CN106062590B - A kind of manufacturing method of high-durability silver mirror - Google Patents

A kind of manufacturing method of high-durability silver mirror Download PDF

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CN106062590B
CN106062590B CN201580010120.2A CN201580010120A CN106062590B CN 106062590 B CN106062590 B CN 106062590B CN 201580010120 A CN201580010120 A CN 201580010120A CN 106062590 B CN106062590 B CN 106062590B
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film
layer
durability
silverskin
silver mirror
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CN106062590A (en
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近江健
近江健一
广川智也
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Okamoto Glass Co Ltd
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Okamoto Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

A kind of high-durability silver mirror; by the oxidation film as first layer, the film of the metal selected from the metal with face-centered-cubic crystal structure as the second layer are sequentially formed on base material, as the silverskin of third layer, as the 4th layer of ito film of the thickness in 3~12nm and the protective film as layer 5, and high-durability silver mirror can be obtained.By being formed with from magnesium fluoride (MgF2)/silica (SiO2) the abrasion performance film that is constituted can make high-durability silver mirror have good wear consumption.The semiconductor substrate of glass baseplate or silicon etc. can be used as base material.By being formed with autoxidation silicon (SiO)/silica (SiO on base material2) two layers of basal layer constituted, and obtain high-durability silver mirror using the resin base material of COP etc..By the heat treatment between being carried out 30~90 minutes within the temperature range of 400~500 DEG C, and excellent heat resistance can be assigned.

Description

A kind of manufacturing method of high-durability silver mirror
Technical field
Present invention be about a kind of manufacturing method of the silver of durability (Ag) mirror, can be used not only in camera, In the reflection optical facilities of the optical goods of duplicator, projecting apparatus etc., it can also be used to which there is concentrating solar battery condenser In for motor vehicle reflection optics mechanism arrangement such as the head up display (HUD) of automobile, especially it is relevant to high reflection Rate and can bear harsh use environment excellent durability high-durability silver mirror manufacturing method.
Background technology
The speculum high as reflectivity generally shows the aluminium (Al) of high reflectance in the broader region of visible light Mirror.Aluminium mirror plates aluminium film on the substrate of glass or resin, and the average reflectance under visible ray regions is 90% or so. Under the situation for wanting to further increase reflectivity, the inteferometer coating for improving reflectivity, that is, reflection enhancing coating are formed on aluminium film. The average reflectance of the aluminium mirror of reflection enhancing coating is provided with up to 95% or so.Furthermore average reflectance used herein refers to can The simple average reflectance of reflectivity in the wavelength of 420 light-exposed~680nm.It is also used in identical meanings below.
Silver mirror is then to form silverskin to replace the mirror of above-mentioned known aluminium film, compared with aluminium mirror, in visible light There is broader region higher reflectivity, average reflectance to reach 93% or so.Also, increasing reflection is formed on silverskin Under the situation of film, average reflectance can be promoted to 97% or more.
[existing technical literature]
[patent document]
[patent document 1] Japanese Unexamined Patent Publication 2000-241612 bulletins.
[patent document 2] Japanese Unexamined Patent Publication 2003-4919 bulletins
No. 4307921 bulletins of [patent document 3] Japanese Patent
[patent document 4] Japanese Unexamined Patent Publication 2007-147667 bulletins
[patent document 5] Japanese Unexamined Patent Publication 2010-19875 bulletins
[patent document 6] Japanese Unexamined Patent Publication 2012-47856 bulletins
[non-patent literature]
[non-patent literature 1] " the alloy components additive effect for influencing the corrosion resistance of Ag films " Kobe Steel's technical report VOL.52,No.2,Sept.2002
[non-patent literature 2] " exploitation of the mixed gas corrosion check method of corresponding Asia environment ", SONY, the 7th electricity The reliability seminar of sub-component, 7S-8, November.1997
Invention content
It is being reflected in the device of optical facilities with projecting apparatus etc., a large amount of speculum is used in order to change light path.And In the reflection optical facilities of continuous repeated reflection, the light quantity of the optical module of final purpose is reached, it will be because of the reflection of speculum Rate and order of reflection, and the exponentially reduction of function.Therefore, a large amount of speculum need be used by having in reflecting optical facilities Under situation, in order to keep the reflectivity of speculum in a high reflectance, how to increase light quantity to ensure brightness, become one it is non- Often important project.
