CN104245303A

CN104245303A - Infrared-shielding film and infrared-shielding element

Info

Publication number: CN104245303A
Application number: CN201380018223.4A
Authority: CN
Inventors: 三好正纪
Original assignee: Konica Minolta Opto Inc
Current assignee: Konica Minolta Inc; Konica Minolta Opto Inc
Priority date: 2012-04-05
Filing date: 2013-04-04
Publication date: 2014-12-24
Also published as: WO2013151136A1; JPWO2013151136A1

Abstract

The present invention relates to an infrared-shielding film having a substrate, a dielectric multilayer film comprising a high-refractive-index layer and a low-refractive-index layer, and a layer which includes flat plate-shaped metal particles. The present invention makes it possible to provide an infrared-shielding film having excellent transparency, in which discoloration over time is suppressed, and to provide an infrared-shielding element that is provided with the infrared-shielding film.

Description

Infrared ray shielding film and infrared shield

Technical field

The present invention relates to infrared ray shielding film and infrared shield.

Background technology

In recent years, fit in building, the fenestrated membrane in glass pane face of automobile is subject to extensive utilization.One of them, have the film of function possessing and suppress ultrared intrusion, prevent Indoor environment excessive temperature from raising, decrease the use of air-cooling system, achieve energy-saving.

As the ultrared method of blocking-up, commercially availablely there is the film of the infrared ray absorbing type applying the infrared ray-absorbing layer containing infrared absorbent on film, film applies the film of the reflection-type of the layer of reflected infrared ray and has the film of mode of these two kinds of functions concurrently.As an example of this film, there is the film utilizing sputtering, evaporation to form metal film on film two sides.Such film can make infrared ray not invade indoor in summer, makes to be discharged into indoor outdoor infrared reflection in the winter time to indoor, thus embodiment heat insulating function, in addition, can also the thermal-insulation function of combining efficient rate, all realize energy-saving in season in winter in summer two.

Because light energy conversion is heat energy by the film of infrared ray absorbing type, so the temperature of its glass attached easily raises, the risk of thermal fracture improves, but with regard to infrared reflection type, its risk is little, and range of application also becomes large.

The film of infrared reflection type has the technology of layered dielectric tunic, discloses following film: utilize on base material, apply coating fluid and stacked rubbing method by film (such as with reference to Japanese Unexamined Patent Publication 8-110401 publication, Japanese Unexamined Patent Publication 2007-331296 publication) alternately laminated for floor different for refractive index; At the film (such as with reference to United States Patent (USP) the 4th, 368, No. 945 descriptions) etc. of the laminate film containing argent of the 3-tier architecture of the thick tungsten oxide/silver/tungsten oxide of the polyester film stacked certain films in surface.

In addition, in Japanese Unexamined Patent Publication 2011-252213 publication and Japanese Unexamined Patent Publication 2011-253094 publication, disclose by spread plate shape metallic on base material and be arranged in plane and form the technology of the high metal system infrared-reflecting layers of electromagnetic wave permeable.

Summary of the invention

But, above-mentioned Japanese Unexamined Patent Publication 8-110401 publication, Japanese Unexamined Patent Publication 2007-331296 publication and United States Patent (USP) the 4th, in order to improve infrared reflection rate, stacked number becomes many, causes because bed boundary increases the problem that the transparency of film reduces in the film existence of the infrared reflection type recorded in 368, No. 945 descriptions.

In addition, in the technology described in Japanese Unexamined Patent Publication 2011-252213 publication and Japanese Unexamined Patent Publication 2011-253094 publication, if infrared reflection rate will be improved by making tabular metallic absorb infrared ray while reflected infrared ray, then also become large by absorbing the heating caused, the risk of thermal fracture uprises.In addition, there are the following problems, that is, the oxidation of metallic is accelerated because of the heating of film, its result cause film through time variable color.

On the other hand, the general construction method of fenestrated membrane is as follows: after the adhesive surface spraying water have the glass surface and film that will attach this film, will fit each other, constructor uses scraper plate etc. to be extruded by the moisture between film and glass surface.Therefore, heat insulation, the metal film of adiabatic membrane owing to having more than 2 layers on the two sides of base material with metal level as above-mentioned fenestrated membrane, the unfavorable condition of burden so the drying that there is moisture slowly dewaters when constructing.

In addition, even if the operation through squeezing the water out, moisture also must remain, and during to this water drying, is difficult to show sufficient bonding force.Particularly, when using thicker base material, the drying of moisture and so-calledly dewater slow, the end of film can be peeled off from glass surface sometimes.Particularly in its properties, adiabatic membrane is used to cold district mostly, and slower in the winter dryness of cold district, the possibility that therefore film is peeled off uprises further.Therefore, seeking the film playing good adaptation when being attached at glass surface etc. always.

Therefore, the object of the invention is to, provide a kind of transparency excellent, can suppress through time variable color infrared ray shielding film and possess the infrared shield of this infrared ray shielding film.

Another order of the present invention is, provides a kind of adaptation of the attaching object to glass surface etc. good and has excellent heat insulating function and the infrared ray shielding film of thermal-insulation function, and possessing the infrared shield of this infrared ray shielding film.

The present inventor etc. conduct in-depth research in view of above-mentioned problem.Consequently find surprisingly, utilize the infrared ray shielding film of the multilayer dielectric film having and comprise high refractive index layer and low-index layer and the layer containing tabular metallic can solve above-mentioned problem, thus complete the present invention.

Above-mentioned purpose of the present invention forms realization by following.

That is, infrared ray shielding film of the present invention has base material, comprises the multilayer dielectric film of high refractive index layer and low-index layer and the layer containing tabular metallic.

In addition, infrared shield of the present invention is provided with above-mentioned infrared ray shielding film at least one side of matrix.

Accompanying drawing explanation

Figure 1A is the schematic isometric of an example of the shape representing tabular metallic, and is the figure representing roughly hexagonal tabular metallic.

Figure 1B is the schematic isometric of an example of the shape representing tabular metallic, and is the figure of the tabular metallic representing roughly disc-shape.

Fig. 2 A is the schematic section of existence representing the layer containing tabular metallic that the present invention relates to, and is the figure representing desirable existence.

Fig. 2 B is the schematic section of the existence representing the layer containing tabular metallic that the present invention relates to, and is the figure that the plane of base material and the plane angulation (θ) of tabular metallic are described.

Fig. 2 C is the schematic section of the existence representing the layer containing tabular metallic that the present invention relates to, and is the figure of the domain of the existence of layer on the depth direction of infrared ray shielding film represented containing tabular metallic.

Fig. 3 A represents that the layer of the interior subsides infrared ray shielding film made in embodiment forms the schematic cross-section of (interior subsides formation 1).

Fig. 3 B represents that the layer of the interior subsides infrared ray shielding film made in embodiment forms the schematic cross-section of (interior subsides formation 2).

Fig. 3 C represents that the layer of the outer subsides infrared ray shielding film made in embodiment forms the schematic cross-section of (outer subsides formation 3).

Fig. 3 D represents that the layer of the interior subsides infrared ray shielding film made in embodiment forms the schematic cross-section of (outer subsides formation 4).

Fig. 3 E represents that the layer of the outer subsides infrared ray shielding film made in comparative example forms the schematic cross-section of (layer forms 5).

Detailed description of the invention

Infrared ray shielding film of the present invention has base material, comprises the multilayer dielectric film of high refractive index layer and low-index layer and the layer containing tabular metallic.Infrared ray shielding film of the present invention is by having multilayer dielectric film, thus when being used as fenestrated membrane, by the near infrared ray reflective from sunlight, it is made not invade indoor, function is played thus as shielding film, in addition, by utilizing the layer containing tabular metallic can reflect to the middle infrared (Mid-IR) of outdoor release, far infrared to indoor, thus also function is played as adiabatic membrane.Like this, infrared ray shielding film of the present invention is due to except having multilayer dielectric film, also there is layer containing tabular metallic further, even if therefore the number of plies of multilayer dielectric film is few, also can obtain good infrared reflection rate (infrared screening effect), the transparency of film improves.In addition, due to the light quantity of the layer incided containing tabular metallic can be reduced, so the caloric value of the layer containing tabular metallic can be reduced, can suppress film through time variable color.Like this, according to the present invention, can provide the transparency excellent, can suppress through time variable color infrared ray shielding film and possess the infrared shield of this infrared ray shielding film.

As the basic optical characteristic of infrared ray shielding film of the present invention, as the transmissivity of the visible region shown in JIS R3106:1998, preferably more than 40%, more preferably more than 60%.In addition, as the reflectivity in the region of wavelength 900nm ~ 1400nm, preferably more than 50%, more preferably more than 70%.In addition, the transmissivity in the region of wavelength 900nm ~ 1400nm is preferably less than 30%.

In addition, infrared ray shielding film of the present invention is formed across above-mentioned base material at the layer containing above-mentioned tabular metallic and above-mentioned multilayer dielectric film, when the area of above-mentioned base material being set to A and the occupied area of above-mentioned tabular metallic is set to B, the area occupation ratio C represented by following formula 1 is preferably more than 15% and is less than 90%.Should illustrate, the detailed assay method of above-mentioned base material area A and occupied area B as described later.

C [%]=(B/A) × 100 ... (formula 1)

The infrared ray shielding film of this formation, by becoming above-mentioned formation, can also improve adaptation glass surface etc. being attached to object.

Be difficult to obtain sufficient bonding force before the water drying that general fenestrated membrane exists between the object and film of the cling films such as glass surface.Therefore, when as prior art, fenestrated membrane contains metal film, water is not easily dry, and the end of film can be peeled off from glass surface sometimes.

For this problem, because multilayer dielectric film and the layer containing tabular metallic are formed across base material, so when using water to carry out the attaching of film, the effect that water becomes easily dry can be expected.

And, about the layer containing tabular metallic, by making the area occupation ratio shared by this tabular metallic be less than 90%, thus becoming easy removing at film and the water attached between object, consequently easily obtaining sufficient bonding force.That is, greatly can improve film to the adaptation attaching object, the stripping of film can be prevented.On the other hand, if make area occupation ratio be more than 90%, then the drying of water is slack-off.

Like this, by making the area occupation ratio of tabular metallic be less than 90%, thus dehydration accelerates, and can improve the adaptation of film, if but make this area occupation ratio too small, be then difficult to obtain sufficient effect of heat insulation, insulation effect.Therefore, by making area occupation ratio be more than 15%, the layer containing tabular metallic can be utilized to obtain sufficient effect of heat insulation, insulation effect, the adaptation of infrared ray shielding film can not only be improved, effect of heat insulation and insulation effect can also be improved.In other words, according to aforesaid way, can provide good to the adaptation of the attaching objects such as glass surface and there is excellent heat insulating function and the infrared ray shielding film of thermal-insulation function, and possessing the infrared shield of this infrared ray shielding film.

In addition, cause film variable color for the mould produced by the water remained and the problem points that product life shortens, the present inventor has also found that infrared ray shielding film of the present invention can solve the new effect of this problem points.As the formation of multilayer dielectric film, as detailed below, the formation containing water-soluble resin is mostly adopted.Like this, in fenestrated membrane containing water-soluble resin, if this film of Long-Time Service under conditions of high humidity, then cause film especially easily variable color due to the impact of mould.

On the other hand, known infrared ray shielding film of the present invention by utilizing the bactericidal action of the metals such as silver, thus also can obtain making the multilayer dielectric film not effect of product life significant prolongation by mould infringement.In order to obtain higher anti-mold effect, layer preferably containing metals such as silver, the layer namely containing tabular metallic and multilayer dielectric film adjoin, even if but these layers are formed across base material as infrared ray shielding film of the present invention, also can obtain sufficient anti-mold effect.Thinking that its reason is the layer by possessing in a part for infrared ray shielding film containing tabular metallic, the breeding that the layer containing tabular metallic suppresses mould can be utilized, the effect that the expansion that can obtain the breeding scope making mould thus postpones.

Below, the inscape of infrared ray shielding film of the present invention is described in detail.

[base material (supporter)]

As the base material (supporter) used in infrared ray shielding film of the present invention, be preferably film support.Film support can be transparent, also can be opaque, can use various resin molding.As its concrete example, each resin moldings such as poly-(methyl) acrylate, PETG (PET), PEN (PEN), Merlon (PC), polyarylate, polystyrene (PS), aromatic polyamide, polyether-ether-ketone, polysulfones, polyether sulfone, polyimides, PEI can be enumerated, and then the resin molding etc. be laminated by the above-mentioned resin molding of more than 2 layers can be enumerated.From the view point of cost, obtain easiness, preferably use PETG (PET), PEN (PEN), Merlon (PC) etc.

The thickness of the base material that the present invention relates to is preferably 5 ~ 200 μm, is more preferably 15 ~ 150 μm.Base material is overlapping by more than 2, and now, the kind of base material can be identical, also can be different.

In addition, the transmissivity of the visible region shown in the preferred JIS R3106:1998 of the base material that the present invention relates to is more than 85%, is more preferably more than 90%.If be the scope of such transmissivity, then the transmissivity of visible region shown in JIS R3106:1998 when forming infrared ray shielding film is reached more than 40% favourable, thus preferably.

The base material that the present invention relates to can utilize known conventional method manufacture.Such as, utilize extruder to become the resin melting of material, utilize ring-like mould, T-shaped mould carries out extruding and make its quenching, the base material do not stretched amorphous and non-oriented in fact can be manufactured thus.In addition, by the base material do not stretched is utilized uniaxial tension, tentering formula successively biaxial stretch-formed, tentering formula simultaneously biaxial stretch-formed, tubular type simultaneously the known method such as biaxial stretch-formed flowing (longitudinal axis) direction of base material or with the direction of the flow direction of base material (transverse axis) at a right angle on stretch, stretch support body can be manufactured.Stretching ratio now suitably can be selected according to the resin becoming substrate material, but distinguishes preferably 2 ~ 10 times on y direction and X direction.

As mentioned above, base material can be unstretching film, also can be stretched film, but from viewpoints such as raising intensity, suppression thermal expansions, preferred stretched film.

In addition, from the view point of dimensional stability, relaxation process, off-line heat treatment can be carried out for the base material that the present invention relates to.After the heat fixation of relaxation process preferably in the stretching film making process of above-mentioned polyester film, carry out in the operation till the winding after taking out in the stenter of horizontal stretching or from stenter.Relaxation process is preferably carried out at treatment temperature is 80 ~ 200 DEG C, more preferably 100 ~ 180 DEG C.In addition, length direction, width are all preferred to carry out in the scope that relaxation rate is 0.1 ~ 10%, is more preferably 2 ~ 6% to process with relaxation rate.Through supporter heat resistance raising by the above-mentioned off-line heat treatment of enforcement of relaxation process, and then dimensional stability becomes good.

The base material that the present invention relates to preferably in film-forming process to one or two sides with presence painting bottom coating coating fluid.In the present invention, the primary coat in film making process is called online primary coat.As to the resin used in the useful base coat liquid of the present invention, can enumerate mylar, acrylic acid modified polyester resin, polyurethane resin, acrylic resin, vinylite, permalon, polymine vinylidene resin, polyethylene imine resin, polyvinyl alcohol resin, modified polyvinylalcohol resin or gelatin etc., these may be used singly or as a mixture of two or more.Also known additive can be added in these priming coats.Above-mentioned priming coat can utilize the known methods such as the coating of roller coat, intaglio plate, scraper for coating, dip-coating, spraying to apply.As the coating weight of above-mentioned priming coat, preferably 0.01 ~ 2g/m ²(drying regime) left and right.

[layer containing tabular metallic]

The layer containing tabular metallic that the present invention relates to is formed in the one side of base material.Layer containing tabular metallic can be single layer structure, also can be the stepped construction of more than 2 layers.In addition, the material of metallic can be used alone, and also can combine two or more and use.

The material of metallic is not particularly limited, such as, under can enumerating the normal temperature states such as gold, silver, copper, aluminium, gallium, indium, zinc, rhodium, palladium, iridium, nickel, platinum, manganese, iron, zirconium, molybdenum, chromium, tungsten, tin, germanium, lead, antimony stable metal simple-substance, or the alloy of these metals.Wherein, preferred stability in use is high gold, silver, copper.And, particularly preferably use silver.That is, the layer containing tabular metallic is preferably at least containing tabular silver particles.

(tabular metallic)

As above-mentioned tabular metallic, as long as the particle be made up of 2 principal planes is just not particularly limited, suitably can select according to object.As the example from the shape during top view of principal plane, such as, can enumerate roughly hexagon (with reference to Figure 1A), roughly disc-shape (with reference to Figure 1B), general triangular etc.Wherein, high from the view point of luminous ray transmissivity, be preferably roughly hexagon, roughly disc-shape.

