK, MEK or toluene, dimethylbenzene The high material of the hydrophobicitys such as esters of gallic acid.These solvents can use a kind or combine two or more and use.
[forming method of infrared ray shielding layer]
As an embodiment of the infrared ray shielding layer for forming the present invention, add in solvent and be dispersed with infrared ray absorbing Dispersion liquid and adhesive resin, metal salt, other additives of property particulate etc. and prepare moldable resin composition, can by this Thermoplastic resin composition is coated in the first demoulding film surface of the present invention and forms coated film, and makes evaporation of the solvent from the coated film And the method formed.At this time, since the coated film of uniform infrared ray shielding layer can be formed, therefore it is preferred that in the first mold release film table Face forms above-mentioned substrate layer.Furthermore it is possible to above-mentioned surface treatment is carried out to the first demoulding film surface.
As the coating method of moldable resin composition, as long as coating can uniformly be formed in the first mold release film Film, is not particularly limited, and can use stick coating method, gravure coating method, spraying process, dip coating etc..
As the dried thickness of infrared ray shielding layer, average layer thickness in the range of 0.1~50 μm, be preferably 1~ In the range of 30 μm, in the range of particularly preferably 2~20 μm.If thickness is more than 0.1 μm, can play infrared ray The degree of absorbability contains infrared ray-absorbable particulate, if it is less than 50 μm, the resistance to Fractured of film improves.Cause This, in the case of containing a effective amount of infrared ray-absorbable particulate for shielding infrared ray, as film, preferably has sufficiently resistance to Long property, and it is appropriately designed not have the degree of crannied generation to carry out.
[2.3] with UV-absorbing layer, infrared ray-absorbing layer functional layer used at the same time
As with above-mentioned electromagnetic wave shielding (UV-absorbing layer, infrared ray-absorbing layer) functional layer used at the same time, Preferable hard conating and infrared-reflecting layers in the present invention are illustrated.
[hard conating]
The hard conating of the present invention refers to the layer that pencil hardness is H~8H.In the range of particularly preferably 2H~6H.
Pencil hardness be by the hard conating of making when damping 2 is small under conditions of 25 DEG C of temperature, relative humidity 60% after, make The experiment pencil as defined in JIS S 6006, is measured and obtains according to evaluating pencil hardness method as defined in JIS K 5400 The value arrived.
As the moldable resin for hard conating, can enumerate：Polysiloxane-based, melamine class, epoxies, acrylic acid The organics such as esters, multifunctional (methyl) acrylic compounds apply material firmly；The inorganics such as silica apply material etc. firmly.Its In, from the viewpoint of bonding force is good, productivity is excellent, preferably using (methyl) esters of acrylic acid, multifunctional (methyl) third Hard apply of alkene acid compounds forms material.Here, (methyl) acrylic acid represents acrylic acid and methacrylic acid.
In addition, in hard conating, high marresistance, is preferably carried out cured with passing through cross-linking reaction in order to obtain Resin is the layer of main component, more preferably active wire solidified resin.
As above-mentioned active wire solidified resin, preferably using ultraviolet curable resin.As uv curing resin, do not have It is particularly limited to, such as can be from Adeka Optomer KR, the Adeka Optomer KR- of Adeka Optomer BY series 400、Adeka Optomer KR-410、Adeka Optomer KR-550、Adeka Optomer KR-566、Adeka Optomer KR-567, Adeka Optomer BY-320B (more than, (strain) ADEKA manufacture), KOEIHARD A-101-KK, A-101-WS、C-302、C-401-N、C-501、M-101、M-102、T-102、D-102、NS-101、FT-102Q8、MAG-1- P20, AG-106, M-101-C (more than, wide honor chemical industry (strain) manufacture), PHC2210 (S), the PHCX-9 (K- of SEIKABEAM 3)、PHC2213、DP-10、DP-20、DP-30、P1000、P1100、P1200、P1300、P1400、P1500、P1600、SCR900 (more than, industrial (strain) manufacture of refining big day), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (more than, Daicel Allnex (strain)), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (more than, DIC (strain) manufactures), AULEX No.340clear (Network リ ヤ) (Chinese coating (strain) manufacture), SUNRAD H-601R (make by Sanyo's chemical conversion industry (strain) Make), SP-1509, SP-1507 (more than, Showa macromolecule (strain) manufacture), RCC-15C (Grace Japan (strain) manufactures), Aronix M-6100, Aronix M-8030, Aronix M-8060 (more than, East Asia synthesis (strain) manufacture) are or other commercially available Suitably select and utilize in material.
For the coating composition of ultraviolet curable resin layer, solid component concentration is preferably the model of 10~95 mass % In enclosing, appropriate concentration is selected according to coating method.
As for by uv curing resin by photocuring reaction and formed cure by the light source of film layer, as long as The light source of ultraviolet is produced, can be used.Specifically, above-mentioned light source can be used.
Irradiation condition is different because of respective lamp, and irradiate light quantity is 20~1200mJ/cm2Left and right, preferably 50~ 1000mJ/cm2., can be by using having absorption maximum in this region near ultraviolet ray region into visible ray regions Sensitizer and use.