Most popular as high reflectivity mirror is increasing reflective aluminum mirror, even what transmission can also be functioned as protective film Under situation of the reflection enhancing coating to improve reflectivity, average reflectance at most only reaches 95% or so, for requiring higher anti- Penetrate in the purposes of rate that there will be the problems that can not be corresponded to.
High-durability is also critically important other than with high reflectance.These speculums will can constantly receive strong light, and It is exposed at high temperature because of light absorption.Can thus be required will be in a long time if under the situation for receiving light or heat Maintain high reflectance.Also, in the concentrating solar battery gradually popularized in recent years, it is used in the light-to-current inversion of aggregation sunlight Convex mirror in the optical facilities of component, or vehicular applications used in the head up display of automobile etc. convex mirror, due to needing It compared with known projection-type projecting apparatus purposes, more to be wanted for a long time by outside exposure to room or under environment same outside room Ask it to have：Prolonged durability, for the durability of corrosive gas caused by general urban district, make near shore With lower by salt damage durability.
On the other hand, above-mentioned silver mirror has reflectivity more higher than aluminium mirror in the broader region of visible light, in setting It is equipped under the situation in the increasing reflecting layer also functioned as protective layer, average reflectance reaches 97% or more.However and aluminium film It compares, since the durability of silverskin is low and easily corrodes, not applicable problem is had in the purposes for require high-durability.
It is due to the reason that when the adhesion deficiency between substrate, film is stripped or damages that the durability of silverskin is low. In addition, also learning in the case where bearing the situation of heat or ultraviolet light, silver atoms are easy mobile and then condensation and form bulky grain, therefore film becomes Must be uneven, and reflectivity is made to reduce.Its deteriorate degree in the case where long-time is by the situation exposure to high temperature or ultraviolet light particularly Significantly.For example concentrating solar battery condenser is by exposure under such environment.
To on common metal salt damage or corrosion, can substantially be construed as caused by electrolyte or reactant gas Caused by metal ionization and chemical reaction (such as oxidation etc.).Therefore also same about silver mirror, make electrolyte that can not reach gold Belong to, and it is made not by exposure to be important in corrosivity atmosphere.For this purpose, for metal film powerful protective film presence very It is important, however its defencive function is considered not complete enough in the structure of known silver mirror.It is contemplated that depositing in the environment Under the situation for the corrosive gas for having sulphurous acid gas, hydrogen sulfide gas and chlorine etc, these corrosive gas, which pass through, to be protected Cuticula is combined with silver atoms, becomes silver sulfide (AgS) or silver chlorate (AgCl) and melanism, thus causes reflection impaired.
Under the influence of this temperature and environmental factor, even if silver mirror reaches 97% or so Gao Ping instantly after manufacturing Equal reflectivity, but after being examined by various durabilities, that is, reflectivity will decline after prolonged use, because And it is unable to maintain that the situation of initial performance is in the majority.Such temperature and the peculiar absolutely not phenomenon of environmental factor, seem to be set to sea The concentrating solar battery in bank area or the automobile in general urban district of walking are the objects in this way by continuous exposure.
It is such in order to solve the problems, such as, it then there has been the motion for the technology for making the sub- high-durability of silver mirror.Such as non-special Just being disclosed in sharp document 1 has by the method that metalized ag is promoted durability.However, also describing the alloy because of silver simultaneously Change and is easy the content for making reflectivity reduce.
In patent document 1, in order to improve the adherence for being formed in the silverskin on resin substrate, announcement has following technology, Be initially formed the basal layer that autoxidation silicon fiml (SiO films) is constituted, then by between silicon oxide film and silverskin by metal film (such as copper film) is intervened wherein as middle layer, and the adhesion between resin substrate is made to be promoted, so obtain moisture-proof or Silver mirror of excellent durability.But the content of patent document 1 is in order to improve the adherence of resin substrate and silverskin, as silver The protective film of the surface side of film, reflection enhancing coating only double as being protective film, moisture, electrolysis for the surface side from silverskin Durability of matter and corrosive gas etc. is not then any to be referred to, meets used for solar batteries or automobile for example whether having With the specification of strict demand be also not any record.