As roughly hexagon, as long as utilizing transmission electron microscope (TEM) from being roughly hexagon during the top view tabular metallic of principal plane, being just not particularly limited, suitably can selecting according to object.Such as hexagonal angle can be sharp-pointed angle, also can be round and smooth angle, but from the viewpoint of reducing the absorption of visible region, angle is preferably round and smooth angle.As the round and smooth degree at angle, be not particularly limited, can suitably select.

As roughly disc-shape, as long as utilizing transmission electron microscope (TEM) from being there is no angle and rounded shape during the top view tabular metallic of principal plane, being just not particularly limited, can suitably selecting.

Roughly the ratio of hexagon or the roughly tabular metallic of disc-shape is relative to total number of tabular metallic, preferably more than 60 number %, more preferably more than 65 number %, further preferred more than 70 number %.If the ratio of above-mentioned tabular metallic is above-mentioned scope, then luminous ray transmissivity improves.

The average grain diameter of tabular metallic is not particularly limited, and can suitably select, but preferred 70nm ~ 500nm, more preferably 100nm ~ 400nm.If average grain diameter is above-mentioned scope, then can obtain sufficient infrared reflection energy, mist degree diminishes, and the transparency improves.Should illustrate, above-mentioned average grain diameter refers to the mean value of the principal plane diameter (maximum length) of optional 200 dull and stereotyped particles from the image utilizing tem observation particle to obtain.

Can contain the different tabular metallic of more than two kinds of average grain diameter in the layer containing tabular metallic, now, the peak of the average grain diameter of tabular metallic is more than 2, can have 2 average grain diameters.

The coefficient of variation in the size distribution of above-mentioned tabular metallic is preferably less than 30%, is more preferably less than 10%.If the above-mentioned coefficient of variation is above-mentioned scope, then become more sharp-pointed containing the ultrared reflecting wavelength regions in the layer of tabular metallic.

Here, the coefficient of variation in the size distribution of above-mentioned tabular metallic is such as the value (%) obtained in the following way, namely, the distribution of the particle diameter of use in the calculating of above-mentioned average grain diameter 200 tabular metallics is marked and drawed, obtain the standard deviation of size distribution, divided by the mean value (average grain diameter) of the principal plane diameter (maximum length) obtained by said method.

As the aspect ratio of above-mentioned tabular metallic, be not particularly limited, suitably can select according to object, but uprise from the view point of by the reflectivity of visible region long wavelength side near infrared light region, be preferably more than 2, be more preferably 2 ~ 30, more preferably 4 ~ 25.If above-mentioned aspect ratio is above-mentioned scope, then infrared reflection rate is greatly variable, and mist degree can diminish.Should illustrate, aspect ratio refers to the value (L/d) (with reference to Figure 1A and Figure 1B) that the average grain diameter (average equivalent circular diameter) (L) of tabular metallic obtains divided by averaged particles thickness (d) of tabular metallic.The principal plane spacing of averaged particles thickness and tabular metallic is suitable, such as, AFM (AFM) can be utilized to measure.

As the method utilizing above-mentioned AFM to measure averaged particles thickness, be not particularly limited, suitably can select, such as, can enumerate and drip the particle dispersion containing tabular metallic on the glass substrate and make it dry and measure the method etc. of the thickness of 1 tabular metallic.

The content (adhesion amount) of the tabular metallic in the layer containing tabular metallic is preferably 0.01 ~ 1g/m ²(10 ~ 1000mg/m ²), be more preferably 0.02 ~ 0.5g/m ²(20 ~ 500mg/m ²), be particularly preferably 0.025 ~ 0.15g/m ²(25 ~ 150mg/m ²).

(manufacture method of tabular metallic)

As the manufacture method of above-mentioned tabular metallic, such as, can enumerate the liquid phase methods etc. such as chemical reduction method, photochemical reduction, electrochemical reducing.Wherein, from the view point of shape and size controlling, preferred chemical reduction method, photochemical reduction etc.After synthesis hexagon or leg-of-mutton tabular metallic, such as, utilize nitric acid, sodium sulfite, Br ^-, Cl ^-the dissolving kind of dissolving silver Deng halide ion etc. carries out etch processes, or utilizes heating to carry out burin-in process, makes the angle rust of hexagon or leg-of-mutton tabular metallic thus, can obtain the tabular metallic of roughly hexagon or roughly disc-shape.

Should illustrate, as the manufacture method of above-mentioned tabular metallic, than that described above, also can adopt in advance after crystal seed is fixed on the surface of the transparent base such as film, glass, make metallic (such as Ag) crystalline growth become flat method.

In order to give desired characteristic, further process can be implemented for above-mentioned tabular metallic.As such process, be not particularly limited, such as, can enumerate and form high index of refraction shell, add the various additives such as dispersant, antioxidant etc.

In order to improve the transparency of visible region further, the high-index material that the transparency that above-mentioned tabular metallic can be used in visible region is high is coated to.

As above-mentioned high-index material, be not particularly limited, such as, can enumerate TiO _x, BaTiO ₃, ZnO, SnO ₂, ZrO ₂, NbO _xdeng.

As above-mentioned coating method, be not particularly limited, such as, can adopt as Langmuir, 2000,16 volumes, p.2731-2735, report forms TiO by four titanium butoxide being hydrolyzed on the surface of tabular metallic _xthe method of layer.

In addition, when being difficult to directly form high index of refraction shell on above-mentioned tabular metallic, after synthesizing tabular metallic as mentioned above, suitably SiO can be formed ₂, polymer shell, then form metal oxide layer on this shell.Use TiO _xduring material as high index of refraction shell, due to TiO _xthere is photocatalytic activity, so worry can make the matrix deterioration of dispersion tabular metallic, therefore can form TiO according to object on tabular metallic _xafter layer, suitably form SiO ₂layer.

In order to suppress the oxidation of the metals such as the silver forming this tabular metallic, above-mentioned tabular metallic can adsorb the antioxidant such as mercapto-tetrazole, ascorbic acid.In addition, for oxidation resistant object, the oxidation sacrifice layers such as Ni can be formed on the surface of tabular metallic.In addition, for suppress oxygen through object, also can use SiO ₂be coated to Deng metal oxide film.

For giving dispersed object, above-mentioned tabular metallic can add the low-molecular-weight dispersant containing N element, S element, P element, such as quaternary ammonium salt, amine, the dispersants such as high molecular weight dispersant.

(planar orientation)

In the layer containing above-mentioned tabular metallic, tabular metallic preferably its principal plane carries out planar orientation relative to the surface of base material with the scope of regulation.

From the view point of raising infrared reflection rate, above-mentioned tabular metallic preferably distributes (partially existing) in approximate horizontal unevenly relative to substrate plane.

As such planar orientation, as long as the principal plane of tabular metallic and the surface of base material become almost parallel mode with the scope specified, just be not particularly limited, but the angle of preferred planar orientation is 0 ° ~ ± 40 °, be more preferably 0 ° ~ ± 30 °, more preferably 0 ° ~ ± 20 °, be particularly preferably 0 ° ~ ± 5 °.If be above-mentioned scope, then infrared reflection rate improves.

Here, Fig. 2 A ~ Fig. 2 C represents in infrared ray shielding film of the present invention, the schematic cross-section of the existence of the tabular metallic 1 in the layer 2 containing tabular metallic.Fig. 2 A is the figure of the desirable existence of the tabular metallic 1 represented in the layer 2 containing tabular metallic.Fig. 2 B is the figure that the plane of base material 3 and the principal plane angulation (± θ) of tabular metallic 1 are described.Fig. 2 C represents the figure of the layer 2 containing tabular metallic at the domain of the existence of the depth direction of infrared ray shielding film.

In Fig. 2 B, the extended line angulation (± θ) of the surface of base material 1 and the principal plane of tabular metallic 3 or principal plane is corresponding to the scope of the regulation in above-mentioned planar orientation.Namely, when planar orientation refers to the cross section observing infrared ray shielding film, the state that inclination angle (± θ) shown in Fig. 2 B is little, especially represents that in Fig. 2 A, the surface of base material 1 and the principal plane angulation (θ) of tabular metallic 3 are the state of 0 °.If the principal plane of tabular metallic 3 is preferably within ± 40 ° relative to the θ in the angle of the planar orientation on the surface of base material 1, i.e. Fig. 2 B, is more preferably ± 30 ° within, then the provision wavelengths of infrared ray shielding film (such as, from visible region long wavelength side near infrared light region) reflectivity improve, mist degree diminishes, thus preferably.

(evaluation method of planar orientation)

Whether carry out the evaluation method of planar orientation as the principal plane of tabular metallic relative to the surface of above-mentioned base material, such as, can enumerate and make suitable cross-sectional slice and the base material peace plate-shape metal particle observed in this section carries out the method evaluated.Specifically, following method can be enumerated: cross-sectional sample or the cross-sectional slice sample of infrared ray shielding film razor, slicer, FIB (FIB) etc. being made infrared ray shielding film, use various microscope (such as, sweep electron microscope (SEM), electric field radioactive SEM (FE-SEM) etc.) observe this sample, evaluate according to gained image.

In above-mentioned infrared ray shielding film, the binding agent of coating tabular metallic during swelling, can make cross-sectional sample or cross-sectional slice sample by utilizing the diamond segment cutting being installed on slicer with the sample under the state of liquid nitrogen frozen because of water.In addition, in infrared ray shielding film, the binding agent of coating tabular metallic during swelling, can not make cross-sectional sample or cross-sectional slice sample because of water yet.

As long as whether the observational technique of the cross-sectional sample of making described above or cross-sectional slice sample the principal plane of confirmatory sample middle plateform shape metallic can carry out planar orientation relative to the surface of base material and be just not particularly limited, such as, can enumerate the observational technique employing SEM, FE-SEM, transmission electron microscope (TEM), light microscope etc.For FE-SEM can be utilized during above-mentioned cross-sectional sample to observe, for TEM can be utilized during above-mentioned cross-sectional slice sample to observe.When evaluating with FE-SEM, preferably there is the spatial resolution at the shape that clearly can judge tabular metallic and inclination angle (Fig. 2 B ± θ).

(existence range of tabular metallic)

In infrared ray shielding film of the present invention, as shown in Figure 2 C, when the plasma resonance wavelength of the metal formed containing the tabular metallic 3 in the layer 2 of tabular metallic is set to λ and the refractive index of the medium in the layer 2 containing tabular metallic is set to n, the above-mentioned layer 2 containing tabular metallic preferably exists with the scope of (λ/n)/4 on the depth direction of the horizontal plane from infrared ray shielding film.If be this scope, then the effect that the phase place of the back wave on the surface of infrared ray shielding film and back side Air Interface separately strengthens mutually increases, and can improve luminous ray transmissivity and infrared ray maximum reflectivity.

The plasma resonance wavelength X forming the metal containing the tabular metallic in the layer of tabular metallic that the present invention relates to is not particularly limited, but from the view point of imparting infrared reflection performance, be preferably 400nm ~ 2500nm, from the view point of the mist degree (scattering) reducing visible region, be more preferably 700nm ~ 2500nm.

As the medium in the layer containing tabular metallic, be not particularly limited, such as, can enumerate the inorganic matters etc. such as the macromolecules such as the natural polymers such as polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, plexiglass, polycarbonate resin, Corvic, saturated polyester resin, polyurethane resin, gelatin or cellulose, silica, aluminium oxide.

The refractive index (n) of above-mentioned medium is preferably 1.4 ~ 1.7.

(occupied area of tabular metallic and area occupation ratio)

Seen from above during infrared ray shielding film of the present invention, namely tabular metallic time viewed from the stacked direction of multilayer dielectric film, layer containing tabular metallic relative to base material area A shared by the aggregate value of area, the area occupation ratio C namely as the ratio of the occupied area B of tabular metallic is represented by following formula (1).

C [%]=(B/A) × 100 ... (formula 1)

Should illustrate, when infrared ray shielding film have multilayer contain the layer of tabular metallic time, by under the state that these are folded layer by layer viewed from stacked direction time the occupied area of tabular metallic be set to B.In other words, when the tabular metallic of one deck and another layer is completely overlapping each other, only measure the area of the tabular metallic part of the large layer of area, when this particle fraction is overlapping, the area in the periphery of the particle that measurement overlaps each other.

Above-mentioned area occupation ratio C specifically utilizes and carries out measuring, calculating with 30000 times of observable SEM images.Below, its step is illustrated.

First, the optional position shooting SEM image on infrared ray shielding film.Next, gained SEM image is carried out binaryzation with the form of black white image, obtain the occupied area b of total as actual measurement of the area of the part that there is tabular metallic.On the other hand, the area of the field range of SEM image is set to a.Then, the area occupation ratio c surveyed is obtained based on following formula (2).

C [%]=(b/a) × 100 ... (formula 2)

Above-mentioned series of steps is carried out in any 3 positions on infrared ray shielding film, using the area occupation ratio C of the mean value of the value of obtained c as above-mentioned formula 1.In addition, the pass of the substrate area A in above-mentioned formula (1) and the area a of occupied area B and field range, the occupied area b of actual measurement is A:a=B:b.

In infrared ray shielding film of the present invention, area occupation ratio C is preferably more than 15%, is more preferably more than 20%.If above-mentioned area occupation ratio C is above-mentioned scope, then ultrared maximum reflectivity improves, and fully obtains effect of heat insulation and insulation effect.

The higher limit of area occupation ratio C is not particularly limited, and such as, need in the purposes of the transparency at the glass etc. of gazebo, this higher limit is preferably less than 90%.In addition, need in the purposes of electromagnetic shielding at automotive glass etc., this higher limit is preferably less than 100%.In addition, if area occupation ratio C is less than 90%, then when the attaching of infrared ray shielding film being arranged at the objects such as glass, becoming and easily dewater, also can obtain the effect that adaptation improves.In addition, the infrared ray shielding film that to have containing area occupation ratio C be the layer of tabular metallic in above-mentioned scope also can obtain effective anti-mold effect.

That is, in infrared ray shielding film of the present invention, area occupation ratio C is preferably more than 15% and is less than 90%.Area occupation ratio C is more preferably 20% ~ 85%, and then is particularly preferably 55% ~ 80%.By being 20% ~ 85%, high effect of heat insulation and insulation effect can be obtained, and extremely good adaptation can be obtained.In addition, by being 55% ~ 80%, infrared ray shielding film all extremely good in effect of heat insulation, insulation effect, adaptation are all can be obtained.In addition, in above-mentioned scope, infrared ray shielding film also has good anti-mold effect.

In the layer containing tabular metallic, be that the formation method of the layer of the tabular metallic of above-mentioned scope is at following detailed description containing area occupation ratio C.

(average interparticle distance of tabular metallic)

From the view point of luminous ray transmissivity and ultrared maximum reflectivity, what the present invention relates to is preferably more than 1/10 of the average grain diameter of tabular metallic containing the average interparticle distance adjoining tabular metallic in the layer of tabular metallic in the horizontal direction.

If tabular metallic average interparticle distance is in the horizontal direction above-mentioned scope, then ultrared maximum reflectivity improves.In addition, from the view point of luminous ray transmissivity, the average interparticle distance of horizontal direction preferably uneven (random).If random, then not easily cause the absorption of luminous ray, luminous ray transmissivity improves.

Here, above-mentioned tabular metallic average interparticle distance in the horizontal direction refers to the mean value of the interparticle distance of 2 adjacent particles.In addition, above-mentioned average interparticle distance is random to be referred to " when obtaining the two-dimensional autocorrelation of the brightness value when SEM image containing the tabular metallic of more than 100 being carried out binaryzation, beyond initial point, not having significant maximal point ".

In infrared ray shielding film of the present invention, as shown in Fig. 2 A ~ Fig. 2 C, tabular metallic is configured with the form of the layer containing tabular metallic.

As shown in Fig. 2 A ~ Fig. 2 C, the layer containing tabular metallic can be made up of individual layer, also can be made up of multilayer.When being made up of multilayer, the screening performance corresponding to the wavelength band domain will giving heat-proof quality can be given.

(the formation method of the layer containing tabular metallic)

As the formation method of the layer containing tabular metallic that the present invention relates to, be not particularly limited, can be formed according to known method.Such as, coating can be preferably adopted to coordinate the rubbing method of the coating fluid containing tabular metallic of mentioned component and formed.By using rubbing method, the area occupation ratio C shared by above-mentioned tabular metallic easily can be controlled.Specifically, the tabular metallic that the method illustrated in medium and employing above-mentioned (manufacture method of tabular metallic) obtains is made an addition in suitable solvent, prepare coating fluid, use line rod to wait the thickness (thickness under non-drying regime) adjusted when being coated with this coating fluid, area occupation ratio C can be controlled as desired scope thus.In addition, after applied coating solution, by adjusting the temperature (baking temperature) during drying, adjustable tabular metallic relative to the angle (above-mentioned θ) of base material, therefore, as its result, can control area rate C.Should illustrate, if improve baking temperature, then the value of above-mentioned θ is close to 90 °, can reduce the area occupation ratio C shared by tabular metallic.In addition, the adhesion amount of tabular metallic is adjusted by suitably regulating the concentration of coating fluid, also can control area rate C.