As the dried thickness of hard conating, average layer thickness is preferably 1~20 μm in the range of 0.1~30 μm In the range of, in the range of particularly preferably 3~15 μm.In the case that it is more than 3 μm, sufficient durability, resistance to punching can obtain Hitting property.It it is preferably less than 15 μm in addition, from the viewpoint of bendability or economy.
For the formation of hard conating, it can be formed as follows：Such as organic solvent is dissolved in active wire solidified resin Obtained from hard conating formation be coated with coating fluid, then, irradiate active wire in drying or after dry.Applied as hard The coating method of layer coating composition, is not particularly limited, and can use such as gravure coating machine, dip coating machine, reverse painting Method known to applying machine, bar coating machine, dispensing coating machine, ink-jet method etc. is coated with.Exist preferably using above-mentioned coating method On one surface of moldable resin base material, it is coated in the range of 0.1~100 μm of wet layer thickness.
In addition, hard conating can be 1 layer, or more than 2 layers of sandwich construction.
In addition, in order to assign anti-glare to hard conating, in addition to preventing and the closely sealed of other materials and improving scratch resistance Property etc., inorganic or organic particulate can also be added in the coating composition of hard conating.
As the average grain diameter of fine-particle powder, in the range of 0.01~10 μm, for usage amount, coordinated, it is excellent Phase selection is for 100 mass parts of ultraviolet curable resin composition, in the range of 0.1~20 mass parts.In order to assign anti-dazzle effect Fruit, 0.1~1 μm of the average grain diameter of 1~15 mass parts is used preferably with respect to 100 mass parts of ultraviolet curable resin composition In the range of particulate.
In order to improve the heat resistance of hard conating, can select not suppressing the antioxidant of photocuring reaction and use.Can be with Enumerate for example：Hindered phenol derivative, propane thioic acid derivative, phosphite derivative thing etc..Specifically, for example,： 4,4 '-thiobis (6- tert-butyl group 3- methylphenols), 4,4 '-butane double (the 6- tert-butyl group -3- methylphenols), 1,3,5- tri- (3,5- di-t-butyl -4- hydroxybenzyls) isocyanuric acid ester, 2,4,6- tri- (3,5- di-t-butyl -4- hydroxybenzyls) equal front three Benzene, two-octadecyl -4- hydroxyl -3,5- di-t-butyl benzylphosphates etc..
Solvent can be contained in hard coat layer coating solution, can be as needed suitably containing solvent so as to be diluted Material.
As organic solvent contained in coating fluid, such as can be from hydro carbons (toluene, dimethylbenzene), alcohols (methanol, second Alcohol, isopropanol, butanol, cyclohexanol), ketone (acetone, methyl ethyl ketone, methylisobutylketone), esters (methyl acetate, acetic acid second Ester, methyl lactate), glycol ethers, suitably select in other organic solvents, or these material mixings are utilized.Preferably using Containing propylene glycol monoalkyl ether (carbon number as alkyl is 1~4) or propylene-glycol monoalky lether acetic acid esters (as alkyl Carbon number be 1~4) etc. more than 5 mass %, the above-mentioned organic solvent in the range of more preferably 5~80 mass %.
For hard conating, JIS B 0601 can be formed:The arithmetic average roughness Ra of defined is less than in 2013 0.05 μm, more preferably less than 0.002~0.04 μm of the hard conating with good even surface.
Arithmetic average roughness (Ra) is preferably measured with the surface roughness measurement device of light interference type, such as can be made The non-planar contact surfaces fine shape measuring device (WYKONT-2000) manufactured with WYKO companies is measured.
In addition, as the material for playing the function that prevents adhesion, the component identical with above-mentioned component can be used, i.e., using phase It is minimum in the range of 0.005~0.1 μm of the volume average particle size of 0.1~5 mass parts for 100 mass parts of resin combination Particulate.
Can be hydrophilic by known thermoplastic resin, heat-curing resin or gelatin etc. in the hard conating for the present invention The adhesives such as property resin are mixed and used with above-mentioned active energy line curing resin.These resins preferably have pole in the molecule thereof Property group.As polar group, can enumerate：-COOM、-OH、-NR2、-NR3X、-SO3M、-OSO3M、-PO3M2、-OPO3M ( This, M represents hydrogen atom, alkali metal or ammonium, and X represents to form the acid of amine salt, and R represents hydrogen atom, alkyl) etc..
In addition, having carried out the heat resistance of cured layer to improve, can select that the antioxygen of photocuring reaction will not be suppressed Agent and use.For example,：Hindered phenol derivative, propane thioic acid derivative, phosphite derivative thing etc..It is specific and Speech, for example,：4,4 '-thiobis (6- tert-butyl group 3- methylphenols), 4,4 '-butylidenebis (the 6- tert-butyl group -3- methyl Phenol), 1,3,5- tri- (3,5- di-t-butyl -4- hydroxybenzyls) isocyanuric acid ester, (the 3,5- di-t-butyl -s 4- of 2,4,6- tri- Hydroxybenzyl) mesitylene, two (octadecyl) -4- hydroxyl -3,5- di-t-butyl benzylphosphates etc..