As for patent document 2 in order to promote the adhesion between substrate and silverskin, it is formed with autoxidation aluminium film (Al2O3Film) The basal layer constituted.And it also discloses to have and is also formed with pellumina and oxidation titanium film (TiO on silverskin2Film) and then change Kind corrosion resistance.However, the purpose of patent document 2 is to improve adherence and durability with the few number of plies, though having improves adhesive tape stripping Description from property does not have durability of the moisture of the surface side from silverskin, electrolyte and corrosive gas etc. still then Have it is any refer to, for whether having that meet the specification of used for solar batteries or automobile strict demand be also not any Record.
Patent document 3 is then to recite to be formed in the speculum of reflectance coating on resin substrate, resin substrate and reflection It is formed with the Ranvier's membrane that autoxidation aluminium film is constituted between film, and forms dialling with fluorine-containing silicon compound on reflectance coating Moisture film, by preventing the intrusion from the moisture or electrolyte of resin substrate side and film surface side from preventing the corrosion of reflectance coating, And can take into account well ensures excellent reflection characteristic and durability.Though however 3 revealed technology of patent document recites 97% or more reflectivity is existed simultaneously with durability, but there is no the protections for forming acidification or corrosion to silverskin from silverskin From the point of view of film, whether durability, which has, meets in high temperature inspection used for solar batteries or automobile for electrolyte or corrosivity gas The requirement of body is still unknown number.
Patent document 4 is then using the aluminium oxide (Al for being recorded in patent document 22O3) basal layer, be then thereon used as It is recorded in the middle layer nichrome film (Ni-Cr alloy film) of patent document 1, corrodes in order to prevent, is formed on silverskin Autoxidation aluminium film and silicon dioxide film (SiO2Film) the upper buffer layer that is constituted, and it is formed with autoxidation to improve reflectivity The reflection enhancing coating that titanium film is constituted.However, though revealed technology recites by thermal cycle inspection, height in patent document 4 After warm high humidity is examined, high temperature exposure is examined and salt spraytest, 99% or more high reflectance still remain, but from From the point of view of there is no formation for the heat of silverskin, oxidation and the protective film of corrosion (preventing oxidation film) on silverskin, durability It is so not whether to have the requirement met in high temperature inspection used for solar batteries or automobile for electrolyte or corrosive gas Know number.
Patent document 5 is then the sequence stacking of the protective layer constituted according to basal layer, silver layer, plurality of layers on substrate It is formed by reflectance coating, in the plurality of layers for constituting protective layer, is set as not oxygen-containing by by the layer to connect with silver layer Si layers, and then promoted oxidation prevent effect and moisture-proof.By using Si layers, and obtain stable high reflectance.But Effect and moisture-proof are prevented in order to improve oxidation in patent document 5, though disclosing has the top in silverskin directly to form protective film Technology, but its only implement high temperature place examine with high temperature and humidity examine, if having satisfaction for used for solar batteries High temperature examine or durability etc. of corrosive gas as the prolonged durability required by the behaviour in service of automobile still It is so unknown number.
Patent document 6 is then that under forming the situation in the reflecting layer containing silver on resin base material, this is penetrated in order to block Reflecting layer and make resin base material deteriorate UV light, announcement have the reflecting plate that ITO layer is formed between reflecting layer and resin base material. Among this, in order to make long-term weatherability, gas barrier property and the transparency and deposit, announcement, which has, also to be formed film thickness on the reflecting layer and exists The structure of the ITO layer of 7~15nm or so.However, patent document 6 is related to the reflecting plate of luminaire, technical field or Purposes is different from the present invention.Therefore, membrane structure is also different from the speculum of optical instrument and optical device, uses melamine Resin coating film is also different as this point of basic film or protective film.In addition, silverskin is clamped by ito film, though it can bear with one The long-time of the mercury vapor lamp of fixed intensity is irradiated, but whether is sustained other durabilities and examined, and especially automobile is wanted The durability inspection asked is still unknown number.
Furthermore with the hyaline membrane of the hyaline membrane of high refractive index and low-refraction alternately it is most change layer by layer made of multilayer be situated between Although plasma membrane mirror also can reach high reflectance by the interference effect of light, compared with aluminium mirror or silver mirror, can obtain high anti- The wavelength region for penetrating rate is narrow, in addition to the number of plies for reaching the required film of high reflectance is extremely more, as a result so that cost It is excessively high, it is not popularized other than specific use.