More specifically, the area occupation ratio in order to the ratio making the occupied area as the tabular metallic relative to base material area becomes above-mentioned preferred scope, preferably makes baking temperature be 50 ~ 150 DEG C, makes the adhesion amount of tabular metallic be 10 ~ 200mg/m ².About baking temperature, be more preferably 60 ~ 100 DEG C, in addition, about adhesion amount, be more preferably 25 ~ 150mg/m ².

As above-mentioned rubbing method, such as, can enumerate spin-coating method, dip coating, extrusion coating methods, stick coating method, mould painting method, gravure coating process etc.

In addition, the method utilizing the method such as LB embrane method, self-organization method, injection coating to make tabular metallic planar orientation can also be used.

As the method making tabular metallic planar orientation, in order to improve adsorptivity, the planar orientation of tabular metallic to base material, the method utilizing electrostatic interaction to make its planar orientation can be adopted.Specifically, during the surface band negative electricity of tabular metallic (such as, be scattered in the state in the medium of the negatively charged such as citric acid), positively charged is (such as in advance can to adopt surface by making base material, substrate surface is modified with amino etc.), improve electrostatic planar orientation and carry out the method for planar orientation.In addition, when the surface of tabular metallic is hydrophily, block copolymer, Microcontact printing method etc. can be utilized to make the surface of base material be pre-formed the island structure of hydrophilic and hydrophobic, utilize hydrophobe interaction to carry out the interparticle distance of chain of command orientation peace plate-shape metal particle.

Should illustrating, in order to promote planar orientation, after coating is containing the coating fluid of tabular metallic, the operation by the press bonding roller such as stack, laminating roll can be carried out.

The thickness of the layer containing tabular metallic is not particularly limited, but is preferably 0.1 μm ~ 10 μm, is more preferably 0.5 ~ 8 μm.

(other composition)

The layer containing tabular metallic that the present invention relates to can contain various additive, such as solvent, binding agent, surfactant, antioxidant, sulfur resistive agent, anticorrosive, infrared absorbent, ultra-violet absorber, colouring agent, viscosity modifier, anticorrisive agent etc. as required.

[multilayer dielectric film]

Infrared ray shielding film of the present invention has the multilayer dielectric film containing high refractive index layer and low-index layer.And, this multilayer dielectric film can be formed on the face with the side same side being formed with the above-mentioned layer containing tabular metallic relative to base material, in addition, the face with the opposition side, side being formed with the above-mentioned layer containing tabular metallic can be also formed on relative to this base material.That is, the layer containing tabular metallic and dielectric tunic can be formed on a face side of base material, or they also can be formed across base material.As the material forming multilayer dielectric film, known material can be used, such as, can enumerate metal oxide particle, polymer and their combination etc.

About metal oxide particle, as the example of high-index material, titanium dioxide (TiO can be enumerated ₂), zirconium dioxide (ZrO ₂), tantalum pentoxide (Ta ₂o ₅) etc., as the example of low-index material, silica (SiO can be enumerated ₂), magnesium fluoride (MgF ₂) etc., as the example of medium-index materials, aluminium oxide (Al can be enumerated ₂o ₃) etc.The dry type such as vapour deposition method, sputtering method masking method can be utilized these metal oxide particle maskings.

The polymer contained in multilayer dielectric film is not particularly limited, as long as the polymer that can form multilayer dielectric film is just not particularly limited.

Such as, as polymer, the polymer recorded in Japanese Unexamined Patent Application Publication 2002-509279 publication can be used.As concrete example, such as, can enumerate PEN (PEN) and isomers (such as, 2,6-thereof, Isosorbide-5-Nitrae-, 1,5-, 2,7-and 2,3-PEN), polyalkylene terephthalates (such as, PETG (PET), polybutylene terephthalate (PBT), and poly terephthalic acid-1,4-CHDM ester), polyimides (such as, polyacrylimide), PEI, random isotactic polystyrene, Merlon, polymethacrylates (such as, polyisobutyl methacrylate, polypropylmethacryla,es, polyethyl methacrylate, and polymethyl methacrylate (PMMA)), polyacrylate (such as, butyl polyacrylate, and PMA), cellulose derivative (such as, ethyl cellulose, acetylcellulose, cellulose propionate, acetobutyrate, and celluloid), polyalkylene polymer (such as, polyethylene, polypropylene, polybutene, poly-second propylene, and poly-(4-methyl) amylene), fluorinated polymer (such as, perfluoroalkoxy resin, polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer, Kynoar, and polychlorotrifluoroethylene), chlorinated polymeric (such as, Vingon and polyvinyl chloride), polysulfones, polyether sulfone, polyacrylonitrile, polyamide, organic siliconresin, epoxy resin, polyvinyl acetate, polyetheramides, ionomer resin, elastomer (such as, polybutadiene, polyisoprene and neoprene), and polyurethane.As copolymer, copolymer [such as, (a) terephthalic acid (TPA) or its ester of such as applicable PEN, (b) M-phthalic acid or its ester, (c) phthalic acid or its ester, (d) alkanediol, (e) cycloalkanes glycol (such as, cyclohexanedimethanol glycol), (f) alkane dicarboxylic acid and/or (g) Cycloalkane dicarboxylic acid (such as, cyclohexane cyclohexanedimethanodibasic) and 2,6-, Isosorbide-5-Nitrae-, 1,5-, the copolymer of 2,7-and/or 2,3-naphthalene dicarboxylic acids or their ester], copolymer [such as, (a) naphthalenedicarboxylic acid or its ester of polyalkylene terephthalates, (b) M-phthalic acid or its ester, (c) phthalic acid or its ester, (d) alkanediol, (e) cycloalkanes glycol (such as, cyclohexanedimethanol glycol), the copolymer of (f) alkane dicarboxylic acid and/or (g) Cycloalkane dicarboxylic acid (such as, cyclohexane cyclohexanedimethanodibasic) and terephthalic acid (TPA) or its ester], and styrol copolymer (such as, SB and SAN), 4,4-dibenzoic acid and ethylene glycol.In addition, each layer can contain the mixture (such as, the mixture of syndiotactic polystyrene (SPS) and random isotactic polystyrene) of 2 kinds or its above above-mentioned polymer or copolymer respectively.

Can by above-mentioned polymer as United States Patent (USP) the 6th, that records in 049, No. 419 descriptions utilizes melt extruding and stretching to form multilayer dielectric film of polymer like that.In the present invention, as the preferred compositions of polymer forming high refractive index layer and low-index layer, PEN/PMMA, PEN/ Kynoar, PEN/PET can be enumerated.

In addition, as polymer, the polymer recorded in No. 2010-184493, Japanese Unexamined Patent Publication can be used.Specifically, the polyester (hereinafter also referred to as polyester B) of polyester (hereinafter also referred to as polyester A) and the residue containing at least 3 kinds of dihydroxylic alcohols derived from ethylene glycol, the spiroglycol and butanediol can be used.Just be not particularly limited as long as polyester A has the structure that dicarboxylic acids composition and glycol component polycondensation obtain, such as can enumerate PETG, PTT, polybutylene terephthalate (PBT), poly-2,6-(ethylene naphthalate), poly terephthalic acid-1,4-CHDM ester, poly-diphenylglycollic acid glycol ester.Polyester A also can be copolymer.Here, copolyester refers to the structure having and use the dicarboxylic acids composition of more than at least 3 kinds altogether and glycol component to carry out polycondensation and obtain.As dicarboxylic acids composition, terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1 can be enumerated, 4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-diphenyl sulfone dioctyl phthalate, adipic acid, decanedioic acid, dimeric dibasic acid, cyclohexane cyclohexanedimethanodibasic and their ester formative derivative etc.As glycol component, ethylene glycol, 1 can be enumerated, 2-propane diols, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, diethylene glycol, PAG, 2,2-two (4 '-beta-hydroxy ethoxyl phenenyl) propane, Soquad, 1,4-CHDM, the spiroglycol and their ester formative derivatives etc.Polyester A is preferably PETG or PEN.

Above-mentioned polyester B contains the residue of at least 3 kinds of dihydroxylic alcohols derived from ethylene glycol, the spiroglycol and butanediol.As typical example, have to have and make spent glycol, the spiroglycol and butanediol copolymerization and polyester that the copolyester of structure that obtains or the polyester of structure that uses these 3 kinds of dihydroxylic alcohols to carry out being polymerized by having and obtain are obtained by mixing.If this formation, then easily carry out processing and forming and not easily splitting occur, thus preferably.In addition, the polyester of the residue of polyester B preferably containing at least 2 kinds of dicarboxylic acids derived from terephthalic acid (TPA)/cyclohexane cyclohexanedimethanodibasic.Such polyester comprises copolyesters terephthalic acid (TPA)/cyclohexane cyclohexanedimethanodibasic copolymerization obtained or the polyester polyester containing terephthalic acid residue and the polyester containing cyclohexanedicarboxylic acid are obtained by mixing.Polyester containing cyclohexanedicarboxylic acid makes the difference of mean refractive index in the face of mean refractive index and B layer in the face of A layer become greatly, can obtain the multilayer dielectric film of high reflectance.In addition, due to little with the glass transition temperature difference of PETG or PEN, thus shaping time not easily excessive tensile and also not easily splitting occurs, thus preferably.

In addition, also preferably water soluble polymer is used as polymer.That is, multilayer dielectric film is preferably containing water soluble polymer.Water soluble polymer is not due to an organic solvent, so environmental pressure is little, in addition, flexibility is high, thus bending time the durability of film improve, thus preferably.As water soluble polymer, such as, polyvinyl alcohol can be enumerated, PVP class, polyacrylic acid, AA-AN copolymerization thing, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylate copolymer, or the acrylic resin such as acrylic acid and acrylic ester copolymers, Styrene-acrylic copolymer, Styrene-methyl Acrylic Acid Copolymer, styrene-t-acrylate copolymer, styrene-α-methylstyrene-acrylic copolymer, or the styrene acrylic resins such as styrene-α-methylstyrene-acrylic acid and acrylic ester copolymers, styrene-styrene sodium sulfonate copolymers, Styrene And Chloroalkyl Acrylates 2-hydroxy methacrylate copolymer, Styrene And Chloroalkyl Acrylates 2-hydroxy methacrylate-styrene sulfonic acid potassium copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-maleate copolymer, vinyl acetate-crotonic acid copolymer, the synthesizing water-solubility macromolecules such as vinyl acetate based copolymer and their salt such as vinyl acetate-acrylic copolymer, the water-soluble macromolecules etc. such as gelatin, thickening polysaccharide.Wherein, as more preferred example, from the view point of operability when manufacturing and the flexibility of film, polyvinyl alcohol, PVP class and copolymer, gelatin, thickening polysaccharide (particularly cellulose family) containing it can be enumerated.These water soluble polymers can be used alone or two or more kinds may be used use.

In the polyvinyl alcohol preferably used in the present invention, except comprising the common polyvinyl alcohol that obtained by polyvinyl acetate Ester hydrolysis, also comprise modified polyvinylalcohol.As modified polyvinylalcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonionic modified polyvinyl alcohol, vinyl alcohol system polymer can be enumerated.

The polyvinyl alcohol that vinyl acetate Ester hydrolysis is obtained preferably use average degree of polymerization be more than 800 polyvinyl alcohol, particularly preferably use average degree of polymerization be the polyvinyl alcohol of 1000 ~ 5000.In addition, saponification degree is preferably 70 ~ 100 % by mole, is particularly preferably 80 ~ 99.5 % by mole.

As cation-modified polyvinyl alcohol, such as in order to have in the main chain at above-mentioned polyvinyl alcohol as recorded in Japanese Laid-Open Patent Publication 61-10483 publication or side chain, primary ~ uncle is amino, the polyvinyl alcohol of quaternary ammonium group, by the copolymer saponification of the ethylene unsaturated monomer and vinyl acetate with cationic groups being obtained.

As the ethylene unsaturated monomer with cationic groups, such as can enumerate (2-acrylamido-2,2-dimethyl ethyl) trimethyl ammonium chloride, (3-acrylamido-3,3-dimethyl propyl) trimethyl ammonium chloride, N-vinyl imidazole, N-vinyl-glyoxal ethyline, N-(3-dimethylaminopropyl) Methacrylamide, hydroxyethyl trimethyl ammonium chloride, (2-methacryiamidopropyl) trimethyl ammonium chloride, N-(1,1-dimethyl-3-dimethylaminopropyl) acrylamide etc.The ratio of the monomer of the cation modified group of cation-modified polyvinyl alcohol is preferably 0.1 ~ 10 % by mole relative to vinyl acetate, is more preferably 0.2 ~ 5 % by mole.

As anion-modified polyvinyl alcohol, such as, can enumerate the polyvinyl alcohol with anionic property group as recorded in Japanese Unexamined Patent Publication 1-206088 publication, as the vinyl alcohol recorded in Japanese Laid-Open Patent Publication 61-237681 publication and Japanese Laid-Open Patent Publication 63-307979 publication and the copolymer of vinyl compound and the modified polyvinylalcohol with water soluble group as recorded in Unexamined Patent 7-285265 publication with water soluble group.

In addition; as nonionic modified polyvinyl alcohol; such as can enumerate a part of addition polyalkylene oxide group at vinyl alcohol as recorded in Japanese Unexamined Patent Publication 7-9758 publication and the polyvinyl alcohol derivative obtained; as what record in Japanese Unexamined Patent Publication 8-25795 publication, there is the vinyl compound of hydrophobic group and the block copolymer of vinyl alcohol; there is the silanol-modified polyvinyl alcohol of silanol group, there is the reactive group modified polyvinylalcohol etc. of acetoacetyl, carbonyl, carboxyl isoreactivity group.In addition, as vinyl alcohol system polymer, EXCEVAL (registration mark, Co., Ltd. Kuraray system), Nichigo G polymer (trade name, the Nippon Synthetic Chemical Industry Co., Ltd's system) etc. can be enumerated.Polyvinyl alcohol also can be used together the degree of polymerization, modification kind dispar two or more.

As the gelatin used in the present invention, outside delime process gelatin, acid treatment gelatin can also be used, also can use the enzyme analyte of the hydrolysate of gelatin, gelatin in addition.

As the thickening polysaccharide used in the present invention, such as can enumerate usually known natural simple polysaccharide, natural complex polysaccharide class, synthesize simple polysaccharide and synthesis complex polysaccharide class, for the details of these polysaccharides, can refer to " biochemical topical reference book (the 2nd edition), Tokyo chemistry is published with people ", " food industry " the 31st volume (1988) 21 pages etc.

The thickening polysaccharide mentioned in the present invention is the polymer of carbohydrate, there is multiple hydrogen bond group in molecule, cause intermolecular hydrogen bond force different because of temperature, be thus viscosity when possessing low temperature and high temperature time the polysaccharide of the large characteristic of differences in viscosity, if add metal oxide microparticle further, then the viscosity being considered to be caused by the hydrogen bond with this metal oxide microparticle is caused to rise when low temperature.With regard to its viscosity ascensional range, being the viscosity of 40 DEG C produces the rising of preferred more than 1.0mPas polysaccharide by adding, is the polysaccharide possessing the viscosity ascending ability being more preferably more than 5.0mPas, more preferably more than 10.0mPas.

As thickening polysaccharide used in the present invention, such as can enumerate β 1-4 glucan (such as, carboxymethyl cellulose, carboxyethyl cellulose etc.), galactan (such as, agarose, agaropectin etc.), galactomannans (such as, locust bean gum, guar gum etc.), xyloglucan (such as, tamarind gum etc.), glucomannan (such as, konjacmannan, from the Glucomannan of timber, xanthans etc.), gala glucomannan (such as, glycan from needlebush), arabogalactan (such as, from the glycan of soybean, glycan etc. from microorganism), grape rhamnosan (such as, gellan gum etc.), glycosaminoglycan (such as, hyaluronic acid, keratan sulfate etc.), alginic acid and alginate, agar, kappa-carrageenan, lambda-carrageenan, ι-carragheen, furcellarans etc. are from the natural macromolecule amylose class etc. of red algae.Particularly, when containing metal oxide particle as described later, the viewpoint never reducing the dispersion stabilization of metal oxide particles is set out, and preferably its Component units does not have the polysaccharide of carboxyl, sulfinyl.As such polysaccharide, such as, preferably only by pentoses such as Arabinose, D-ribose, 2-deoxyribosyl, D-wood sugars, the polysaccharide that the hexoses such as D-Glucose, D-Fructose, D-MANNOSE, D-galactolipin are formed.Specifically, main chain can be preferably used as to be glucose and side chain is the xyloglucan of wood sugar and known tamarind gum; Be mannose as main chain and side chain is the galactomannans of galactolipin and known guar gum, locust bean gum, tara gum; Main chain is galactolipin and side chain is the arabogalactan of arabinose.