In addition, in the hard conating of the present invention, can within the scope of the effect of the invention, further according to need Coordinate various additives.Such as antioxidant, ultra-violet stabilizer, ultra-violet absorber, surfactant, stream can be used Flat agent, antistatic agent etc..
[infrared-reflecting layers]
As the electromagnetic wave shielding of the present invention, preferably infrared-reflecting layers are used together with above-mentioned infrared ray-absorbing layer.
As the infrared-reflecting layers, it is not particularly limited, can uses No. 6049419 explanations of U.S. Patent Application No. Commercially available infrared reflection film (3M SCOTCHTINT (registration mark) MultiLayer of 3M companies manufacture described in book NANO series：There is the transparent infrared reflection of the light transmission less than 20% in the range of 850~1100nm of optical wavelength Film) or Japanese Unexamined Patent Publication 2012-81748 publications record multilayer film (make the thermoplastic of more than two kinds with different optical properties Property resin alternately each more than 50 layers films formed of lamination.Average reflectance under 400~700nm of optical wavelength is less than 15%, And the average reflectance under 900~1200nm of optical wavelength is more than 70%), or contain Japanese No. 2012/057199 publication of table again The metal oxide of record and the high refractive index layer of adhesive and the low-index layer near infrared ray that alternately lamination multilayer forms Reflectance coating etc..
Wherein, as infrared-reflecting layers, it is however preferred to have the reflecting layer of the sandwich construction of following laminated construction：It will contain At least more than 3 layers of the high refractive index layer and low-index layer lamination of metal oxide and adhesive.Infrared-reflecting layers it is preferred Form have the form of low-index layer and the high refractive index layer alternately alternating layer laminate that lamination forms.
It should be noted that in this specification, high index of refraction will be known as relative to the high layer of the opposing party's refractive index refractive index Layer, will be known as low-index layer relative to the low index layer of the opposing party's refractive index.
Also, as the optical characteristics of infrared-reflecting layers, the transmission of the visible region shown in JIS R3106-1998 Rate is preferably more than 50%, is preferably more than 75%, and more preferably more than 85%, additionally, it is preferred that 900~1400nm's of wavelength There is the region more than reflectivity 50% in region.
As the material for forming infrared-reflecting layers, known material can be used, can be enumerated for example：Metal aoxidizes Thing particle, polymer and combinations thereof etc..At least any layer of low-index layer and high refractive index layer preferably comprises metal Oxide particle, contains metal oxide particle more preferably two layers.
Example of the metal oxide particle as high-index material, can enumerate titanium dioxide (TiO2), zirconium dioxide (ZrO2), tantalum pentoxide (Ta2O5) etc., as the example of low-index material, silica (SiO can be enumerated2), magnesium fluoride (MgF2) etc., these metal oxide particles can be made to be scattered in polymerization thing liquid and be coated film.
Polymer contained in infrared-reflecting layers is not particularly limited, as long as infrared-reflecting layers can be formed Polymer, is not particularly limited.
For example, as polymer, the polymer described in Japanese Unexamined Patent Application Publication 2002-509279 publications can be used.As Concrete example, can enumerate for example：Polyethylene naphthalate (PEN) and its isomers (such as 2,6-PEN, 1,4-PEN, 1,5- PEN, 2,7-PEN and 2,3-PEN), poly terephthalic acid alkyl diol ester it is (such as polyethylene terephthalate (PET), poly- Mutual-phenenyl two acid bromide two alcohol ester and poly- 1,4- hexamethylenes terephthalic acid (TPA) dialkylene glycol ester), polyimides (such as poly- third Alkene acid imide), polyetherimide, random polystyrene, makrolon, polymethacrylates (such as polyisobutyl group methyl-prop Olefin(e) acid ester, poly- propyl methacrylate, polyethyl methacrylate and polymethyl methacrylate (PMMA)), polyacrylic acid (such as ethyl cellulose, acetyl group are fine for ester (such as poly- butyl propyleneglycol acid esters and polymethacrylates), cellulose derivative Tie up element, cellulose propionate, acetylcellulose butyrate and nitrocellulose), polyolefin polymer (such as polyethylene, poly- third Alkene, polybutene, polyisobutene and poly- (4- methyl) amylene), fluorinated polymer (such as perfluoroalkoxy resin, polytetrafluoroethyl-ne Alkene, fluorinated ethylene propylene copolymer, polyvinylidene fluoride and polychlorotrifluoroethylene), chlorinated polymeric (such as gather inclined two chloroethene Alkene and polyvinyl chloride), it is polysulfones, polyether sulfone, polyacrylonitrile, polyamide, organic siliconresin, epoxy resin, polyvinyl acetate, poly- Ether amide, ionomer resin, elastomer (such as polybutadiene, polyisoprene and chloroprene rubber) and polyurethane.Copolymerization Copolymer [such as (a) terephthalic acid (TPA) or its ester, (b) different phthalic acid or its ester, (c) O-phthalic of thing, such as PEN Acid or its ester, (d) alkanediol, (e) ring alkanediol (such as cyclohexanedimethanol glycol), (f) alkane dicarboxylic acid, and/or (g) ring alkane dicarboxylic acid (such as cyclohexane dicarboxylic acid) and 2,6 naphthalene dicarboxylic acid, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2, 7- naphthalene dicarboxylic acids, and/or the copolymer of 2,3- naphthalene dicarboxylic acids or their ester], polyalkylene glycol terephthalate is total to Polymers [such as (a) naphthalene dicarboxylic acids or its ester, (b) M-phthalic acid or its ester, (c) phthalic acid or its ester, (d) alkane two Alcohol, (e) ring alkanediol (such as cyclohexanedimethanol glycol), (f) alkane dicarboxylic acid, and/or (g) cycloalkane dicarboxylic acids (example Such as cyclohexane dicarboxylic acid) and the copolymer of terephthalic acid (TPA) or its ester] and styrol copolymer (such as styrene-butadiene Copolymer and styrene-acrylonitrile copolymer), the double benzoic acid of 4,4- and ethylene glycol also is adapted for.