The purpose of the present invention is to provide a kind of high-durability silver mirror, is provided simultaneously with high anti-possessed by fine silver (Ag) mirror Penetrate rate, and with the excellent durability that will not be inferior to aluminium mirror or silver alloy mirror, such mirror not only meets and makes For durability required in the optical goods situation of projecting apparatus in known main application etc., for long-time exposure In heat and the light-focusing type solar power generation condenser of light, or comprising long-time exposure in general urban district with room external environment phase The product of the reflection optical facilities of close etc automobile, can also provide and improve durability to the silver mirror of usable level.
For more specifically, even if realizing can be provided under long lasting for the situation for bearing heat or ultraviolet light, silver atoms It can't assemble, possess the homogeneity of film, and high-durability silver mirror that reflectivity will not reduce, in addition, even if in environment Have under situation existing for the corrosive gas of sulphurous acid gas, hydrogen sulfide gas, oxides of nitrogen gas, chlorine etc, these Gas is combined with silver atoms, and the melanism as AgS or AgCl etc., keeps the impossible height of the situation that reflection is weakened durable Property silver mirror.
It is above-mentioned known in order to solve the problems, such as the present invention, it is a kind of high-durability silver mirror, which is characterized in that in base The oxidation film as first layer is sequentially formed on material, as in the metal with face-centered-cubic crystal structure certainly of the second layer The film of selected metal, as the silverskin of third layer, as the 4th layer of thickness in the ito film of 3~12nm and as the 5th The protective film of layer.
High-durability silver mirror of the present invention has the institute's structure from the first layer to layer 5 for respectively playing good function At basic membrane structure.As the base material that can be used in the present invention, continues in-depth study by many inventors, find whether Use the tree of the semiconductor substrate of glass baseplate or silicon (Si) substrate etc, cyclic olefin polymerization resin (COP resins) etc Aliphatic radical material has the basic membrane structure constituted from the first layer to layer 5 even with the metal machine material of brass etc Silver mirror, all there is high reflectance and good durability.
In the present invention, in special requirement under the situation of the durability (abrasion performance) of abrasion, preferably, the 5th On the protective layer of layer, the silica (SiO as abrasion performance film is formedX) film, magnesium fluoride (MgF2) film or this two layers film. In this SiOXThe mark of film refers to having autoxidation silicon fiml to the meaning of the film of the oxidizability between silicon dioxide film, in order to prevent The reduction of reflectivity caused by light absorption, it is generally desirable to silicon dioxide film.Silicon oxide film as abrasion performance film and fluorination After magnesium film or two tunic of magnesium fluoride/silica are made comparisons, two tunic of magnesium fluoride/silica shows most excellent abrasion performance Property.
In the present invention, in order to reach known unexistent high-durability, preferably, formed on the glass substrate from this first It to the 5th layer, or is formed after the abrasion performance film, is had in 400~500 DEG C of temperature on the layer 5 Heat treatment in range between 30~90 minutes.Can bear the base material being heat-treated under this temperature range can enumerate：Glass baseplate, Semiconductor substrate or metal base.On the other hand, it since resin base material can deteriorate at this temperature for holding, can not carry out The heat treatment.Furthermore it is recorded as under 400~500 DEG C of situation, refers to 400 DEG C or more 500 DEG C of meanings below, it is recorded as 30~ Under 90 minutes situations, refer to 90 minutes 30 minutes or more the meanings below.It is also used later as same meaning.
The essential structure of the present invention is in membrane structure of the formation from the first layer to layer 5 on various base materials.Also, After being used using glass baseplate, silicon (Si) substrate as the semiconductor substrate of representative or metal base as base material, even if these base materials The effect for bearing light or heat is also hardly gone bad, and film will not be made to deteriorate the gas of deep-etching occurs, from this point on From the point of view of can more show its excellent durability.
In the present invention, the basis for the adhesion of the oxidation film of first layer acting as ensuring between base material and silver (Ag) film Layer.Even if forming the silverskin of high reflection layer directly on base material, since abrasion etc. can be such that silverskin is peeled off immediately from base material, but formed Its adherence will be promoted after oxidation film.The effect for the basal layer being made of oxidation film is also the oxygen for being captured from base material side diffusion Gas prevents the oxidation of silverskin in turn.Therefore, necessity that oxidation film does not form stoichiometrically completely, or anaerobic condition Composition.Although the oxidation film of anaerobic condition can show light absorption mostly, since first layer is formed in silver in the present invention The downside (substrate side) of film therefore the reflectivity that silverskin will not be reduced, so not causing problems.