In the present invention, can be used together two or more thickening polysaccharides.

The weight average molecular weight of water soluble polymer is preferably 1000 ~ 200000, is more preferably 3000 ~ 40000.Should illustrate, in this manual, weight average molecular weight adopts the value using gel permeation chromatography (GPC) to record under the condition determination shown in following table 1.

Table 1

[table 1]

Solvent: 0.2M NaNO ₃, NaH ₂pO ₄, pH7

Post: Shodex Column Ohpak SB-802.5HQ, 8 × 300mm and Shodex Column Ohpak SB-805 HQ, the combination of 8 × 300mm

Column temperature: 45 DEG C

Sample solution concentration: 0.1 quality %

Detector: RID-10A (Shimadzu Scisakusho Ltd's system)

Pump: LC-20AD (Shimadzu Scisakusho Ltd's system)

Flow: 1ml/min

Calibration curve: use the calibration curve made with Shodex Standard GFG (water system GPC) post Standard P-82 standard substance Propiram (Pullulan)

In the present invention, in order to make water soluble polymer solidify, curing agent can be used.

As curing agent used in the present invention, as long as be just not particularly limited with water soluble polymer generation curing reaction, but when water soluble polymer is polyvinyl alcohol, preferred boric acid and salt thereof, in addition, known curing agent can be used, be generally have can from the compound of the compound of the group that water soluble polymer reacts or the different groups promoting water soluble polymer to have reaction each other, suitably select according to the kind of water soluble polymer.As curing agent except boric acid and and salt except concrete example, such as can enumerate epoxy curing agent (diglycidyl ether, ethylene glycol diglycidylether, 1, 4-butanediol diglycidyl ether, 1, 6-2-glycidyl butylcyclohexane, N, N-diglycidyl-4-glycidyl-oxyaniline, D-sorbite polyglycidyl ether, glycerine polyglycidyl ether etc.), aldehyde system curing agent (formaldehyde, glyoxal etc.), active halogen prime system curing agent (2, 4-bis-chloro-4-hydroxyl-1, 3, 5-s-triazine etc.), active ethylene group based compound (1, 3, 5-tri--acryloyl group-six hydrogen-s-triazine, divinyl sulfonyl methyl ether etc.), al alum etc.

When water soluble polymer is gelatin, such as can enumerate organic hard coat agents such as vinyl sulfone compound, urea-formaldehyde condensate, carbamide condensation product, epoxy compound, aziridine based compound, active olefin class, isocyanates based compound, the inorganic polyvalent metallic salts etc. such as chromium, aluminium, zirconium.

Should illustrate, the form of copolymer when above-mentioned polymer is copolymer can be any one in block copolymer, random copolymer, graft copolymer, alternate copolymer.

For the preferred form of multilayer dielectric film, from the view point of can large area, aspect with low cost and bending time or hot and humid time film durability improve, preferred use polymer, except multilayer dielectric film is only except the form that polymer is formed, also preferably multilayer dielectric film contains the form of polymer and metal oxide particle further.

To except being also described containing the form of metal oxide particle containing except polymer.By making multilayer dielectric film contain metal oxide particle, the refringence between each index layer can be increased, stacked number can be reduced, the transparency of film can be improved thus, thus preferably.In addition, have stress relax work, film physical property (bendability time bending and time hot and humid) puies forward advantages of higher.Metal oxide particle is contained in the arbitrary film forming multilayer dielectric film, but preferred form is that at least high refractive index layer contains the form of metal oxide particle, and preferred form is high refractive index layer and the form of low-index layer all containing metal oxide particle.That is, preferred high refractive index layer and low-index layer contain metal oxide particle.

As metal oxide particle, such as, can enumerate titanium dioxide, zirconium dioxide, tantalum pentoxide, zinc oxide, silica (synthesis amorphous silica, cataloid etc.), aluminium oxide, colloidal alumina, lead titanates, red lead, chrome yellow, zinc yellow, chromium oxide, iron oxide, iron oxide black, cupric oxide, magnesia, magnesium hydroxide, magnesium fluoride, strontium titanates, yittrium oxide, niobium oxide, europium oxide, lanthana, zircon, tin oxide etc.

The average grain diameter of metal oxide particle is preferably below 100nm, is more preferably 4 ~ 50nm, more preferably 5 ~ 40nm.The average grain diameter of metal oxide particle is obtained as follows: with electron microscope observation particle itself or at the cross section of layer or the surperficial particle occurred, measure the particle diameter of 1000 Arbitrary Particles, obtain its simple average value (number is average).Here, the particle diameter of each particle is by supposing that the diameter of the bowlder equal with its projected area represents.

The content of the metal oxide particle in each index layer, relative to the gross mass of index layer, is preferably 20 ~ 90 quality %, is more preferably 40 ~ 75 quality %.

As metal oxide particle, preferably use the solia particle be selected from titanium dioxide, silica and aluminium oxide.

In low-index layer, preferably use silica (silica) as metal oxide particle, more preferably use acid colloidal silica sol.

(silica)

As silica (silica) spendable in the present invention, preferably can enumerate the silica, cataloid or the silica etc. that synthesized by vapor phase method that are synthesized by common damp process, in the present invention, as the silica particle particularly preferably used, silica particle cataloid can enumerated or synthesized by vapor phase method.

The particle dispersion liquid of preferable alloy oxide particle before mixing with cation property copolymer is the state being dispersed to primary particle.

Such as, when for above-mentioned vapor phase method silica particle, the average grain diameter (particle diameter under the dispersion liquid state before being coated with) of the primary particle of the metal oxide microparticle disperseed with the state of primary particle is preferably below 100nm, be more preferably 4 ~ 50nm, more preferably 4 ~ 20nm.

As the silica synthesized by vapor phase method that the primary particle average grain diameter preferably used further is 4 ~ 20nm, the such as commercially available AEROSIL having Nippon Aerosil Inc..The jet flow induction mixer etc. that this vapor phase method silica particle easily such as utilizes three Tian Cunli to grind Industrial Co., Ltd in water carries out attraction dispersion, thus can be dispersed to primary particle relatively easily.

As this commercially available at present fumed silica, the various AEROSIL of Nippon Aerosil company meet above-mentioned condition.

The cataloid preferably used in the present invention obtains in the following way, that is, utilization acid etc. is made sodium metasilicate generation double decomposition or makes sodium metasilicate by resinbed, obtain silicon dioxide gel, by heat aging for gained silicon dioxide gel.

The preferred average grain diameter of cataloid is generally 5 ~ 100nm, but the average grain diameter of more preferably 7 ~ 30nm.

The silica synthesized by vapor phase method and cataloid can carry out cation-modified to its surface, in addition, also can process with Al, Ca, Mg and Ba etc.

As the metal oxide particle contained in high refractive index layer, preferred TiO ₂, ZnO, ZrO ₂, from the view point of the stability of the composition of the containing metal oxide particle described later for the formation of high refractive index layer, more preferably TiO ₂(TiO 2 sol).In addition, at TiO ₂in, especially the catalytic activity of rutile-type is lower than Detitanium-ore-type, so the weatherability of high refractive index layer or adjacent layer uprises, and then refractive index is high, therefore preferred rutile-type.

(titanium dioxide)

The manufacture method of TiO 2 sol

The 1st operation in the manufacture method of fine particle of rutile-form titanium dioxide is the operation (operation (1)) being carried out by the titanium dioxide hydrates at least a kind of alkali compounds be selected from the hydroxide of alkali-metal hydroxide and alkaline-earth metal processing.

Titanium dioxide hydrates obtains by the hydrolysis of the water-soluble titanium such as titanium sulfate, titanium chloride compound.The method of hydrolysis is not particularly limited, and can apply known method.Wherein, the titanium dioxide hydrates obtained preferably by the pyrohydrolysis of titanium sulfate.

Above-mentioned operation (1) is such as undertaken by such as under type, that is, in the waterborne suspension of above-mentioned titanium dioxide hydrates, add above-mentioned alkali compounds, carries out processing (making it reaction) under the condition of set point of temperature with the stipulated time.

The method making above-mentioned titanium dioxide hydrates become waterborne suspension is not particularly limited, and is undertaken by adding above-mentioned titanium dioxide hydrates and stir in water.The concentration of suspension is not particularly limited, such as, be preferably TiO ₂concentration becomes the concentration of 30 ~ 150g/L in suspension.By making concentration be in above-mentioned scope, can efficiency carry out well reacting (process).

As at least a kind of alkali compounds be selected from the hydroxide of alkali-metal hydroxide and alkaline-earth metal used in above-mentioned operation (1), be not particularly limited, NaOH, potassium hydroxide, magnesium hydroxide, calcium hydroxide etc. can be enumerated.The addition of the above-mentioned alkali compounds in above-mentioned operation (1) is preferably 30 ~ 300g/L with the alkali compounds densimeter reacted in (process) suspension.

Above-mentioned operation (1) is preferably carried out at reaction (process) temperature of 60 ~ 120 DEG C.Reaction (process) time is different because reaction (process) temperature is different, but is preferably 2 ~ 10 hours.Reaction (process) preferably by add in the suspension of titanium dioxide hydrates NaOH, potassium hydroxide, magnesium hydroxide, calcium hydroxide the aqueous solution carry out.Reaction (process) after, will react (process) mixture cool, as required with in the inorganic acids such as hydrochloric acid with after, carry out filtering, washing, titanium dioxide hydrates particulate can be obtained thus.

In addition, as the 2nd operation (operation (2)), the compound that can obtain by carboxylic compound and the above-mentioned operation of mineral acid reason (1).In the manufacture of rutile titanium dioxide particulate, the method for the compound obtained by the above-mentioned operation of mineral acid reason (1) is known method, but can also use carboxylic compound to adjust particle diameter except using inorganic acid.

Above-mentioned carboxylic compound is the organic compound with-COOH base.As above-mentioned carboxylic compound, preferably there is preferably more than 2, the polycarboxylic acids of more preferably 2 ~ 4 carboxyls.Above-mentioned polycarboxylic acids has the configurational energy to metallic atom, so supposition suppresses the cohesion between particulate by coordination, can suitably obtain rutile titanium dioxide particulate thus.

As above-mentioned carboxylic compound, be not particularly limited, such as, can enumerate the dicarboxylic acids such as oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, propylmalonic acid, maleic acid; The hydroxyl polycarboxylic acids such as malic acid, tartaric acid, citric acid; The aromatic series polycarboxylic acids such as phthalic acid, M-phthalic acid, benzene-1,2,3-tricarboxylic acid, trimellitic acid; Ethylenediamine tetra-acetic acid etc.Wherein, can simultaneously and use compound of more than two kinds.

Should illustrate, all or part of of above-mentioned carboxylic compound can be the corrective (such as, having the organic compound of-COONa group etc.) of the organic compound with-COOH base.

As above-mentioned inorganic acid, be not particularly limited, such as, can enumerate hydrochloric acid, sulfuric acid, nitric acid etc.Above-mentioned inorganic acid preferably adds by the mode that the concentration in liquid becomes 0.5 ~ 2.5 mole/L, more preferably become 0.8 ~ 1.4 mole/L to react (process).

Above-mentioned operation (2) is preferably as follows carries out: make the compound obtained by above-mentioned operation (1) be suspended in pure water, under stirring, heat as required.Carboxylic compound and inorganic acid can add simultaneously also can add successively, preferably add successively.Interpolation can be add inorganic acid after the carboxylic compound of interpolation, also can be add carboxylic compound after interpolation inorganic acid adds.

Such as can enumerate following method: in the suspension of the compound obtained by above-mentioned operation (1), add carboxylic compound, start heating, reach preferably more than 60 DEG C in liquid temperature, more preferably add inorganic acid after more than 90 DEG C, limit maintains liquid temperature limit and stirs the preferably 15 minutes ~ method (method 1) of 5 hours, more preferably 2 ~ 3 hour; Heat the suspension of the compound obtained by above-mentioned operation (1), reach preferably more than 60 DEG C in liquid temperature, more preferably add inorganic acid after more than 90 DEG C, from interpolation inorganic acid, add carboxylic compound after 10 ~ 15 minutes, limit maintains liquid temperature limit and stirs the preferably 15 minutes ~ method (method 2) etc. of 5 hours, more preferably 2 ~ 3 hour.By adopting these methods to carry out, the particulate rutile titanium dioxide be applicable to can be obtained.

Adopt said method 1 when carrying out above-mentioned operation (2), above-mentioned carboxylic Compound Phase is for the TiO of 100 % by mole ₂, preferably use 0.25 ~ 1.5 % by mole, more preferably use with the ratio of 0.4 ~ 0.8 % by mole.If the addition of carboxylic compound is above-mentioned scope, then can obtain the particle of intended particle size, the rutilization of particle efficiently carries out.

Adopt said method 2 when carrying out above-mentioned operation (2), above-mentioned carboxylic Compound Phase is for the TiO of 100 % by mole ₂, preferably use 1.6 ~ 4.0 % by mole, more preferably use with the ratio of 2.0 ~ 2.4 % by mole.

If the addition of carboxylic compound is above-mentioned scope, then can obtain the particle of intended particle size, the rutilization of particle efficiently carries out, in addition, also favourable at economic aspect.In addition, if add above-mentioned carboxylic compound after 10 ~ 15 minutes from interpolation inorganic acid, then the rutilization of particle carries out efficiently, can obtain the particle of intended particle size.

In above-mentioned operation (2), preferably terminate rear cooling in reaction (process), then neutralize, to become pH5.0 ~ pH10.0.Above-mentioned neutralization can utilize the alkali compounds such as sodium hydrate aqueous solution, ammoniacal liquor to carry out.Carry out after neutralization filtering, washing, thus can by the rutile titanium dioxide separation of particles of target.

In addition, as the manufacture method of titanium dioxide fine particles, the known method recorded in " titanium oxide-physical property and application technology " (leave nothing usable to the invading enemy learn p255 ~ 258 (2000) skill report hall publish Co., Ltd.) etc. can be used.

In addition, as other manufacture method of the metal oxide particle containing TiO 2 particles, can refer to Japanese Unexamined Patent Publication 2000-053421 publication and (coordinate alkyl silicate as dispersion stabilizer, the silicon in this alkyl silicate is converted into SiO ₂amount with the titanium in titanium dioxide is converted into TiO ₂the weight ratio (SiO of amount ₂/ TiO ₂) be 0.7 ~ 10 TiO 2 sol), Japanese Unexamined Patent Publication 2000-063119 publication is (with TiO ₂-ZrO ₂-SnO ₂composite colloids particle as core, by its surface WO ₃-SnO ₂-SiO ₂the colloidal sol that is coated to of composite oxides colloidal particle) etc. in the item recorded.

In addition, TiO 2 particles can be coated to siliceous hydrous oxide.The amount of coating of siliceous hydrated compound is preferably 3 ~ 30 quality %, is more preferably 3 ~ 10 quality %, more preferably 3 ~ 8 quality %.If this is because amount of coating is below 30 quality %, then the desired refractive index of high refractive index layer can be obtained, if amount of coating is more than 3%, then stably particle can be formed.

As the method being coated to TiO 2 particles with siliceous hydrous oxide, known method manufacture can be adopted, such as, can refer to Japanese Unexamined Patent Publication 10-158015 publication and (process of Si/Al hydrous oxide is carried out to rutile titanium dioxide; Make the surface of the titanium oxide after the solution flocculation of the hydrous oxide of silicon and/or aluminium in the basic region of metatitanic acid filter cake separate out and carry out the manufacture method of surface-treated TiO 2 sol), Japanese Unexamined Patent Publication 2000-204301 publication (is coated to the composite oxides of the oxide of Si and Zr and/or Al and the colloidal sol that obtains to rutile titanium dioxide.Hydrothermal treatment consists), Japanese Unexamined Patent Publication 2007-246351 publication (in the hydrosol of the titanium oxide flocculation of moisture titanium dioxide solution obtained, adds formula R1 _nsiX _4-n(in formula, R1 is C1-C8 alkyl, glycidyl oxygen base replaces C1-C8 alkyl or C2-C8 alkenyl, X is alkoxyl, n is 1 or 2) organoalkoxysilane or titanium dioxide there is the compound of coordination as stabilizing agent, in basic region, interpolation pH is carried out to the solution of sodium metasilicate or silicon dioxide gel and regulates slaking, manufacture the method for the titania hydrosol be coated to by the hydrous oxide of silicon thus) etc. in the item recorded.

The volume average particle size of TiO 2 particles is preferably below 30nm, is more preferably 1 ~ 30nm, more preferably 5 ~ 15nm.If volume average particle size is below 30nm, then little from mist degree and the viewpoint of visible light transmission excellence and preferably.

Here the volume average particle size mentioned refers to the volume average particle size being scattered in primary particle in medium or offspring, can utilize laser diffraction/mensuration such as scattering method, dynamic light scattering method.