Also, each layer distinguishes the mixture that can include two kinds or above-mentioned polymer or copolymer more than it (between such as The mixture of stereospecific polymerized styrene (SPS) and random polystyrene).These polymer can be used alone, and can also combine It is two or more and use.
Above-mentioned polymer can be passed through polymer as described in No. 6049419 specifications of U.S. Patent Application No. Melting extrusion and stretching and form infrared-reflecting layers.Additionally, it is preferred that it is used as polymer using other water soluble polymers.
In addition, it can contain in high refractive index layer or low-index layer for the infrared-reflecting layers of the present invention ultraviolet Light absorbers, anti-fading agent, curing agent, anion, cation or non-ionic various surfactants, fluorescent whitening agent, sulphur The pH such as acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate regulators, defoamer, diethylene glycol etc. lubricate Various additives known to agent, preservative, antistatic agent, delustering agent etc..
The manufacture method of infrared-reflecting layers is not particularly limited, and can use coetrusion, extrusion by melting etc..As Extrusion by melting, as the method described in No. 6049419 specifications of U.S. Patent No., by the melting extrusion of polymer and The method for forming infrared-reflecting layers is stretched, in addition, can be enumerated to water-based high refractive index layer coating fluid and low-refraction Layer is alternately carried out wet coating and the method for being dried and forming laminated body with coating fluid.
As to water-based high refractive index layer wet coating is alternately carried out with coating fluid with coating fluid and low-index layer Method, preferably using the coating method being exemplified below.Preferably using for example：Rolling method, stick coating method, air knife coating process, spraying Coating process, No. 2761419 specifications of coating method or U.S. Patent No., the slip described in No. 2761791 specification etc. Funnel rubbing method, extrusion coating method etc..In addition, as the mode for carrying out multiple layers double-layer coating, can be applied for gradually double-layer Cloth, or while double-layer is coated with.
The thickness of high refractive index layer coating fluid and low-index layer coating fluid in infrared-reflecting layers can pass through Adjustment coating weight to control as above-mentioned preferable thickness in drying.
In addition, refractive index ratio of the reflection produced by the bed boundary of above-mentioned adjoining dependent on interlayer, therefore, the refractive index ratio Bigger, reflectivity is higher.In addition, when being observed with monofilm, make the reflected light of layer surface and the light path of the reflected light in layer bottom When difference becomes the relation that nd=wavelength/4 represents, the reflected light enhancing for making to produce based on phase difference can be controlled, can be with Improve reflectivity.Here, n is refractive index, d is the physics thickness of layer.By using the optical path difference, reflection can be controlled.Can be with The refractive index and thickness of each layer, the reflection of control ultraviolet light, visible ray or near infrared light are controlled using the relation.
I.e., it is possible to according to the refractive index of each layer, the thickness of each layer, each layer lamination form and improve particular wavelength region Reflectivity.
Above-mentioned infrared-reflecting layers (predominantly reflect the layer of near infrared region, and also reflect region of ultra-red and far-infrared band The layer of the light of domain wavelength) particular wavelength region that is improved since reflectivity can be changed, ultraviolet reflecting layer can be set to Or visible light reflecting layer.That is, if particular wavelength region reflectivity being improved is set as ultraviolet range, purple is become Outside line reflecting layer, if set to visible region, then as visible light reflecting layer.
[3] adhesive layer
The functional sheet of the present invention is to assign for the adhesiveness that makes functional sheet note invest glass pane and other items Purpose sets adhesive layer.
As the main material of adhesive layer, the polymer substances such as elastomer or synthetic resin can be enumerated, according to glued material Use condition of component etc. after material or bonding and it is suitably selected.It can enumerate for example：Vinyl acetate resin, acrylic resin, Vinyl acetate-acrylic resin, acetate-vinyl chloride resin, vinyl acetate resins, ethylene-acrylic acid tree Fat, polyamide, polyvinyl alcohol acetal resin, polyvinyl alcohol, polyester resin, polyurethane resin, carbamide resin, melamine Resin, phenolic resin, resorcinol resin, epoxy resin, polyimide resin, natural rubber, chlorobutylene rubber etc..
Preferably there is the material of durability relative to ultraviolet, preferably acrylic resin (acrylic adhesive) or have Machine silicones (polysiloxanes bonding agent).Wherein, from the viewpoint of adhesion properties or cost, preferred acrylic adhesive.It is special It is not preferred solvent class and type of latex type acrylic adhesive, more preferably solvent from the aspect of the control of peel strength is easy Acrylic adhesive., can be with as monomer in the case of using polymerisation in solution polymer as solvent system acrylic adhesive Use known material.