Oxidation film is formed as first layer, though because of the adherence between oxidation film and the glass baseplate for being all oxide Good reason, but in the present invention, even semiconductor substrate other than glass baseplate or under the situation of metal base, as first Layer and form oxidation film.This is because considering even semiconductor substrate or metal base, the surface of these base materials also can shape At the reason for having thin oxide film.
As the type of oxidation film, although various oxidation films made of vapour deposition process or sputtering method capable of being utilized to form a film, Preferably, being selected from pellumina (Al2O3Film), silica (SiO2Film) film or oxidation titanium film (TiO2Film) among any .The reason is that the oxidation film of these is easy film forming, residual stress is small, and the reason that the adherence between glass substrate is good.This A little oxidation films does not also have to the necessity stoichiometrically formed.Though for example, the composition of pellumina is stoichiometrically It is so Al2O3, in of the invention, it is necessary to must be Al2O3, can also be that the composition of a little anaerobic condition (is recorded as Al2O3-XSituation it is a lot of).
As oxidation film, after pellumina, silicon dioxide film or oxidation titanium film, the high-durability of the present invention can be improved Various durabilities of silver mirror.And.It is best with pellumina to improve heat resistance.
It is formed in the film of the adherence between base material and silverskin for improving silverskin, although known is with the left sides 40~200nm Right film thickness is formed, the oxidation film of first layer in the present invention, with compared with its for thin film thickness just very enough, particularly for The film thickness formation of 10nm~60nm or so.Certainly, even performance will not occur to be formed with the film thickness of 60nm or more On problem, but need pay attention to being easy to happen membrane stress this point.It is opposite that in 10nm thickness below, there will be for from glass The capture performance of the etchant gas of glass substrate-side becomes insufficient risk.
Connecing between oxidation film and silverskin of the film of the metal of the second layer of the present invention in order to improve base material and first layer The middle layer for the property.Therefore the film of metal rich in ductility normally due to be easily deformed, therefore can weaken via tensile stress or cut Shearing stress etc. can remove the strength of silverskin.In addition, since oxygen atom is affinity, there is the moisture prevented from substrate side Diffusion and lead to the effect of the oxidation of silverskin.Importantly, being from face-centered cube used in crystal structure in the present invention Metal in the film of metal selected.It is stood for the center of area this is because the upper layer of the film of the metal is formed by the crystal structure of silverskin The reason of cube.By use with silverskin have identical face centered cubic crystal structure metal film as middle layer, energy The crystallographic for improving silverskin, so as to improve reflectivity.
Although aluminium (Al), copper (Cu), nickel (Ni), platinum can be enumerated as the metal with face centered cubic crystal structure (Pt), golden (Au) etc., preferably, as the metal used in the present invention either one or two of among aluminium film, copper film or nickel film. The metal phase pair of these it is relatively inexpensive, and be easy film forming, and due to lattice constant also with silver lattice constant it is more close, It can expect the crystallization of promotion silverskin.
Once the film of the metal of the second layer as the present invention can promote the crystal of silverskin using aluminium film, copper film or nickel film Change, and durability can be promoted.Also, it is best with nickel film to improve heat resistance.
The thickness of the film of the metal is very enough as long as having 10~60nm or so.Relative to resin base material in patent document 1 Although using the copper film of the thickness of 100~200nm as middle layer, the film of metal thinner in the present invention is with regard to enough. In patent document 3, pellumina is formed with the thickness of 20~60nm as first layer, though thereon with the thickness shape of 20~60nm At nickel-chromium alloy layer, in of the invention, the film compared with its thin metal can be used.It can not be improved thickening the film of metal Oxidation-protective effect or crystallization facilitation effect, but membrane stress raising or increase expense this point can be made even more unfavorable.On the contrary If skiving to 10nm hereinafter, can then make the decreased effectiveness of mitigation tensile stress or shear stress, and decline from crystallographic From the point of view of, have the risk for causing the crystallization facilitation effect of silverskin to disappear.