Specifically, with electron microscope observation particle itself or at the cross section of index layer or the surperficial particle occurred, measure the particle diameter of 1000 Arbitrary Particles, separately there is d ₁, d ₂d _id _kthe particle of particle diameter respectively with n1, n2 ... ni ... in the group of nk the metal oxide particle existed, the volume of each particle is set to v _itime, use volume average particle size m _v={ Σ (v _id _i)/{ Σ (v _i) volume that represents is weighted, and calculates average grain diameter.

In addition, in the present invention, cataloid complex emulsions also can use as metal oxide in low-index layer.With regard to the cataloid complex emulsions preferably used in the present invention, the central part of particle forms using polymer or copolymer etc. as main component, under the cataloid existent condition recorded in Japanese Laid-Open Patent Publication 59-71316 publication, Japanese Laid-Open Patent Publication 60-127371 publication, utilized by the monomer with ethene unsaturated bond known emulsion polymerization to be polymerized and obtain.As the particle diameter of cataloid being applicable to this compound emulsion, be preferably less than 40nm.

As the cataloid used in the preparation of this complex emulsions, the cataloid of the primary particle of 2 ~ 100nm usually can be enumerated.As ethene monomer, such as can enumerate and there is the alkyl that carbon number is 1 ~ 18, aryl or allylic (methyl) acrylate, styrene, AMS, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, propionate, acrylamide, N hydroxymethyl acrylamide, ethene, butadiene etc. are known material in latex industry, as required, in order to improve the compatibility with cataloid further, also vinyltrimethoxy silane can be used, VTES, the vinyl silanes of γ-methacryloxypropyl trimethoxy silane etc. and so on, in addition, in order to make the stably dispersing of emulsion, secondarily can use (methyl) acrylic acid, maleic acid, maleic anhydride, fumaric acid, the anionic monomers such as butenoic acid.Should illustrate, ethene monomer and can use two or more as required.

In addition, the ratio of the ethene monomer/cataloid in emulsion polymerisation is preferably 100/1 ~ 200 with solid constituent ratiometer.

In the colloidal silica silicon compound emulsion used in the present invention, as preferred emulsion, the emulsion that glass transition temperature is the scope of-30 ~ 30 DEG C can be enumerated.

In addition, as the upper preferred material of composition, the ethene such as acrylate, methacrylate monomer can be enumerated, as particularly preferred composition, the copolymer of the copolymer of (methyl) acrylate and cinnamic copolymer, (methyl) alkyl acrylate and (methyl) acrylic acid aralkyl ester, (methyl) alkyl acrylate and (methyl) benzyl acrylate can be enumerated.

As the emulsifying agent used in emulsion polymerisation, such as, can enumerate polyoxyethylene base polyether sulphur acid sodium-salt, lauryl sulfonic acid sodium salt, alkyl benzene sulphonate sodium salt, ethylene nonyl phenyl ether nitric acid sodium salt, polyoxyethylene base sulfosuccinic acid ester sodium salt, sulfapropyl monoalkyl sodium maleate salt etc.

(other additive)

In each index layer forming dielectric stack film, as required, various additive can be contained.

Specifically, anion, cation or non-ionic various surfactant can be contained; The dispersant such as polycarboxylic acids ammonium salt, allyl ether copolymer, benzene sulfonic acid sodium salt, graft compound system dispersant, polyethylene glycol type nonionic system dispersant; The acylates such as acetate, propionate or citrate; The organic ester plasticizer such as single basic organic acid ester, polybase organic acid esters, the plasticizer such as phosphoric acid plasticizer such as organic phosphoric acid plasticizer, organic phosphorous acid plasticizer; The ultra-violet absorber recorded in Japanese Laid-Open Patent Publication 57-74193 publication, Japanese Laid-Open Patent Publication 57-87988 publication and Japanese Laid-Open Patent Publication 62-261476 publication, the anti-fading agent recorded in Japanese Laid-Open Patent Publication 57-74192 publication, Japanese Laid-Open Patent Publication 57-87989 publication, Japanese Laid-Open Patent Publication 60-72785 publication, Japanese Laid-Open Patent Publication 61-146591 publication, Japanese Unexamined Patent Publication 1-95091 publication and Japanese Unexamined Patent Publication 3-13376 publication etc.; The fluorescent whitening agent recorded in Japanese Laid-Open Patent Publication 59-42993 publication, Japanese Laid-Open Patent Publication 59-52689 publication, Japanese Laid-Open Patent Publication 62-280069 publication, Japanese Laid-Open Patent Publication 61-242871 publication and Japanese Unexamined Patent Publication 4-219266 publication etc.; The pH adjusting agents such as sulfuric acid, phosphoric acid, acetic acid, citric acid, NaOH, potassium hydroxide, potash; Defoamer; The lubricants such as diethylene glycol; Anticorrisive agent; Antistatic additive; The known various additive such as delustering agent.

(formation of multilayer dielectric film)

As long as forming (stacked film) of at least stacked unit be made up of high refractive index layer and low-index layer of the multilayer dielectric film that the present invention relates to, as the upper limit of the sum of high refractive index layer and low-index layer, be preferably less than 300 layers, namely below 150 unit.Be more preferably 250 layers (125 unit) below, further be successively preferably 100 layers (50 unit) below, 40 layers (20 unit) below, 30 layers (15 unit) below, 20 layers (10 unit) below.By reducing the number of plies, productivity ratio improves, and can suppress the reduction of the transparency caused by the scattering of stacked interface.

In addition, as long as the formation of multilayer dielectric film of the present invention at least one said units stacked, such as, can be the most top layer of stacked film, orlop all becomes the stacked film of high refractive index layer or low-index layer.

In multilayer dielectric film of the present invention, as the preferred refractive index of high refractive index layer, be preferably 1.60 ~ 2.40, be more preferably 1.65 ~ 2.10.In addition, the refractive index of low-index layer of the present invention is preferably 1.30 ~ 1.50, is more preferably 1.34 ~ 1.50.

In multilayer dielectric film, from the view point of improving infrared reflection rate with few number of plies, preferably design the specific refractivity of high refractive index layer and low-index layer significantly, but in the present invention, for at least one in the unit be made up of high refractive index layer and low-index layer, this preferably adjacent high refractive index layer and the refringence of low-index layer are more than 0.1, are more preferably more than 0.3, more preferably more than 0.4.

In addition, in dielectric stack film of the present invention, adjacent high refractive index layer and the refringence of low-index layer are preferably more than 0.1, but when having multilayer high refractive index layer and low-index layer respectively as mentioned above, preferred all index layers all meet the scope specified in the present invention.But most top layer, orlop can be the formations beyond the scope that specifies in the present invention.

The reflectivity of particular wavelength region is determined by the refringence of 2 layers that adjoin (high refractive index layer and low-index layers) and stacked number, and refringence is larger, more can obtain identical reflectivity with few number of plies.For this refringence and the necessary number of plies, commercially available optical design software can be used to calculate.Infrared ray screening rate such as in order to obtain more than 90%, if refringence is less than 0.1, then what need more than 100 layers is stacked, and not only productivity ratio reduces, and the scattering at stacked interface becomes large, and the transparency reduces.From the view point of raising reflectivity with reduce the number of plies, refringence does not have the upper limit, but about 1.40 is the limit in fact.

With regard to above-mentioned refringence, obtain the refractive index of high refractive index layer and low-index layer by the following method, by both differences as refringence.

As required, use base material, make each index layer with individual layer, after this sample is cut into 10cm × 10cm, obtain refractive index by the following method.As spectrophotometer, use U-4000 type (Hitachi Co., Ltd's system), to each sample with measure after the face (back side) of opposition side, face carries out roughened process, light absorption process is carried out with the spraying of black, prevent the reflection of light overleaf, measure the reflectivity of visible region (400nm ~ 700nm) with the condition of 5 degree of normal reflections at 25 points, obtain mean value, obtain mean refractive index by its measurement result.

With material form be only polymer dielectric stack film compared with, owing to containing metal oxide particle in high refractive index layer, so the refractive index of high refractive index layer can be improved, even if minimizing is laminated with the unit number of high low-index layer and becomes film, high infrared reflection rate also can be obtained.

The integral thickness of infrared ray shielding film of the present invention is preferably 12 μm ~ 315 μm, is more preferably 15 μm ~ 200 μm, more preferably 20 μm ~ 100 μm.

Should illustrate, in this manual, as the term of " high refractive index layer " and " low-index layer ", refer to when the adjacent refringence of 2 layers is compared, using index layer high for refractive index as high refractive index layer, using index layer low for refractive index as low-index layer.Therefore, during 2 index layers that the term as " high refractive index layer " and " low-index layer " adjoins in each index layer being conceived to formation optical reflectance coating, all modes except the mode that each index layer has identical refractive index are comprised.

(manufacture method of multilayer dielectric film)

Multilayer dielectric film of the present invention is formed by folding the unit be made up of high refractive index layer and low-index layer at layers on substrates.Specifically, except as above-mentioned United States Patent (USP) the 6th, 049, the method recorded in No. 419 descriptions utilizes melt extruding of polymer like that and stretches to be formed beyond the method for multilayer dielectric film, also can enumerate the high refractive index layer coating fluid of alternately wet water system and low-index layer coating fluid and dry and form the method for duplexer.

As alternately the high refractive index layer coating fluid of wet water system and the method for low-index layer coating fluid, the following coating method enumerated preferably can be used.Such as preferably can use rolling method, stick coating method, air knife coating method, spraying process, curtain coating processes or United States Patent (USP) the 2nd, 761, No. 419 descriptions, United States Patent (USP)s the 2nd, the sliding hopper rubbing method (slide hopper coating), extrusion coating methods etc. recorded in 761, No. 791 descriptions etc.In addition, carrying out multi-layer coated mode as to multilayer, can be successively multi-layer coated, also can be simultaneously multi-layer coated.

As the viscosity of high refractive index layer coating fluid when carrying out simultaneously multi-layer coated and low-index layer coating fluid, when using sliding hopper rubbing method, be preferably the scope of 5 ~ 100mPas, the more preferably scope of 10 ~ 50mPas.In addition, when using curtain coating mode, be preferably the scope of 5 ~ 1200mPas, the more preferably scope of 25 ~ 500mPas.

In addition, as coating fluid viscosity 15 DEG C time, be preferably more than 100mPas, be more preferably 100 ~ 30000mPas, more preferably 3000 ~ 30000mPas, be preferably 10000 ~ 30000mPas.

As coating and drying means, preferably the high refractive index layer coating fluid of water system and low-index layer coating fluid are heated to more than 30 DEG C, after being coated with, the temperature of the film of formation is temporarily cooled to 1 ~ 15 DEG C, drying is carried out more than 10 DEG C, it is further preferred that as drying condition, carry out under the condition of the scope of wet-bulb temperature 5 ~ 50 DEG C, film surface temperature 10 ~ 50 DEG C.In addition, as the type of cooling after being just coated with, from the view point of the painting film uniformity formed, preferably carry out to be horizontally disposed with mode.

The thickness (dried thickness) of every floor height index layer is preferably 20 ~ 1000nm, is more preferably 50 ~ 500nm.

The thickness (dried thickness) of every layer of low-index layer is preferably 20 ~ 800nm, is more preferably 50 ~ 350nm.

The mode that can become as thickness during preferred dry shown in above-mentioned by the coating thickness of high refractive index layer coating fluid and low-index layer coating fluid is coated with.

[infrared ray shielding film]

The thickness of the entirety of infrared ray shielding film of the present invention is preferably 12 μm ~ 315 μm, is more preferably 15 μm ~ 200 μm, more preferably 20 μm ~ 100 μm.

Infrared ray shielding film of the present invention is under base material or with on the most surface layer of base material opposition side, for the object of additional further function, conductive layer can be had, antistatic layer, gas-barrier layer, easy bonding layer (bonding layer), stain-proofing layer, deodorizing layer, drip layer, slippery layer, hard conating, anti abrasion layer, antireflection layer, electromagnetic shielding layer, UV-absorbing layer, infrared ray-absorbing layer, printed layers, fluorescent light-emitting layer, hologram layer, peel ply, adhesive layer, adhesive layer, infrared ray barrier layer (metal level except high refractive index layer of the present invention and low-index layer, liquid crystal layer), dyed layer (luminous ray absorbed layer), more than a kind in the functional layers such as the middle film layer utilized in laminated glass.Below, be described as the adhesive layer of preferred functional layer, infrared ray-absorbing layer and hard conating.

< adhesive layer >

Infrared ray shielding film of the present invention can arrange adhesive layer in arbitrary most face, top layer (wherein, not comprising barrier film).Adhesive layer is such as the layer arranged to attach infrared ray shielding film of the present invention to glass surface etc.

As the adhesive forming adhesive layer, being not particularly limited, such as, can exemplary propylene acid be adhesive, silicon system adhesive, polyurethane series adhesive, polyvinyl butyral resin system adhesive, ethane-acetic acid ethyenyl ester system adhesive etc.

When infrared ray shielding film of the present invention is fitted in glass pane, from the view point of again stretching, reorientating, preferably use window water spray and the adhesive layer of this infrared ray shielding film of fitting at the glass surface of moisture state, namely so-called water pastes method.Therefore, the weak acrylic adhesive of bonding force under the wet condition that water exists can be preferably used in.

The acrylic adhesive used can be any one in solvent system and emulsion system, but from the view point of easily improving bonding force etc., preferred solvent system adhesive, wherein, the adhesive preferably obtained by polymerisation in solution.As the raw material when being manufactured this solvent system acrylic adhesive by polymerisation in solution, such as the formant becoming skeleton, ethyl acrylate can be enumerated, butyl acrylate, 2-EHA, the acrylate such as 2-ethyl hexyl acrylate, as the comonomer for improving cohesiveness, vinyl acetate can be enumerated, acrylonitrile, styrene, methyl methacrylate etc., in addition, in order to promote to be cross-linked, give stable bonding force, in addition, also bonding force is to a certain degree kept in presence of water, as the monomer containing functional group, methacrylic acid can be enumerated, acrylic acid, itaconic acid, hydroxyethyl methacrylate, GMA etc.In the adhesive phase of this stacked film, as principal polymeric, owing to especially needing high viscosity, so the material with lower glass transition temperatures (Tg) as butyl acrylate etc. is particularly useful.

In this adhesive layer, as additive, such as, can contain stabilizing agent, surfactant, ultra-violet absorber, fire retardant, antistatic additive, antioxidant, heat stabilizer, lubricant, filler, painted, bonding conditioning agent etc.Particularly, when using as window subsides as the present invention, in order to suppress by the deterioration of UV-induced infrared ray shielding film, the interpolation of ultra-violet absorber is also effective.

The thickness of adhesive layer is preferably 1 ~ 100 μm, is more preferably 3 ~ 50 μm, more preferably 10 ~ 30 μm.If be more than 1 μm, then there is the trend that cohesive improves, sufficient bonding force can be obtained.On the contrary, if be less than 100 μm, then not only the transparency of infrared ray shielding film improves, and after infrared ray shielding film is attached at glass pane, does not also cause cohesion to destroy, have the trend of not residual adhesive on glass surface during stripping between adhesive layer.

< infrared ray-absorbing layer >

Infrared ray shielding film of the present invention can have infrared ray-absorbing layer at an arbitrary position.

As the material contained in infrared ray-absorbing layer, be not particularly limited, such as, can enumerate ultraviolet curable resin, Photoepolymerizationinitiater initiater, infrared absorbent etc.

Ultraviolet curable resin is more excellent, in addition, also favourable from the viewpoint of the dispersiveness of the metal oxide of tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), heat conductivity than hardness, flatness with other resin-phase.As ultraviolet curable resin, as long as by the ultraviolet curable resin being solidified to form hyaline layer, just can use without particular limitation, such as, can enumerate organic siliconresin, epoxy resin, vinyl ester resin, acrylic resin, allyl ester resin etc.From the view point of hardness, flatness, the transparency, more preferably acrylic resin.

From the view point of hardness, flatness, the transparency, aforesaid propylene acid resin is preferably containing, for example the reactive silicon dioxide particle (following, also referred to as " reactive silicon dioxide particle ") having imported the photonasty group with photopolymerization reaction on surface recorded in No. 2008/035669, International Publication.Here, as the photonasty group with optical polymerism, the polymerism unsaturated group etc. represented by (methyl) acryloxy can be enumerated.In addition, ultraviolet curable resin also can such as, containing with the compound with the photonasty group generation photopolymerization reaction of photopolymerization reaction being directed to this reactive silicon dioxide particle surface, having the organic compound of polymerism unsaturated group.In addition, following material can be used as reactive silicon dioxide particle, that is, the hydrolysable silanes that polymerism unsaturated group is modified utilizes the hydrolysis of hydrolyzable silyl group between silicon dioxide granule, generate siloxy and carry out the material of chemical bonding.Here, the average grain diameter of reactive silicon dioxide particle is preferably 0.001 ~ 0.1 μm.By making average grain diameter be such scope, can balance and meet the transparency, flatness, hardness well.