Such as stabilizer, surfactant, ultra-violet absorber, fire retardant, antistatic can be contained in the adhesive layer Agent, antioxidant, heat stabilizer, lubricant, filler, colouring agent, bonding regulator etc. are used as additive.Particularly such as this hair It is bright used like that as window patch in the case of, for the deterioration of infrared shield film caused by suppressing ultraviolet, add ultraviolet Light absorbers are also effective, preferably using above-mentioned ultra-violet absorber.
The thickness of adhesive layer is preferably in the range of 0.5~10 μm, in the range of more preferably 2~10 μm.If it is More than 0.5 μm, then there are the tendency that cementability improves, when functional sheet is fitted in article, it can obtain sufficient bonding Power.On the contrary, if it is less than 10 μm, not only the transparency of functional sheet improves, but also is attached by functional sheet After glass pane and other items, cohesional failure will not be caused in bonding interlayer when being peeled off, existing will not remain in glass surface The tendency of bonding agent.
As the coating method of adhesive, arbitrary known method can be used, such as dispensing coating machine is preferably listed Method, intaglio plate roll coater method, blade coating machine method, flush coater method, air knife coating process, dip coating, transfer printing etc., can individually or group Close and use.Solution suitably can be made with the solvent that can dissolve adhesive in these materials, or uses the painting disperseed Cloth liquid applies, and as solvent, can use known thing.
For the formation of adhesive layer, electromagnetic wave shielding can be applied directly to using previous application pattern, in addition, Can also primary coating in stripping film and make its dry after, fit in electromagnetic wave shielding and transfer adhesive.At this time Drying temperature preferably reduces residual solvent as far as possible, therefore, drying temperature or time do not have it is specific, preferably preferably 50~150 Drying time in the range of being set 10 seconds~5 minutes in temperature in the range of DEG C.
[4] use method, the purposes of functional sheet
The functional sheet of the present invention passes through in adhesive layer of the inner side of the second mold release film configuration with cementability, Ke Yi Peel off the second mold release film and expose adhesive layer, then, across the adhesive layer in the room of the windowpane of vehicle or building and other items Interior (in-car or indoor) side or outdoor side attach the functional layer with electromagnetic wave shielding performance.In addition, by the functional layer Outermost layer configuration hard conating, can to electromagnetic wave shielding layer surface assign marresistance.
Fig. 2 is the schematic diagram of example when representing to fit in the functional sheet of the present invention into article.
By the first mold release film 1, be adjacent to the functional layer 2 of the first mold release film 1, be adjacent to functional layer 2 adhesive layer 4 and The functional sheet 10 of the invention that second mold release film 5 is formed peels off the second mold release film 5 and exposes adhesive layer 4 first, is being bonded Article (being herein glass 6) on be bonded for example, by soaking etc..Thereafter, after squeezing out for the water soaked, by first Mold release film 1 is peeled off from functional layer 2 and completes the fitting of functional layer 2.In the face for the first mold release film for having peeled off functional layer 2 On formed with hard conating 7 when, traumatic resistance improve, so it is preferred that.
In addition, in order to which functional layer is fitted in article without making its produce wrinkle or gauffer etc., the when preferably soaking Peeling force between one mold release film and the functional layer of adjoining is bigger than the peeling force between adhesive layer and the article being bonded, and is being bonded And after water is squeezed out, the peeling force between the first mold release film and the functional layer of adjoining is preferably than adhesive layer with being bonded between article Peeling force is small.
[purposes of functional sheet]
Functional sheet provided by the present invention can be applied to the field of broadness.Such as conduct has ultraviolet screener layer Or the electromagnetic wave shielding sheet material of infrared ray shielding layer, as the outdoor window of building or the window purposes of vehicle or fit in tool There is the purposes of the article of curve form, preferably using the functional sheet of the present invention.Particularly preferably it is used as the curved surface with stereoscopic article There is no the electromagnetic wave shielding sheet material of wrinkle or gauffer during adhered shape.
The functional sheet of the present invention can be preferably used as ultraviolet shielding material or infrared shield material and across viscous Conjunction layer fits in resin forming article beyond glass and other items.If the present invention functional sheet it is transparent, such as by The functional sheet of the present invention is bonded on using black combination as the instrument board of the automobile of coating material, can be maintained black Color, and absorb hot line with imitating, reduce indoor temperature and rise.
Embodiment
Hereinafter, enumerate embodiment and specifically describe the present invention, but the present invention is not limited to these.It should be noted that The expression of " part " or " % " is used in embodiment, but as long as without specified otherwise, represents " mass parts " or " quality % ".
Embodiment 1
[making of functional sheet 101]
The functional sheet shown in Fig. 1 (A) is made as steps described below.
The is used as using biaxial stretch-formed polypropylene (Oji F-Tex (strain) E-201F, 50 μm of thickness (in table 1, being denoted as PP)) One mold release film, is prepared infrared ray shielding layer coating composition according to following, is coated using dispensing coating machine.With regard to coating For, thickness is adjusted, optical concentration is coated for 0.12.Thickness is adjusted, dry thickness is coated for 3.0 μm.