Third layer is the silverskin as highly reflecting films.Although as silverskin is lower closer to ultraviolet range reflectivity, But there is the reflectivity high compared with aluminium film under the broader region of visible light, be suitable as reflectance coating.Silverskin in the present invention is with 100 The thickness of~200nm or so is formed as preferable.As thin compared with 100nm, reflectivity can be made insufficient.Especially in short wavelength side Reflectivity has the tendency of reduction, such as at wavelength 380nm, silverskin in 50nm when 100nm compared with about decline 1%.Opposite reflectivity and durability if thicker than 200nm is almost unchanged.Due to the price of the silver as filmogen Costliness, from a cost perspective, if in the range of meeting reflectivity or durability, it would be desirable to keep it thin as far as possible.
The silverskin of third layer wishes to be constituted by being substantially free of the fine silver of the ingredient other than silver in the present invention.Silverskin In, although it is inevasible to be mixed into the impurity not removed due to the purifying of silver, in order to reach high reflectance, It wishes to be constituted by being substantially free of the fine silver of the ingredient other than silver.According to the description of non-patent literature 1, though can expect by It is added and promotes its durability among the metal to silver of palladium (Pd) or niobium (Nb) etc, but other than the exception of a part, nothing Method avoids the reduction of reflectivity.From the point of view of this point, among the present invention, high reflectivity is wished as film forming ag material in order to obtain The silver material of 3N grades (99.9% or more) or more can be used by hoping.It is a feature of the present invention that maintaining the high reflection with fine silver It is not to promote durability by the alloying of silver while rate, but it is durable to be promoted by the effect of membrane structure entirety Property.
4th layer of ito film is referring to the deterioration for preventing silverskin, and reach high reflection among the membrane structure of the present invention It is very important film for the film of the deterioration preventing layer of rate and excellent durability.It is formed directly into silverskin through by thin ito film Top, can prevent formed as layer 5 protective film when silverskin because aoxidize etc. deterioration.The silverskin in order to prevent such as inventor Deterioration which kind of membrane material the most suitable layer as the top for being formed directly into silverskin has been carried out continuing deep grind Study carefully, result is not found out other than ito film while meeting the object of high reflectance and excellent durability both sides.For making Under situation with the very thin metal film of nickel, niobium, titanium (Ti) etc. to replace ito film, although as some effects of silverskin oxidation are prevented Fruit, but to maintain high reflectance, it is necessary to form the very thin film thickness of 1nm or less, the control of film thickness is difficult, thus durability with it is anti- Penetrate rate unstability.
Film thickness as the ito film, it is desirable in the range of 3~12nm, i.e. 3nm or more 12nm or less.Once the film of ITO layer After thickness leaves this range, both high reflectance and superior durable performance and the reduction with obvious effects deposited.That is, thickness is in less than 3nm When or the case where more than 12nm, self film rises instantly, or is examined by durability, and reflectivity can reduce.Although still unclear Chu's ito film it is contemplated that absorption and sorption or combines oxygen and corruption for showing the effect of excellent protecting effect in silverskin Corrosion gas, to prevent the oxidation or corrosion of silverskin.Furthermore though ITO is the oxide that tin oxide is mixed in indium oxide, The ratio of tin oxide can obtain same effect in the range of being 5~20wt%.
Layer 5 is protective film, reinforces the deterioration preventing effect of silverskin by ito film.Its performance prevents moisture or corrosion Property gas is from the surface side diffusion of film to the layer of the effect of silverskin.Although protective film also can be monofilm, preferably formed more Tunic.This is the case where forming the thick film of single layer, and film is easy to take column structure, gap is formed between column and column, because forming For the reason in the path that moisture or corrosive gas are spread to silverskin.By multilayered structure is taken, because can be to column structure Development generates obstruction, and improves the function as protective film.In addition, by the refractive index for each layer for selecting multilayer film appropriate With thickness, it can be made to play the function as the reflection enhancing coating for increasing reflectivity.Furthermore in order to make each layer of multilayer film more cause Densification improves the function of protective film, and it is effective to form film using plasma-based auxiliary or ion auxiliary vacuum evaporation.
Although can be used for obtaining increasing reflection effect there are many combination of the membrane material of protective film, membrane structure and film thickness Fruit, but it is desirable to being avoided that film thickness that its structure is a certain layer is extremely thick and the film thickness of a certain layer is very thin.Extremely thick film thickness can make It is easy development in the crystal growth of column structure carried out by film thickness direction, and as sparse between column structure and column structure Structure, therefore the barrier property for moisture or corrosive gas can be reduced.Very thin layer can then reduce barrier property.