In addition, from the view point of adjustment refractive index, aforesaid propylene acid resin can containing the Component units deriving from fluorine-containing vinyl monomer.As fluorine-containing vinyl monomer, fluoroolefins (such as PVF, vinylidene, tetrafluoroethene, hexafluoropropene etc.), (methyl) acrylic acid partially or completely fluoro-alkyl ester derivant class (such as VISCOAT 6FM (trade name can be enumerated, Osaka Organic Chemical Industry Co., Ltd.'s system), R-2020 (trade name, Daikin Ind Ltd's system) etc., wholly or in part fluorinated ethylene base ethers etc.

As Photoepolymerizationinitiater initiater, known Photoepolymerizationinitiater initiater can be used, can be used alone or combine two or more and use.

As the inorganic infrared absorbent that can contain in infrared ray-absorbing layer, from viewpoints such as luminous ray transmissivity, infrared ray-absorbable, Bet-hedgings in resin, preferred tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), zinc antimonates, lanthanum hexaboride (LaB ₆), containing the tungsten oxide (Cs of caesium _0.33wO ₃) etc.These can be used alone or combine two or more and use.The average grain diameter of inorganic infrared absorbent is preferably 5 ~ 100nm, is more preferably 10 ~ 50nm.If be less than 5nm, then the dispersiveness likely in resin, infrared ray-absorbable reduce.On the other hand, if be greater than 100nm, then likely luminous ray transmissivity reduces.Should illustrate, being determined as follows of average grain diameter is carried out: utilize transmission electron microscope to take, and randomly draws such as 50 its particle diameters of particle assay, calculates its mean value.In addition, when the shape of particle is not spherical, is defined as and measures major diameter and the value that calculates.

The content of above-mentioned inorganic infrared absorbent in infrared ray-absorbing layer, relative to the gross mass of infrared ray-absorbing layer, is preferably 1 ~ 80 quality %, is more preferably 5 ~ 50 quality %.If content is more than 1%, then can show sufficient infrared absorption effect, if be less than 80%, then can the luminous ray of transmission substantial amount.

In infrared ray-absorbing layer, can containing other infrared absorbent such as metal oxide, organic system infrared absorbent, metal complex than that described above in the scope playing effect of the present invention.As the concrete example of other such infrared absorbent, such as, can enumerate diimmonium based compound, aluminium based compound, phthalocyanine based compound, organometallic complex, flower cyanines based compound, azo-compound, polymethine based compound, quinone based compound, diphenyl methane based compound, triphenyl methane based compound etc.

The thickness of infrared ray-absorbing layer preferably 0.1 ~ 50 μm, is more preferably 1 ~ 20 μm.If be more than 0.1 μm, then have the trend that infrared ray absorption ability improves, on the other hand, if be less than 50 μm, then the crack resistance of film improves.

< hard conating >

Infrared ray shielding film of the present invention preferably as the sealer for improving resistance to nuzzling up property at the hard conating of the stacked resin containing utilizing heat, ultraviolet etc. to be cured of the superiors with the opposition side of the side of adhesive layer of base material.In the present invention, especially when becoming the configuration below the layer that base material is positioned at containing tabular metallic, preferably above the layer containing tabular metallic, hard conating is formed.

As the gel-type resin used in hard conating, can enumerate thermohardening type resin, ultraviolet curing resin, but the viewpoint of calm easy-formation is set out, preferred ultraviolet curing resin, wherein, more preferably pencil hardness is at least the ultraviolet curing resin of 2H.Such gel-type resin can be used alone or combines two or more.In addition, gel-type resin can use commercially available product also can use composite.

As such ultraviolet curing resin, such as, can enumerate the so multi-functional acrylate of the acrylic or methacrylic acid esters with polyalcohol and by vulcabond and the multi-functional polyurethane acrylate resin etc. of acrylic or methacrylic acid synthesis with polyalcohol.In addition, polyether resin, mylar, epoxy resin, alkyd resins, spiral shell acetal resin, polybutadiene or the polymercaptan polyenoid resin etc. with acrylic ester functional group can also preferably be used.

In addition, as the reactive diluent of these resins, more low viscous 1,6-cyclohexanediol two (methyl) acrylate can be used, tripropylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, hexylene glycol (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, monomers more than two senses such as neopentyl glycol two (methyl) acrylate, oligomer, and NVP, ethyl acrylate, the esters of acrylic acids such as propyl acrylate, EMA, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, EHMA, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, the methyl acrylic esters such as methacrylic acid nonyl phenyl ester, the derivatives such as tetrahydrofurfuryl methacrylate and caprolactone modification thing thereof, styrene, the monofunctional monomer such as AMS or acrylic acid etc.These reactive diluents can be used alone or combine two or more and use.

In addition, as the sensitising agent (radical polymerization initiator) of these resins, benzoin and the alkyl ethers thereof such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzil methyl ketal can be used; The acetophenones such as acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1-hydroxycyclohexylphenylketone; The Anthraquinones such as tectoquinone, 2-EAQ, 2-amyl anthraquinone; The thioxanthene ketones such as thioxanthones, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone; The ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal; Benzophenone and the azo-compounds etc. such as benzophenone, 4,4-dimethylamino benzophenone.These can be used alone or combine two or more and use.And, can also with the tertiary amine such as triethanolamine, methyl diethanolamine; The light-initiated auxiliary agents etc. such as benzoic acid derivative such as 2-dimethyl ethyl aminobenzoate, 4-dimethyl ethyl aminobenzoate combinationally use.The use amount of these radical polymerization initiators, relative to the polymerizable component of 100 mass parts resins, is preferably 0.5 ~ 20 mass parts, is more preferably 1 ~ 15 mass parts.

Should illustrate, in above-mentioned gel-type resin, as required, known general coating additive can be coordinated.Such as, give the silicon-type of levelling, surface smoothness etc., the loss prevention trauma of the coating additive of fluorine system to cured film surface is effective, in addition, when utilizing ultraviolet as active energy ray, this coating additive is by being exuded to Air Interface, the solidification that can reduce the resin caused by oxygen hinders, even if also can obtain effective state of cure under low exposure intensity condition.

In addition, hard conating is preferably containing inorganic particles.As preferred inorganic particles, the particulate of the inorganic compound containing metals such as titanium, silica, zirconium, aluminium, magnesium, antimony, zinc or tin can be enumerated.From the radioparent viewpoint guaranteeing luminous ray, the average grain diameter of this inorganic particles is preferably below 1000nm, is more preferably the scope of 10 ~ 500nm.In addition, inorganic particles can suppress coming off from hard conating with when forming the adhesion of gel-type resin of hard conating, and therefore the preferred photonasty group with photopolymerization reaction by simple function or polyfunctional acrylate etc. imports to surface.

The thickness of hard conating is preferably 0.1 μm ~ 50 μm, is more preferably 1 ~ 20 μm.If be more than 0.1 μm, then the trend having hard painting property to improve, on the contrary, if be less than 50 μm, then has the trend that the transparency of infrared ray shielding film improves.

Should illustrate, hard conating also can double as above-mentioned infrared ray-absorbing layer.

The formation method > of < adhesive layer, infrared ray-absorbing layer, hard conating

As the painting method of adhesive, arbitrary known method can be used, such as, preferably can enumerate stick coating method, mould is coated with method, intaglio plate rolling method, scraper for coating method, spraying process, air knife coating method, dip coating, transfer printing etc., can be used alone or combinationally use.These methods can suitably use that make solution with the solvent of solubilized adhesive or that adhesive is disperseed coating fluid to apply, and as solvent, can use known solvent.

The formation of adhesive layer can adopt above-mentioned coating method to be directly coated on infrared ray shielding film, in addition, also can be coated on a stripping film and after making its drying, laminating infrared ray shielding film and make adhesive transfer printing.Baking temperature now preferably makes residual solvent reduce as far as possible, and therefore baking temperature, time do not have special provision, but preferably at the temperature of 50 ~ 150 DEG C, arranges the drying time of 10 seconds ~ 5 minutes.In addition, because adhesive has mobility, not yet terminate so just reacted after heat drying, react to make it and terminate and obtain stable bonding force, also need maintenance.Usually, be at room temperature more than about 1 week, in case of heating, such as, 50 DEG C time, preferably more than 3 days.During heating, if make excessive temperature raise, then likely the flatness of plastic foil is deteriorated, and therefore degree of leaving nothing to be desired raises.

The formation method of infrared ray-absorbing layer and hard conating is not particularly limited, preferably utilize stick coating method, mould to be coated with the wet coating method such as method, intaglio plate rolling method, spin-coating method, spray-on process, scraper plate rubbing method, air knife coating method, dip coating, transfer printing, or the dry coating method such as vapour deposition method is formed.

The method be cured as utilizing Ultraviolet radiation, by irradiating the ultraviolet of the wavelength region of the preferably 100 ~ 400nm, the more preferably 200 ~ 400nm that are sent by ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc lamp, metal halide lamp etc., or the electron beam irradiating below the 100nm wavelength region sent by the electron-beam accelerator of scan-type, curtain type carries out.

The lamination order > of < infrared ray shielding film

The lamination order of each layer of infrared ray shielding film of the present invention is not particularly limited.But from the view point of improving effect of the present invention further, preferred multilayer dielectric film, compared with the layer containing tabular metallic, is arranged on the light incident side of light (sunlight).By becoming such formation, multilayer dielectric film can be utilized to reduce the light quantity of the layer injected containing tabular metallic, therefore can reduce the caloric value of the layer containing tabular metallic, higher effect of heat insulation can be obtained.In addition, by becoming above-mentioned formation, also can expect suppress caused by the variable color of tabular metallic film through time variable color.

Infrared ray shielding film of the present invention is roughly divided into (1) and is formed in the one side of base material containing the layer of tabular metallic and the formation of multilayer dielectric film, or (2) are formed containing the layer of tabular metallic and the formation of multilayer dielectric film across base material.Below, be described respectively.

(1) formed containing the layer of tabular metallic and the formation of multilayer dielectric film in the one side of base material

For this formation (1), the mode of pasting (interior subsides) infrared ray shielding film of the present invention in the indoor of glass pane can be adopted.As which, such as can enumerate if under type is as a preferred example, namely, layer, multilayer dielectric film, the adhesive layer containing tabular metallic is stacked gradually at substrate surface, hard conating (Fig. 3 A, interior subsides formation 1) is coated with at the substrate surface of opposition side of the side being laminated with these layers.By becoming such formation, high infrared ray screening effect can be obtained.As long as tabular metal particle layer is identical with the position relationship of multilayer dielectric film, even such as the order of adhesive layer, base material, multilayer dielectric film, layer containing tabular metallic, hard conating is also passable.In addition, between multilayer dielectric film and the layer containing tabular metallic, also other functional layer, base material can be had.

In addition, in this formation (1), it also can be the mode of putting up (pasting) infrared ray shielding film of the present invention in the outside of glass pane outward.If enumerate the preferred example in which, then form for following: stack gradually multilayer dielectric film, the layer containing tabular metallic, adhesive layer at substrate surface, then be coated with hard conating at the substrate surface of opposition side of the side being laminated with these layers.In the same manner as the situation of interior subsides, as long as the layer containing tabular metallic is identical with the position relationship of multilayer dielectric film, it can be such as just the order (Fig. 3 C, outer subsides formation 3) of adhesive layer, base material, layer containing tabular metallic, multilayer dielectric film, hard conating.In addition, between multilayer dielectric film and the layer containing tabular metallic, also other functional layer, base material can be had.

(2) formed containing the layer of tabular metallic and the formation of multilayer dielectric film across base material

Infrared ray shielding film of the present invention also can be form multilayer dielectric film in base material one side, and the another side of base material is formed the mode of the layer containing tabular metallic.That is, can be multilayer dielectric film and containing tabular metallic layer each other across base material formed mode.

In such formation, the position relationship of the layer containing tabular metallic, multilayer dielectric film and base material preferably rises from the side that light (such as, sunlight) is incident and is configured according to the order of multilayer dielectric film, base material, layer containing tabular metallic.

For this formation (2), the mode of putting up (interior subsides) infrared reflection film of the present invention in the indoor of glass pane can be adopted.Thereby, it is possible to obtain extra high infrared ray screening effect.As which, such as can enumerate if under type is as a preferred example, namely, at the layer of the one side side of base material configuration containing tabular metallic, and in the face configuration multilayer dielectric film of its opposition side, take base material as benchmark, stacked hard conating on the layer containing tabular metallic, stacked adhesive layer (Fig. 3 B, interior subsides formation 2) in multilayer dielectric film.If the scope of above-mentioned lamination order, then also can insert other layer between the layers.

In addition, in this formation (2), it also can be the mode of putting up (pasting) infrared ray shielding film of the present invention in the outside of glass pane outward.If enumerate the preferred example in which, then form for following: the hard conating stacking gradually multilayer dielectric film and this multilayer dielectric film coating on a surface of base material, the another side of base material stacks gradually the layer containing tabular metallic and the adhesive layer (Fig. 3 D, outer subsides formation 4) being coated to this layer.In addition, in the same manner as interior subsides mode, if be the scope of above-mentioned lamination order, then also can insert other layer between the layers.

Should illustrate, in above-mentioned interior subsides mode, outer subsides mode, be more preferably interior subsides mode.

In interior subsides mode, take base material as benchmark, adhesive layer is not only configured in the side of the layer be formed with containing tabular metallic, is also configured in the side being formed with multilayer dielectric film.In other words, in interior subsides mode, become following formation: when film being attached at glass surface etc., not only spray water to the closely-related layer containing tabular metallic of water rem oval, also between multilayer dielectric film and glass surface, spray water.Therefore, by adopting interior subsides mode, the effect obtaining good adaptation can maximally have been given play to when not making water rem oval reduce.

[infrared shield]

Infrared ray shielding film of the present invention can be applicable to field widely.Such as, the window subsides films such as the heat ray reflection film of heat ray reflecting effect or agricultural hot house film etc. is given by the equipment that is exposed to for a long time in sunlight as the window be fitted in outside the room of building, automotive window etc., as long as improving weatherability, suppressing the object of the excessive rising of indoor temperature, just can use.In addition, the automobile infrared ray shielding film clamped between the glass and glass of the laminated glass etc. of automobile is also suitable as.Now, owing to the sealing of infrared ray shielding film can be completely cut off with extraneous air, so from the viewpoint of durability preferably.

The infrared ray shielding film that the present invention relates to is specially adapted to directly or via adhesive and glass or the parts that replace the matrixes such as the resin of glass to fit.

That is, the invention provides the infrared shield that infrared ray shielding film of the present invention is at least simultaneously set at matrix.

As matrix, preferably plastic substrate, metallic matrix, ceramic matrix, cloth-like matrix etc., can be arranged at the matrix of film-form, tabular, spherical, cubic, the various shape such as rectangular-shaped by infrared ray shielding film of the present invention.Wherein, the ceramic matrix of preferred tabular, more preferably arranges the infrared shield of infrared ray shielding film of the present invention on a glass.As the example of glass plate, such as, can enumerate the float flat glass recorded in JIS R3202:1996 and polishing plate glass, as thickness of glass, be preferably 0.01mm ~ 20mm.

As the method arranging infrared ray shielding film of the present invention on matrix, preferably use and on infrared ray shielding film, be coated with adhesive layer as mentioned above and the method being attached at matrix across adhesive layer.

As applying method, the dry adhered directly putting up film on matrix, the method for carrying out water subsides laminating as mentioned above can be applied, but do not enter between matrix and infrared ray shielding film to make air, in addition, from the view point of the easiness that the location of infrared ray shielding film on matrix etc. is implemented, water method of pasting more preferably is utilized to fit.

Infrared shield of the present invention arranges the mode of infrared reflection film of the present invention at least one side of matrix, but also can be the mode arranged in the multiaspect of matrix or the mode arranging multiple matrix on infrared ray shielding film of the present invention.Such as, can be arrange on the two sides of above-mentioned glass sheet infrared reflection film of the present invention mode, be coated with adhesive layer on the two sides of infrared reflection film of the present invention and make above-mentioned glass sheet fit in the mode of the laminated glass shape on the two sides of infrared reflection film.

Embodiment

Below, enumerate embodiment and further describe the present invention, but the present invention is not by any restriction of these embodiments.Should illustrate, use the expression of " part " or " % " in an embodiment, if not otherwise specified, then represent " mass parts " or " quality % ".