＜ infrared ray shielding layer coating compositions ＞
Then, as adhesive layer, the coating fluid of following cooperations is coated with above-mentioned functional layer.Adjustment thickness is applied Cloth, it is 3.0 μm to make dry thickness.
＜ adhesive layer coating compositions ＞
Finally, using Nakamoto Packs (strain) NS SEPARATOR XA (セ パ レ ー タ ー XA) type (25 μ of thickness M, polyethylene terephthalate film (PET)) as the second mold release film be laminated on above-mentioned adhesive layer, obtain feature Sheet material 101.
[making of functional sheet 102]
In the making of functional sheet 101, following hard conatings are formed with the Rotating fields of Fig. 1 (B), are then identically formed Infrared ray shielding layer, adhesive layer, are laminated with the second stripping film.
The formation ＞ of ＜ hard conatings
Using UV-3701 (Toagosei Co., Ltd's manufacture), it is coated with gravure coating machine in the first mold release film, At 90 DEG C of drying temperature it is dry after, using high-pressure mercury-vapor lamp, as accumulated light 300mJ/cm2Cure coating layer, formed Hard conating, it is 2.0 μm to make dry thickness.
[making of functional sheet 103]
In the making of functional sheet 101, following infrared-reflecting layers are formed with the Rotating fields of Fig. 1 (C), then equally Ground forms infrared ray shielding layer, adhesive layer, is laminated with the second stripping film.
The formation ＞ of ＜ infrared-reflecting layers
Using on the first stripping film can double-layer be coated with sliding hopper apparatus for coating (slip coating machine), by following low foldings Rate layer coating fluid L1 and high refractive index layer coating fluid H1 insulations are penetrated at 45 DEG C, while on 45 DEG C of supporting mass is heated to, Be alternately carried out 9 layers of low-index layer, double-layer is coated with while 8 layers of high refractive index layer amounts to 17 layers, and make high refractive index layer and Low-index layer it is respective dry when thickness be 130nm.
Just after coating, blowing 5 DEG C of cold wind fixes it in 5 minutes.Thereafter, blow 80 DEG C of warm wind and be dried, formed By the 17 layers of near infrared ray reflective formed layer.
[preparation of low-index layer coating fluid L1]
First, using cataloid (the Nissan Chemical Industries strain as the second metal oxide particle of 10 mass % The manufacture of formula commercial firm, SNOWTEX (registration mark) OXS) 680 parts of aqueous solution, (Co., Ltd. is laughable for the polyvinyl alcohol of 4.0 mass % Beautiful manufacture, PVA-103：The degree of polymerization 300, saponification degree 98.5mol%) 30 parts of aqueous solution and 3.0 mass % boric acid aqueous solution 150 parts are mixed and are disperseed.Pure water is added, as a whole, prepares 1000 parts of colloidal silica dispersion L1.
Then, obtained colloidal silica dispersion L1 is heated to 45 DEG C, stirred wherein while adding successively Enter polyvinyl alcohol (manufacture of JAPAN VAM＆POVAL Co., Ltd., the JP-45 as polyvinyl alcohol (B) of 4.0 mass %：Polymerization Degree 4500,86.5~89.5mol% of saponification degree) 760 parts of aqueous solution.Thereafter, the amide sulfo betaine class table of 1 mass % is added Face activating agent (grinding Fine Chemicals Co. Ltd. systems, SOFTAZOLINE (registration mark) LSB-R in river) 40 parts of aqueous solution, Prepare low-index layer coating fluid L1.
[preparation of high refractive index layer coating fluid H1]
(preparation for being set to the Titanium Dioxide Rutile Top grade of the core of core shell particle)
Titanium oxide hydrate is suspended in water, prepare the aqueous suspension of titanium oxide, make to be scaled TiO2When it is dense Spend for 100g/L.Stir that (concentration 10 is rubbed while adding the sodium hydrate aqueous solution of 30L in the suspension of 10L (liter) That/L), then, it is heated to 90 DEG C, when curing 5 is small.Then, neutralized using hydrochloric acid, cleaned after filtering using water.
It should be noted that in above-mentioned reaction (processing), the titanium oxide hydrate as raw material according to known methods, Handled by pyrohydrolysis to obtain titanium sulfate aqueous solution.
The above-mentioned titanium compound for carrying out alkali process is suspended in pure water, and make it to be scaled TiO2When concentration be 20g/L.Stir wherein while adding relative to TiO2Measure as the citric acid of 0.4 mole of %.Thereafter, heated, When the temperature of mixed sols liquid becomes 95 DEG C, adding concentrated hydrochloric acid makes concentration of hydrochloric acid be 30g/L, while fluid temperature is maintained 95 DEG C, while when stirring 3 is small, prepare titanium oxide sol liquid.
As described above, pH the and Z current potentials of the titanium oxide sol liquid measured at 95 DEG C of fluid temperature, as a result, pH It is+40mV for 1.4, Z current potentials.In addition, carry out particle size determination using the Zetasizer Nano of Malvern companies manufacture, as a result, Single dispersing degree is 16%.