As the example of protective film, can with the silicon oxide film of the pellumina of the thickness of 28nm and the thickness of 26nm and Sequence and the formed trilamellar membrane of scheduled thickness come as example the oxidation titanium film of the thickness of 44nm according to this.By this structure, prevent The only attack of the moisture from surface side or corrosive gas for the silverskin of third layer assists the effect of ITO layer, and can borrow Obtain increasing the effect of reflectivity by optical interference.The film of these and the downside (glass substrate (10) side) for being formed in silverskin First layer or the second layer film it is different, can directly influence reflectivity.That is, the film of these is opaque and have the feelings of light absorption Condition, reflectivity will be lowered according to the amount of light absorption.In order to reduce light absorption, it is desirable to which the film of these is close to its change as possible Learn pellumina, silicon dioxide film and the oxidation titanium film of metering composition.Furthermore it is although also contemplated for improve increasing reflecting effect Interference effect is improved to the number of plies can be increased, even if the number of plies to be overlapped to two layers or more again to form five layers or more of increasing reflection Film, but increase reflecting effect can't be opposite promotion, have instead membrane stress it is excessively high and cause film remove doubt.
In the present invention, the base material with circular conical surface or paraboloidal shape is could be used that as base material.Due to these base materials It is not flat base material, becomes to be in the circular cone medial surface or parabolic inner face that are made of recess portion or the circular cone being made of protrusion On outside lateral surface or parabolic, it is formed with the multilayer film by constituting high-durability silver mirror.This situation, according to recess portion or protrusion Position, thickness or the uneven risk of structure for being formed by each layer are high.Silverskin especially as third layer and the 4th layer Protective film on ito film, under the situation for forming the multilayer film for generating interference of light effect, since interference effect makes reflectivity drop It is low and present interference colours be it is bad.Therefore, under the situation using such non-tablet base material, the protective film as layer 5 is wished Silicon dioxide layer film can be used.The present invention can make high reflectance and excellent durability simultaneously in such embodiment It deposits.
In the present invention, preferably, formed from after the oxidation film to the protective film of the layer 5 of the first layer on base material, The heat treatment of 30~90 minutes is carried out within the temperature range of 400~500 DEG C.Here heat treatment refers to being maintained at its temperature Spend the meaning in range.Due to that membrane structure can be made to be densified by heat treatment, and durability can be further increased.After heat treatment It takes out to room temperature, makes its natural cooling.Multilayer film containing silverskin after this high-temperature heat treatment, borrow by known silver atoms Move condensation by thermophoresis and form big crystal grain, result causes film unequal, therefore it is most of can cause reflectivity with it is resistance to The reduction of long property.In extreme situations, the layer above and below also being broken through there is a phenomenon where the silverskin of crystal grain-growth is grown up and is exposed. However, being learnt from the membrane structure of the present invention, even if carrying out such heat treatment, the condensation of silverskin is inhibited.
It is to use as glass baseplate, semiconductor substrate or metal base etc can bear the heat treatment in the present invention The situation of base material, for the purposes for requiring excellent heat resistance, it would be desirable to carry out the heat treatment.
For being heat-treated by through the condition, so that the silverskin will not be condensed and can improve the effect of its durability, Although the effect of one of membrane structure based on the present invention can not be construed to, following explanation can be understood.That is, first, It is contemplated that by heat treatment, the crystallographic of the film of the metal of the second layer and the silverskin of third layer can all be promoted, the order of structure Sequence (crystallographic) improves.It can expect the migration of inhibition silver atoms through crystallographic is improved then.Second, it is contemplated that due to second The metal film of layer and the high adherence of the 4th layer of ito film and silverskin, make the thermal mobility of silver atoms be suppressed, silverskin is simultaneously It does not form granular texture and is the reason being densified.Third, it is also contemplated that being the tin (Sn) contained in ito film between heat treatment Atom forms very thin silver-tin alloy of atomic layer grade with silver atoms in silverskin surface, and reflectivity is made not reduce, and is promoted The effect of durability.
And the effect of the heat treatment not only densification of film only from the second layer until the 4th layer etc., also can the phase Wait for that its effect extends to the densification of the film of the layer 5 to first layer and for protective film.Furthermore heat treatment condition once exceeds After the temperature range, meeting can cause the oxidation of silverskin on the contrary because of the densification of silverskin etc. is insufficient, therefore more bad. Same problem is also will produce in addition, being somebody's turn to do when the range beyond the time is external to be heat-treated.