(embodiment 1-1)

[manufacture of infrared ray shielding film]

< contains the formation > of the layer of tabular silver particles

(making of the coating fluid containing tabular silver particles)

In the sodium citrate aqueous solution 50mL of 2.5mM, add the polystyrolsulfon acid aqueous solution 2.5mL of 0.5g/L, be heated to 35 DEG C.The sodium borohydride aqueous solution 3mL of 10mM is added, while carry out stirring the silver nitrate aqueous solution 50mL that 0.5mM is added on limit with 20mL/min in this solution.This solution is stirred 30 minutes, makes kind of a solution.

Next, in the sodium citrate aqueous solution 132.7mL of 2.5mM, add ion exchange water 87.1mL, be heated to 35 DEG C.In this solution, add the aqueous ascorbic acid 2mL of 10mM, add above-mentioned kind of solution 42.4mL, while stir with 10mL/min, the silver nitrate aqueous solution 79.6mmL of 0.5mM is added on limit.Stir after 30 minutes, add the hydroquinone sulfonic acid aqueous solutions of potassium 71.1mL of 0.35M, add 7 quality % aqueous gelatin solution 200g.

The white depositions mixed liquor of the silver nitrate aqueous solution 107mL of sodium sulfite aqueous solution 107mL and 0.47M of mixing 0.25M is added in this solution.The NaOH aqueous solution 72mL of 0.17M is added immediately after adding above-mentioned white depositions mixed liquor.Now, while the mode being no more than 10 with pH regulates interpolation speed, the NaOH aqueous solution is added on limit.Stirred 300 minutes, obtained the liquid (coating fluid containing tabular silver particles) of tabular silver particles dispersion.

Can confirm obtain containing the coating fluid of tabular silver particles in generate roughly hexagon and flat silver particles.In addition, utilize following methods to measure, result is known generates the tabular silver particles that average equivalent circular diameter is 230nm, averaged particles thickness is 16nm, aspect ratio is 14.3.

(evaluation of tabular silver particles)

The average equivalent circular diameter of tabular silver particles

About the average equivalent circular diameter of tabular silver particles, to the shape of 200 particles of arbitrary extracting from the SEM image observed, the particle of roughly hexagon or roughly disc-shape is set to A, the atypic particles such as tear type are set to B, carry out image analysis, the diameter of equivalent circle that 100 are equivalent to the particle of A is measured, using its mean value as average equivalent circular diameter with digital display calliper.

Averaged particles thickness

The coating fluid containing tabular silver particles obtained is dripped on the glass substrate and drying, uses AFM (AFM) (NanocuteII, Seiko Instruments Inc.) to measure the thickness of a tabular silver particles.Should illustrate, as the condition determination using AFM, be set to Autonomous test type sensor, DFM pattern, measurement range 5 μm, sweep speed 180 seconds/1 frame, number of data points 256 × 256.

Aspect ratio

According to average equivalent circular diameter and the average particle thickness of the tabular silver particles obtained, with average equivalent circular diameter divided by averaged particles thickness, calculate aspect ratio.

(formation of the layer containing tabular silver particles)

At PETG (PET) film of 50 μm of thickness, (Co., Ltd.'s system is spun by Japan, A4300: the easy bonding layer in two sides) on, 20% is become and dry film thickness becomes the mode of 5 μm with the area occupation ratio obtained as mentioned above, the coating fluid containing tabular silver particles obtained in utilizing the coating of line rod above-mentioned, under the baking temperature of 120 DEG C, drying 2 minutes, forms the layer containing tabular silver particles.

(evaluation of the angle of orientation of tabular silver particles)

After the film epoxy resin with the layer containing tabular silver particles made is carried out embedding treatment, cutting off with razor with under the state of liquid nitrogen frozen, making the vertical direction cross-section samples of film.Observe this vertical direction cross-section samples with sweep electron microscope (SEM), to 100 dull and stereotyped particles of silver, calculate the inclination angle (absolute value) relative to base material horizontal plane in the mode of mean value.

The making > of < multilayer dielectric film No.1-1

According to United States Patent (USP) the 6th, 049, that records in No. 419 descriptions melt extrudes method, using the duplexer of PEN (PEN: refractive index 1.65) and polymethyl methacrylate (PMMA: refractive index 1.40) as 1 unit, after stacked 50 unit (counting 100 layers), be drawn into longitudinally 2 times, oblong, carry out heat fixation, cooling, for physical film thickness, PEN layer is made to be 159nm, make PMMA layer be 190nm, make multilayer dielectric film No.1-1.

< contains the layer of tabular silver particles and the laminating > of multilayer dielectric film No.1-1

Make-up machine is utilized to fit in the mode that the layer become as shown in Figure 3A is formed the multilayer dielectric film No.1-1 made and the above-mentioned film with layer containing tabular silver particles.Now, when making the laminating of PET base material side, tension force is 5kg/m, and when making the laminating of multilayer dielectric film side, tension force is 5kg/m, makes roller temperature be 140 DEG C, with the speed of 2m/min by make-up machine, obtains duplexer.

The formation > of < hard conating (HC layer)

In methyl acetate 90 mass parts, add ultraviolet hardening be firmly coated with material (UV-7600B: the Nippon Synthetic Chemical Industry Co., Ltd's system, ultraviolet hardening polyurethane acrylate resin) 7.5 mass parts, then Photoepolymerizationinitiater initiater (IRGACURE (registration mark) 184:Ciba Specialty Chemicals system is added, 1-hydroxycyclohexylphenylketone) 0.5 mass parts being uniformly mixed, make hard coat layer coating solution (HC-1) thus.

Then, on the duplexer made in above-mentioned, to become the mode that the layer shown in Fig. 3 A is formed, utilize the line rod above-mentioned hard coat layer coating solution of coating (HC-1), carry out 3 minutes heated-air dryings at 70 DEG C.Thereafter under air, the ultraviolet curing device (use high-pressure sodium lamp) of Eye Graphics Inc. is utilized, at condition of cure: 400mJ/cm ²under be cured, form the hard conating of thickness 2 μm thus.

The formation > of < adhesive layer

By ethyl acetate 60 mass parts and the mixing of toluene 20 mass parts, then add acrylic adhesive (ARONTAC (registration mark) M-300: Toagosei Co., Ltd's system) 20g and be uniformly mixed, preparing adhesive coating fluid thus.

Adhesive layer adopts and on barrier film, is coated with adhesive layer, the method for fitting with above-mentioned duplexer thereafter.

As barrier film, use the polyester film (Cerapeel (registration mark): Toyo Metallizing Co., Ltd.'s system) that 25 μm thick.Barrier film utilizes line rod coating adhesive coating fluid, 80 DEG C of dryings 2 minutes, makes the film (film of band adhesive layer) of the adhesive layer with thickness 18 μm thus.Formed the mode of (interior subsides formation 1) with the layer become as shown in Figure 3A, utilize make-up machine to be fitted on the above-mentioned duplexer made on the adhesive layer surface of the film of band adhesive layer.Now, when making the laminating on stacked side, tension force is 10kg/m, and when making the laminating of the film of band adhesive layer, tension force is 30kg/m.

As above infrared ray shielding film is made.

(embodiment 1-2)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 100 DEG C, in addition, make infrared ray shielding film in the same manner as embodiment 1-1.

(embodiment 1-3)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 80 DEG C, in addition, make infrared ray shielding film in the same manner as embodiment 1-1.

(embodiment 1-4)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 65 DEG C, in addition, make infrared ray shielding film in the same manner as embodiment 1-1.

(embodiment 1-5)

The making > of < multilayer dielectric film No.1-2

(preparation of low-index layer coating fluid)

Water-soluble resin PVA224 (Co., Ltd. Kuraray system is added while stirring in pure water 500 mass parts, saponification degree 88 % by mole, the degree of polymerization 1000) 10.0 mass parts, add water-soluble resin R1130 (Co., Ltd. Kuraray system again, silanol-modified polyvinyl alcohol) 5.0 mass parts, then water-soluble resin AZF8035 (the Nippon Synthetic Chemical Industry Co., Ltd's system) 2.0 mass parts are added, mixing limit, limit is warming up to 70 DEG C, make it dissolve, obtain the aqueous solution of water-soluble resin thus.

Then, in 10 quality % acid silicon dioxide sols (SNOWTEX (registration mark) OXS: Nissan Chemical Ind Ltd's system) 350 mass parts of silicon dioxide microparticle containing average grain diameter being 5nm, add the whole amount of the above-mentioned water-soluble resin aqueous solution and mix.Add RAPISOL (registration mark) A30 (Japan Oil Co's system) 0.3 mass parts as anion system surfactant again, stir after 1 hour, be supplemented to 1000.0g with pure water, prepare low-index layer coating fluid thus.

(preparation of TiO 2 sol aqueous dispersion)

Waterborne suspension (the TiO suspended in water making titanium dioxide hydrates ₂concentration 100g/L) in 10L (liter), under agitation to add sodium hydrate aqueous solution (concentration 10 moles/L) 30L, be warming up to 90 DEG C, slaking, after 5 hours, with hydrochloric acid neutralization, is carried out filtering, washing.Should illustrate, in above-mentioned reaction (process), the material that titanium dioxide hydrates use is carried out pyrohydrolysis according to known method to titanium sulfate aqueous solution and obtained.

Make alkali treatment titanium compound with TiO ₂the mode that concentration becomes 20g/L is suspended in pure water, under agitation adds relative to TiO ₂amount is the citric acid of 0.4 % by mole and heats up.After liquid temperature reaches 95 DEG C, the mode becoming 30g/L with concentration of hydrochloric acid adds concentrated hydrochloric acid, while maintenance liquid temperature, stir 3 hours.

Measure pH and the ZETA current potential of the titania sol liquid obtained, consequently pH is 1.4, ZETA current potential is+40mV.And then utilize Malvern Inc. Zetasizer Nano to carry out particle size determination, consequently average grain diameter is 35nm, and single dispersing degree is 16%.In addition, make titanium oxide sol liquid 105 DEG C of dryings 3 hours, obtain particle powder, the JDX-3530 type using JEOL DATUM company to manufacture carries out the mensuration of X-ray diffraction, confirms as rutile-type particle.In addition, volume average particle size is 10nm.

Pure water 4kg is added in 20.0 quality % TiO 2 sol aqueous dispersion 1kg of the rutile titanium dioxide particulate containing volume average particle size 10nm.

(preparation of silicate aqueous solution)

Preparation SiO ₂concentration is the silicate aqueous solution of 2.0 quality %.

(preparation of silica modified TiO 2 particles)

Add pure water 2kg in above-mentioned 10.0 quality % TiO 2 sol aqueous dispersion 0.5kg after, be heated to 90 DEG C.Then, slowly adding above-mentioned silicate aqueous solution 1.3kg, then carry out heating for 18 hours at 175 DEG C in autoclave, and then concentrated, obtaining the titanium dioxide for having Rutile structure and coating is SiO ₂the particle of 20 quality %.

(preparation of high refractive index layer coating fluid)

By silica modified TiO 2 particles colloidal sol aqueous dispersion 28.9 parts, the aqueous solution of citric acid 10.5 parts of 1.92 quality %, the allyl ether copolymer (AKM-0531 of 10 quality % of 20.0 quality % that obtain in above-mentioned, Japan Oil Co's system) the boric acid aqueous solution 9.0 parts mixing of the aqueous solution 2.0 parts and 3 quality %, prepare silica modified TiO 2 particles dispersion liquid.

Then, titanium oxide dispersion is stirred on limit, while add the polyvinyl alcohol (PVA217 of 5.0 quality % in pure water 16.3 parts; Co., Ltd. Kuraray system) aqueous solution 33.5 parts.Then, add the 1 quality % aqueous solution 0.5 part of anionic surfactant's (RAPISOL (registration mark) A30, Japan Oil Co's system), be finally supplemented to 1000 parts with pure water, prepare high refractive index layer coating fluid.

Should illustrate, utilize said method to measure the refractive index of low-index layer, its result is 1.44.The refractive index of the high refractive index layer recorded equally is 1.92.

(formation of multilayer dielectric film)

Use can carry out simultaneously multi-layer coated sliding hopper apparatus for coating, the low-index layer coating fluid of above-mentioned middle preparation and high refractive index layer coating fluid are become the mode of low-index layer with film upper surface side, the stacked number of total is made to become the mode of 12 layers with alternately laminated high refractive index layer and low-index layer further, limit is incubated at 45 DEG C, while multi-layer coated while of carrying out on film.Thereafter, the condition becoming less than 15 DEG C according to face is jetted 1 minute cold wind, and after making it fixing, the warm braw of 80 DEG C of jet, makes it dry, formation multilayer dielectric film No.1-2.Utilize SEM to observe the cross section of film, result is the thickness of low-index layer is 170nm, and the thickness of high refractive index layer is 130nm.

Like this, form multilayer dielectric film No.1-2 and replace multilayer dielectric film No.1-1, in addition, make infrared ray shielding film in the same manner as embodiment 1-1.

(embodiment 1-6)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 100 DEG C, in addition, make infrared ray shielding film in the same manner as embodiment 1-5.

(embodiment 1-7)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 80 DEG C, in addition, make infrared ray shielding film in the same manner as embodiment 1-5.

(embodiment 1-8)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 65 DEG C, in addition, make infrared ray shielding film in the same manner as embodiment 1-5.

(embodiment 1-9)

Use the hard coat layer coating solution (HC-2) made as described below to replace hard coat layer coating solution (HC-1), in addition, make infrared ray shielding film in the same manner as embodiment 1-1.

In methyl acetate 90 mass parts, add ultraviolet hardening be firmly coated with material (UV-7600B: the Nippon Synthetic Chemical Industry Co., Ltd's system) 7.5 mass parts, then add Photoepolymerizationinitiater initiater (IRGACURE (registration mark) 184:Ciba Specialty Chemicals system) 0.5 mass parts and be uniformly mixed.Then, add ATO powder (ultra micron ATO: Sumitomo Metal Mining Co., Ltd's system) 2 mass parts as inorganic infrared absorbent, carry out high-speed stirred with homogenizer, make the hard coat layer coating solution (HC-2) containing infrared absorbent thus.

(embodiment 1-10)

Use above-mentioned hard coat layer coating solution (HC-2) to replace hard coat layer coating solution (HC-1), in addition, make infrared ray shielding film in the same manner as embodiment 1-5.

(embodiment 1-11)

Forming (interior subsides formation 2) with layer as shown in Figure 3 B carries out stacked, in addition, makes infrared ray shielding film in the same manner as embodiment 1-1.

(embodiment 1-12)

Forming (interior subsides formation 2) with layer as shown in Figure 3 B carries out stacked, in addition, makes infrared ray shielding film in the same manner as embodiment 1-5.

(embodiment 1-13)

Forming (outer subsides formation 3) with layer as shown in Figure 3 C carries out stacked, in addition, makes infrared ray shielding film in the same manner as embodiment 1-1.

(embodiment 1-14)

Forming (outer subsides formation 3) with layer as shown in Figure 3 C carries out stacked, in addition, makes infrared ray shielding film in the same manner as embodiment 1-5.

(comparative example 1-1)

Do not form the layer containing tabular silver particles, in addition, make infrared ray shielding film in the same manner as embodiment 1-1.

(comparative example 1-2)

Make the stacked number of multilayer dielectric film be 200 layers, in addition, make infrared ray shielding film in the same manner as comparative example 1-1.

(comparative example 1-3)

Do not form the layer containing tabular silver particles, in addition, make infrared ray shielding film in the same manner as embodiment 1-5.

(comparative example 1-4)

Make the stacked number of multilayer dielectric film be 22 layers, in addition, make infrared ray shielding film in the same manner as comparative example 1-3.

(comparative example 1-5)

Do not form dielectric stack film, in addition, make infrared ray shielding film in the same manner as embodiment 1-4.

(comparative example 1-6)

After making the drying of the layer containing tabular silver particles, thickness is 12 μm, in addition, makes infrared ray shielding film in the same manner as comparative example 1-5.

(comparative example 1-7)

In above-mentioned (formation of the layer containing tabular silver particles), make baking temperature be 100 DEG C, in addition, make infrared ray shielding film in the same manner as comparative example 1-5.

(evaluation)

(infrared reflection rate)

Use spectrophotometer (using integrating sphere, Japan Spectroscopy Corporation's system, V-670 type), the infrared ray shielding film being attached at the thick float flat glass of 3mm is measured to the reflectivity in 850 ~ 1150nm region.During mensuration, except embodiment 1-13 and 1-14, with light, sample is set from the mode of glass surface incidence.On the other hand, the film of embodiment 1-13 and 1-14 arranges sample with light from the mode of the film side incidence being attached at glass.Carry out 3 times to measure, obtain its mean value, as infrared reflection rate.

(insolation absorptivity)

Use spectrophotometer (using integrating sphere, Japan Spectroscopy Corporation's system, V-670 type), according to JIS A5759:2008, insolation absorptivity is measured to the infrared ray shielding film being attached at the thick float flat glass of 3mm.During mensuration, except embodiment 1-13 and 1-14, with light, sample is set from the mode of glass surface incidence.On the other hand, the film of embodiment 1-13 and 1-14 arranges sample with light from the mode of the film side incidence being attached at glass.Mensuration carries out 3 times, obtains its mean value, as insolation absorptivity.