Also, make titanium oxide sol liquid at 105 DEG C it is dry 3 it is small when, obtain the powder particles of titanium oxide.Use Japanese electricity The JDX-3530 types X-ray diffraction measure of the sub- DATUM Co., Ltd. manufacture powder particles, confirm as the titanium oxide of rutile-type Particulate.In addition, the volume average particle size of the particulate is 10nm.
Moreover, addition contains the titanium oxide microparticle of the rutile-type of obtained volume average particle size 10nm in pure water 4kg 20.0 mass % titanium oxide sol aqueous liquid dispersion, obtain the sol solutions of core particle.
(preparation that the core shell particle formed is coated by shell)
The titanium oxide sol aqueous liquid dispersion 0.5kg of 10.0 mass % is added in the pure water of 2kg, is heated to 90 DEG C.Connect , slowly silicate aqueous solution 1.3kg made from addition, and make to be scaled SiO2When concentration be 2.0 mass %, in autoclave In, heat when progress 18 is small at 175 DEG C, further concentrated, as core particle, for Rutile structure Titanium oxide, as clad, obtains as SiO2Core shell particle (average grain diameter：Sol solutions (solid component concentration 10nm) 20 mass %).
(preparation of high refractive index layer coating fluid H1)
Using the core as the first metal oxide particle containing the 20.0 mass % of solid component concentration obtained in above-mentioned Polyvinyl alcohol (the strain formula meeting of 28.9 parts of the sol solutions of shell particles, 10.5 parts of the aqueous citric acid solution of 1.92 mass %, 10 mass % Society's Kuraray manufacture, PVA-103：The degree of polymerization 300, saponification degree 98.5mol%) 2.0 parts of aqueous solution and 3 mass % boric acid it is water-soluble 9.0 parts of liquid is mixed, and prepares core shell particle dispersion H1.
Then, while stirring core shell dispersion liquid H1, while adding the poly- second of conduct as 16.3 parts of pure water and 5.0 mass % Polyvinyl alcohol (Kuraray Co., Ltd.'s manufacture, the PVA-124 of enol (A)：The degree of polymerization 2400,98~99mol% of saponification degree) water 33.5 parts of solution.Further the amide sulfo betaine class surfactant of 1 mass % of addition (grinds Chemicals plants of Fine in river The manufacture of formula commercial firm, SOFTAZOLINE (registration mark) LSB-R) 0.5 part of aqueous solution, using pure water preparation 1000 parts in terms of overall High refractive index layer coating fluid H1.
[making of functional sheet 104]
In the making of functional sheet 101, above-mentioned hard conating and above-mentioned infrared is sequentially formed with the Rotating fields of Fig. 1 (D) Line reflection layer, is then identically formed infrared ray shielding layer, adhesive layer, is laminated with the second stripping film.
[making of functional sheet 105]
In the making of functional sheet 101, infrared ray shielding layer, bonding are identically formed with the Rotating fields of Fig. 1 (E) Layer, forms following resinous coats on adhesive layer, then, is laminated with the second stripping film.
The formation ＞ of ＜ resinous coats
The resinous coat composition of following compositions is prepared, the combination of coating machine coating resin coating is reversed using intaglio plate Thing, it is 2.0 μm to make the thickness after curing.After it is dried 60 seconds in 70 DEG C of baking oven, irradiating ultraviolet simultaneously makes exposure For 120mJ/cm2, make curing of coating, form resinous coat.
The functional sheet 101~105 more than use made implements following evaluation.
《Evaluation 1》
(1) measure of peeling force
The sample of the size of 300mm × 300mm is placed 24 in 23 ± 1 DEG C of temperature, the atmosphere of relative humidity 50 ± 5% More than hour.Then, the width adjustment of sample is 50mm, and length is set to 200mm.Tried using being stretched specified in JIS B 7721 Test machine and measure following peeling force.
The end of the first stripping film or the second stripping film is peeled off from part of functions layer or adhesive layer and is sandwiched In cupping machine, measure and required power is peeled along 180 ° of directions from the end of stripping with draw speed 300m/min.Unit For (mN/50mm).
《Evaluation 2》
The functional sheet 101~105 of use production implements following evaluation.
(1) keeping quality
By the sample of the size of 300mm × 300mm when placement 1500 is small in the environment of 60 DEG C, 90%RH, by visual observation The generation in the crack of overview function layer, is evaluated according to following benchmark.
5：Do not produce
4：When can not learn, but be spied on 100 times of magnifying glasses by visual observation, it can be seen that somewhat produce
3：3 are produced by visual observation to sentence down
2：Produce by visual observation more than at 4
1：Cracking is produced in entire surface
Evaluation more than 3 is qualified.
(2) durability of the infrared shield effect after glass is fitted in
Measured using infrared spectrophotometer (Japan's light splitting system " FT/IR4100 ") by the examination of the size of 300mm × 300mm After sample fits in glass according to the flow of Fig. 2, in the environment of 60 DEG C, 90%RH place 1500 it is small when or so infrared ray inhale The change (measure wavelength 1300nm) of yield.