(haze value)

Use haze meter (Japanese electricity Se Industrial Co., Ltd system, NDH5000), measure according to JISK7136:2000.Haze value 1.5 is practical when being following.

(evaluation of durability)

To the infrared ray shielding film of the thick float flat glass of 3mm be attached at outdoor placement 1 year.Period, for the incidence of sunlight, except embodiment 1-13 and 14, with sunlight, sample is set from the mode of glass surface incidence.On the other hand, the film of embodiment 1-13 and 1-14 arranges sample with sunlight from the mode of the film side incidence being attached at glass.Evaluation utilizes spectrophotometer (using integrating sphere, Japan Spectroscopy Corporation's system, V-670 type), calculates Δ E, measure the change of color by the Lab value before and after placing.Δ E is practical when being less than 0.5.

The formation of the infrared ray shielding film obtained in embodiment 1-1 ~ 1-14 and comparative example 1-1 ~ 1-7 and evaluation result are shown in following table 2.

Table 2

As shown in Table 2 above, infrared ray shielding film of the present invention not only can realize high IR line reflection rate and high transparent, even and if Long-Time Service also can't see the problems such as variable color.

In addition, usual insolation absorptivity is higher, and the heating of film is larger, even but as embodiment 1-9 and 1-10, there is infrared ray-absorbing layer and the film that insolation absorptivity uprises, also can suppress through time variable color.This is presumably because that the layer containing tabular silver particles as variable color position is separated across base material with causing the infrared ray-absorbing layer of heating, so heating is little on the impact of the layer containing tabular silver particles.

(embodiment 2-1)

[manufacture of infrared ray shielding film]

< contains the formation > of the layer of tabular silver particles

(making of the coating fluid containing tabular silver particles)

Due to identical with (making of the coating fluid containing tabular silver particles) in above-described embodiment 1-1, so omit the description here.

(evaluation of tabular silver particles)

Due to identical with (evaluation of tabular silver particles) in above-described embodiment 1-1, so omit the description here.

(formation of the layer containing tabular silver particles)

Prepare the coating fluid containing tabular silver particles that obtains in the above-mentioned solution according to area occupation ratio (being 12% in the such as embodiment 2-1) dilute with water recorded in table 3.(Co., Ltd.'s system is spun by Japan to use line rod this solution to be coated on PETG (PET) film of 50 μm of thickness, A4300: the easy bonding layer in two sides) on, with the baking temperature of 70 DEG C drying 2 minutes, form the layer containing tabular silver particles.Should illustrate, now, the mode becoming 0.03 μm with dry film thickness is coated with.The adhesion amount of tabular silver particles is 20.4mg/m ².

(evaluation of the area occupation ratio shared by tabular silver particles)

In order to measure area occupation ratio to the film with the layer containing tabular silver particles made as mentioned above, sweep electron microscope (society of Hitachi system, S-5000) is used to observe the surface of the layer containing tabular silver particles.Now, multiplying power is set to 30000 times and observes, binaryzation is carried out to the SEM image obtained, calculate the existence part of silver particles and the area of non-existence part, obtain the area occupation ratio of actual measurement.Then, change locates, and obtains the area occupation ratio c of actual measurement by identical step at 3 places, gets its mean value as the area occupation ratio C shared by tabular silver particles.Consequently area occupation ratio C is 12%.

Should illustrating, being shown in table 3 by measuring by step same as described above the area occupation ratio C obtained to following embodiment and comparative example.

(evaluation of the angle of orientation of tabular silver particles)

After the film epoxy resin of the layer had containing tabular silver particles made is carried out embedding treatment, cutting off with razor with under the state of liquid nitrogen frozen, making the vertical direction cross-section samples of film.Utilize sweep electron microscope (SEM) to observe this vertical direction cross-section samples, to 100 dull and stereotyped particles of silver, in the mode of mean value, calculate the inclination angle (absolute value) relative to base material horizontal plane.Consequently, the angle of orientation of gained tabular silver particles is in the scope of 5 ~ 15 °.

The formation > of < hard conating (HC layer)

Hard coat layer coating solution (HC-1) is made in the same manner as above-described embodiment 1-1.

Then, on the above-mentioned duplexer made, the mode formed to become the layer shown in Fig. 3 B utilizes the line rod above-mentioned hard coat layer coating solution of coating (HC-1), carries out 3 minutes heated-air dryings at 70 DEG C.Thereafter, under air, utilize the ultraviolet curing device (high-pressure sodium lamp use) of Eye Graphics Inc., with condition of cure: 400mJ/cm ²be cured, form the hard conating of thickness 3 μm thus.Should illustrate, the thickness of hard conating is obtained by utilizing the cross section of SEM observation hard conating.

< multilayer dielectric film No.2-1 makes >

Utilize the method identical with the multilayer dielectric film No.1-1 in above-described embodiment 1-1, using the duplexer of PEN (PEN: refractive index 1.65) and polymethyl methacrylate (PMMA: refractive index 1.40) as 1 unit, after stacked 120 unit (counting 240 layers), be drawn into longitudinally 2 times, oblong, carry out heat fixation, cooling, for physical film thickness, PEN layer is made to be 159nm, make PMMA layer be 190nm, make multilayer dielectric film No.2-1.

The laminating > of < base material and multilayer dielectric film No.2-1

By the multilayer dielectric film No.2-1 made and the above-mentioned film with layer containing tabular silver particles, the mode formed to become the layer shown in Fig. 3 B utilizes make-up machine to fit.That is, the substrate surface of side not forming the layer containing tabular silver particles is fitted multilayer dielectric film No.2-1.Now, when making the laminating of PET base material side, tension force is 5kg/m, and when making the laminating of multilayer dielectric film side, tension force is 5kg/m, makes roller temperature be 140 DEG C, with the speed of 2m/min by make-up machine, obtains duplexer.

The formation > of < adhesive layer

Adhesive coating fluid is made in the same manner as above-described embodiment 1-1.

As barrier film, use the polyester film (Cerapeel (registration mark): Toyo Metallizing Co., Ltd.'s system) that 25 μm thick.Barrier film utilizes line rod coating adhesive coating fluid, 80 DEG C of dryings 2 minutes, makes the film (film of band adhesive layer) of the adhesive layer with thickness 20 μm thus.Should illustrate, the thickness of adhesive layer is obtained by utilizing the cross section of SEM observation adhesive layer.

Then, formed the mode of (interior subsides formation 2, interior paste with) to become the layer shown in Fig. 3 B, on the duplexer utilizing make-up machine to be fitted on the adhesive layer surface of the film of band adhesive layer to make in above-mentioned.Now, when making the laminating on stacked side, tension force is 10kg/m, and when making the laminating of the film of band adhesive layer, tension force is 30kg/m.

As above infrared ray shielding film is made.

(embodiment 2-2)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 28.9mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-1.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 17%.

(embodiment 2-3)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 96.9mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-1.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 57%.

(embodiment 2-4)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 149.6mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-1.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 88%.

(embodiment 2-5)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 163.2mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-1.Now, in above-mentioned (evaluation of tabular silver particles area occupied rate), area occupation ratio is 96%.

(embodiment 2-6)

In the above embodiments 2-1, form multilayer dielectric film No.2-2 shown below to replace multilayer dielectric film No.2-1, in addition, make infrared ray shielding film in the same manner as embodiment 2-1.

The making > of < multilayer dielectric film No.2-2

Multilayer dielectric film No.2-2 is made in the same manner as the multilayer dielectric film No.1-2 in above-described embodiment 1-5.

(embodiment 2-7)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 28.9mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 17%.

(embodiment 2-8)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 68mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 40%.

(embodiment 2-9)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 96.9mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Should illustrate, now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 57%.

(embodiment 2-10)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 132.6mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 78%.

(embodiment 2-11)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 149.6mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Should illustrate, now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 88%.

(embodiment 2-12)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 154.7mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 91%.

(embodiment 2-13)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 163.2mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Should illustrate, now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 96%.

(embodiment 2-14)

Forming (outer subsides formation 4) with layer as shown in Figure 3 D carries out stacked, and in addition, in above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 96.9mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-1.Should illustrate, now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 57%.

(embodiment 2-15)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 149.6mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-14.Should illustrate, now, in above-mentioned (evaluation of the area occupation ratio shared by tabular silver particles), area occupation ratio is 88%.

(embodiment 2-16)

Forming (outer paste by formation 4, outer subsides with) with layer as shown in Figure 3 D carries out stacked, and in addition, in above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 96.9mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-6.Should illustrate, now, area occupation ratio is 57%.

(embodiment 2-17)

In above-mentioned (formation of the layer containing tabular silver particles), the adhesion amount of tabular silver particles is 132.6mg/m ², in addition, make infrared ray shielding film in the same manner as embodiment 2-16.Should illustrate, now, area occupation ratio is 78%.

(comparative example 2-1)

Do not form the layer containing tabular silver particles, in addition, make infrared ray shielding film in the same manner as embodiment 2-1.

(comparative example 2-2)

Do not form the layer containing tabular silver particles, in addition, make infrared ray shielding film in the same manner as embodiment 2-6.

(comparative example 2-3)

Do not form multilayer dielectric film and the layer containing tabular metallic, replace, as shown in Fig. 3 E (layer forms 5), form 1 layer of metallic reflective coating respectively across base material, in addition, make infrared ray shielding film in the same manner as embodiment 2-1.Should illustrate, metallic reflective coating is formed in the following manner.

PETG (PET) film (Japan spinning A4300: the easy bonding layer in two sides) of 30cm × 30cm size, 50 μm of thickness is put into the vacuum tank of vacuum deposition apparatus, indoor are evacuated to 1.33 × 10 ^-3pa (10 ^-5torr), the temperature of film is remained on 50 DEG C.2 evaporation plate are set in vacuum tank, put the powder of silver rod and indium oxide respectively.First indium oxide is heated to 1200 DEG C, with the evaporation rate of/second is formed the indium oxide tunicle of thickness.Then silver is heated to 1400 DEG C, with the speed of/second will silver-colored tunicle to be formed as indium oxide membranaceous.Again form the indium oxide tunicle of condition same as described above, identical thickness, form the silver-colored tunicle of condition same as described above, thickness again, finally similarly form the indium oxide tunicle of the same terms, thickness, form metallic reflective coating thus.In addition, identical process is implemented to the back side of PET base material, form metal evaporation reflectance coating on two sides.

(evaluation)

(screening performance: sheltering coefficient, the coefficient of overall heat transmission)

Use spectrophotometer (using integrating sphere, Japan Spectroscopy Corporation's system, V-670 type), according to JIS A5759:2008, sheltering coefficient, the coefficient of overall heat transmission are measured to the infrared ray shielding film being attached at the thick float flat glass of 3mm.During mensuration, from the mode of arbitrary glass surface incidence, sample is arranged with light to the sample of embodiment and comparative example.Carry out 3 times to measure, obtain its mean value, respectively as sheltering coefficient, the coefficient of overall heat transmission.

(cohesive)

For the object of the moisture drying state measured after water subsides, evaluate the zygosity (bonding force) after water subsides.The infrared ray shielding film of above-described embodiment and comparative example is cut into 250 × 25mm, on the float flat glass of 125 × 5 × thickness 3mm, pastes to become the mode recorded in JIS A5759:2008.Wherein, to glass surface and film adhesive layer surface spraying construction liquid fitting during stickup, the roller recorded in JIS Z0237:2009 is made to come and go 20 times on film and fit.Should illustrate, construction liquid is the liquid adding neutral lotion Joy (registration mark, P & G Inc.) 2g and make in water 1000g.

After adhesive film described above, preserve in the refrigerator of 10 DEG C, As time goes on take out, carry out the 180 ° of disbonded tests recorded in JIS A5759:2008.When pasting under the state of non-spraying application liquid, peeling force is 12N/25mm (complete tacky state), during spraying application liquid, measures the time (number of days) reaching complete tacky state.It is practical scope when reaching complete tacky state within 3 days.

(anti-mold effect)

By the infrared ray shielding film being attached at the thick float flat glass of 3mm 25 DEG C, place 120 days under the environment of 80%RH.Evaluate the variable color of the film end after placing.This variable color is mould due to the generation of dielectric stack film and variable color (mould erosion) that is that cause, if mould erosion is less than 3mm apart from film end, is then level no problem in practical.

The formation of the infrared ray shielding film obtained in embodiment 2-1 ~ 2-17 and comparative example 2-1 ~ 2-3 and evaluation result are shown in following table 3.

Table 3

As shown in Table 3 above, the number of days that infrared ray shielding film of the present invention reaches needed for complete closed state is short, and be less than 3 days, adaptation is good.In addition, the sheltering coefficient of infrared ray shielding film of the present invention is less than 0.65 and the coefficient of overall heat transmission is less than 5.0, has excellent effect of heat insulation and insulation effect.In addition, the mould erosion of infrared ray shielding film of the present invention is very little, is less than 3mm, therefore can say also have anti-mold effect.

Particularly, the sheltering coefficient of embodiment 2-9 and embodiment 2-10 is less than 0.60, and the coefficient of overall heat transmission is less than 4.0, therefore can say that screening effect is excellent.Further, infrared ray shielding film time reached needed for complete closed state of these embodiments is 1 day, extremely short, and also not by mildew attack, therefore obtains the result that adaptation, effect of heat insulation, insulation effect, anti-mold effect are all extremely excellent.

In addition, if comparing embodiment 2-9 and embodiment 2-16, then the sheltering coefficient of embodiment 2-9, the coefficient of overall heat transmission are all little, in addition, if comparing embodiment 2-10 and embodiment 2-17, then the sheltering coefficient of embodiment 2-10, the coefficient of overall heat transmission are all little, therefore can say interior subsides formation 2 namely in subsides mode formation in, higher effect of heat insulation and screening effect can be obtained.

On the other hand, for the film of embodiment 2-1 and embodiment 2-6, demonstrate that the area occupation ratio existed shared by silver particles is less than the sheltering coefficient of the film of 15%, the coefficient of overall heat transmission is large, the trend that effect of heat insulation, insulation effect are lower.In addition, the area occupation ratio shared by such silver particles is less than in the film of 15%, and mould erosion is more than 3mm, there is the trend that anti-mold effect is lower.In addition, as embodiment 2-5 and embodiment 2-12, the area occupation ratio demonstrated shared by silver particles is that the sheltering coefficient of the film of more than 90%, the coefficient of overall heat transmission are enough little, but till reaching complete closed state, need longer during.

In addition, the application, based on No. 2012-086590, the Japanese patent application No. of applying on April 5th, 2012 with No. 2012-086594, the Japanese patent application No. of applying on the same day, also introduces as a whole with reference to its disclosure.

Symbol description

1,12 base materials,

2,13 containing the layer of tabular metallic,

3 tabular metallics,

11 hard conatings,

14 multilayer dielectric film,

15 adhesive layers,

16 barrier films,

17 metallic reflective coatings.

Claims

1. an infrared ray shielding film, has:

Base material,

Comprise the multilayer dielectric film of high refractive index layer and low-index layer, and

Layer containing tabular metallic.

2. infrared ray shielding film according to claim 1, wherein, described multilayer dielectric film, compared with the described layer containing tabular clipped wire, is arranged at the light incident side of light.

3. infrared ray shielding film according to claim 1 and 2, wherein, the principal plane of described tabular metallic, relative to the surface of described base material, carries out planar orientation with the angle of 0 ° ~ ± 30 °.

4. the infrared ray shielding film according to any one of claims 1 to 3, wherein, described layer containing tabular metallic and described multilayer dielectric film are formed across described base material.

5. the infrared ray shielding film according to any one of Claims 1 to 4, wherein, when the area of described base material being set to A and the occupied area of described tabular metallic is set to B, the area occupation ratio C represented by following formula 1 is more than 15% and is less than 90%,

C [%]=(B/A) × 100 ... (formula 1).

6. the infrared ray shielding film according to any one of Claims 1 to 5, contains further:

Be layered in described containing the hard conating on the layer of tabular metallic, and

Be layered in the adhesive layer in described multilayer dielectric film.

7. the infrared ray shielding film according to any one of claim 1 ~ 6, wherein, the described layer containing tabular metallic contains tabular silver particles.

8. the infrared ray shielding film according to any one of claim 1 ~ 7, wherein, described high refractive index layer and described low-index layer contain metal oxide particle.

9. the infrared ray shielding film according to any one of claim 1 ~ 8, wherein, described multilayer dielectric film contains water soluble polymer.

10. the infrared ray shielding film according to any one of claim 1 ~ 9, further containing infrared ray-absorbing layer.

11. 1 kinds of infrared shields arrange infrared ray shielding film according to any one of claim 1 ~ 10 at least one side of matrix.