5：Do not change
4：1% less than 10%, and infrared absorption rate reduces
3：10% less than 20%, and infrared absorption rate reduces
2：20% less than 30%, and infrared absorption rate reduces
1：More than 30%, infrared absorption rate reduces
Evaluation more than 3 is qualified.
By above evaluation result is shown in table 1.
[table 1]
As shown in Table 1：The functional sheet of the present invention does not produce the irregular, defect after preserving, crack, can tie up for a long time Hold the shielding of infrared ray.
In addition we know：Gauffer when fitting in glass or irregular generation are observed by visual observation, as a result, gauffer does not occur Or it is irregular, can equably joint function layer.
Embodiment 2
[making of functional sheet 201]
In the making of functional sheet 102, the second stripping film is not laminated, in addition, similarly comparison example Functional sheet 201.
[making of functional sheet 202]
In the making of functional sheet 102, the temperature of aging is adjusted, by the stripping of the first stripping film and the second stripping film Power is adjusted to 70mN/50mm, in addition, the similarly functional sheet 202 of comparison example.
[making of functional sheet 203]
In the making of functional sheet 102, the temperature of aging is adjusted, by the stripping of the first stripping film and the second stripping film Power is adjusted to 2400mN/50mm, in addition, the similarly functional sheet 203 of comparison example.
[making of functional sheet 204]
In the making of functional sheet 102, the temperature of aging is adjusted, by the stripping of the first stripping film and the second stripping film Power is adjusted to 70mN/50mm and 2400mN/50mm respectively, in addition, similarly makes the functional sheet 204 of the present invention.
[making of functional sheet 205~223]
In the making of functional sheet 102, the temperature of aging is adjusted, by the stripping of the first stripping film and the second stripping film Power is adjusted to the peeling force of the record of table 2, and makes thickness change as table 2 is recorded of adhesive layer, in addition, similarly makes Make the functional sheet 205~223 of the present invention.
[making of functional sheet 224~232]
In the making of functional sheet 102, spin (strain) single side using Japan on the first stripping film and be easily bonded and gather to benzene Naphthalate film A4100 (100 μm of thickness), and functional layer is formed in easy bonding plane side, further as table 2 is recorded Change the thickness of adhesive layer like that, in addition, similarly make the functional sheet 224~232 of the present invention.
The functional sheet 201~232 of use production implements the keeping quality of embodiment 1 and commenting for infrared shield durability Valency, records the result in table 2.
[table 2]
As shown in Table 2：The functional sheet of the present invention without irregular, defect, crack is produced, can be tieed up for a long time after being saved Hold the shielding of infrared ray.
In addition we know：Gauffer when fitting in glass or irregular generation are observed by visual observation, as a result, the second stripping film The big functional sheet 204 of peeling force is it can be seen that a little gauffer or irregular, but the big feature of peeling force of the first stripping film Sheet material 205~232 does not have gauffer or irregular, can equably joint function layer.
Industrial applicibility
The functional sheet of the present invention is the exterior that can easily fit in application face or the vehicles of building etc. The functional sheet of the 3-dimensional shape in face, built-in face etc., its effectively shielding ultraviolet rays or infrared ray, will not produce irregular, scarce Damage, crack, can maintain the shielding of above-mentioned ultraviolet or infrared ray for a long time, therefore, suitable for building materials purposes, vehicular applications.

Claims (9)

1. a kind of functional sheet, it at least has electromagnetic wave shielding performance, wherein,
Adhesive layer has been sandwiched between first mold release film and second mold release film different from the fissility of adjacent layer and has at least been contained There is the functional layer of one or more layers of electromagnetic wave shielding.
2. functional sheet as claimed in claim 1, wherein,
Required peeling force is set to Pf when first mold release film is peeled off from the adjacent functional layer1, and by described in Required peeling force is set to Pf when second mold release film is peeled off from the adhesive layer2When, meet following formula (P)：
Formula (P) Pf2＜ Pf1。
3. functional sheet as claimed in claim 2, wherein,
In measure under 23 DEG C, 55%RH environment, the peeling force (Pf1) it is more than 2000mN/50mm, and the peeling force (Pf2) it is below 100mN/50mm.
4. such as functional sheet according to any one of claims 1 to 3, wherein,
The electromagnetic wave shielding contains electromagnetic shielding material or electromagnetic wave shielding performance particulate, and contains adhesive resin.
5. such as functional sheet according to any one of claims 1 to 4, wherein,
The electromagnetic wave shielding is the layer of shielding ultraviolet rays or infrared ray.
6. such as functional sheet according to any one of claims 1 to 5, wherein,
The functional layer with first mold release film adjoining is the electromagnetic wave shielding.
7. such as functional sheet according to any one of claims 1 to 5, wherein,
The functional layer with first mold release film adjoining is hard conating or infrared-reflecting layers.
8. such as functional sheet according to any one of claims 1 to 7, wherein,
The thickness of the adhesive layer is in the range of 0.5~10.0 μm.
9. such as functional sheet according to any one of claims 1 to 8, wherein,
There is substrate layer on the surface of the side that connects with the functional layer of first mold release film.
CN201680046687.XA 2015-08-11 2016-07-08 Functional sheet Pending CN107921751A (en)

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Application publication date: 20180417