In the present invention resin base material with cyclic olefin polymer (COP) resin etc for representative can be used as base material.So And under the situation of resin base material, in order to improve the adhesion between base material and film, it is necessary to layer based on substrate surface is formed Two layers of basal layer being made of silicon oxide film/silicon dioxide film.Also, the oxidation film as the first layer uses oxidation Aluminium film is more suitble to.Also can think based on resin base material surface is formed after silicon oxide film/silicon dioxide film of layer, meeting Having makes resin base material surface have the effect of the surface same with glass substrate surface.Furthermore using resin as base material The case where base material, due to resin base material can not heat-resisting 400~500 DEG C of high temperature, aforementioned heat treatment can not be carried out.
In high-durability silver mirror of the present invention, as noted before, if the further shape on the protective film of layer 5 At two tunic of silicon oxide film, magnesium fluoride film or magnesium fluoride/silica as abrasion performance film, then abrasion performance can be significantly promoted Property.At this point, preferable to form abrasion performance film with the thickness of 10~20nm or so.These abrasion performance films, which are not intended to provide, to be increased instead The effect penetrated, but formed to promote abrasion performance.Silicon oxide film, magnesium fluoride or two tunic of magnesium fluoride/silica are suitble to As abrasion performance film be since the film of these is not easy to obtain crystal structure, and because its smooth surface wear strength is high, and It is not easy the reason scratched.In addition, the refractive index from these films is low, it is also especially suitable from the point of view of unobvious this point having scratch It closes.It is formed under the situation of these abrasion performance films, the heat treatment within the temperature range of aforementioned 400~500 DEG C between 30~90 minutes It wishes to carry out again after forming these abrasion performance films.This is because the reason that these abrasion performance films are also densified.
In the present invention, on the protective film of the layer 5 or on the abrasion performance film being formed on the protective film, also The water-repellent oil-repellent film being made of fluorinated organic compounds as most surface layer can be formed with.Water-repellent oil-repellent film is in addition to as table Except the function of the anti-soil film in face, also there is the water that rebounds.Therefore, especially in the environment of exposure to brine, by anti- It plays brine and plays excellent barrier property.From the point of view of water-repellent oil-repellent film itself is water white transparency and also only counts nm film thickness or so, Optical characteristics will not be changed by not interfering with the interference of light.
Furthermore in the present invention, when carrying out the heat treatment, which must form after heat treatment. This is because if formed before the heat treatment, heat treatment can make water-repellent oil-repellent film decompose the reason to disappear.
High-durability silver mirror of the present invention can bear very strict heat resistance inspection when carrying out the heat treatment It tests.Although the condenser used in concentrating solar electricity generation module, even being required to maintain at a high temperature of 300 DEG C After 2000 hours heat resistances are examined, the average reflectance in visible light region is 97% or more, but passes through the heat treatment The present invention high-durability silver mirror can also meet this one require.By with can meet this kind of heat resistance examine it is qualified Durability can be used as silver-colored high-durability silver mirror being exposed under the direct projection of sunlight for a long time.It is such heat-resisting Property the effect that can also be not construed as by membrane structure entirety promote the result of durability with heat treatment.
The saline immersion that high-durability silver mirror of the present invention can bear high concentration is examined (in 30 DEG C and 15% brine Dipping 24 hours) or brine spray inspection, 97% or more average reflectance can be maintained after examining.Saline immersion is examined It tests or brine spray verifies as being arranged is made in the automobile of coastal area in the solar power system of coastal area or walking The one of which of inspection project required by part, in order to evaluate the inspection that the corrosion resistance with height is carried out. Why high-durability silver mirror of the present invention can bear the saline immersion inspection of high concentration or brine spray is examined, and can be construed to Be in conjunction with the effect of ito film, the effect of scheduled heat treatment, effect of the effect of Ranvier's membrane and protective film etc. plyability it Object.
In addition, even if high-durability silver mirror of the present invention is examined by the corrosion resistance gas of JIS H8502 defineds After testing, possessed average reflectance is 97% or more in visible light region.Although this corrosion resistance gas examination makes With the hydrogen sulfide (H of concentration 10ppm2S) gas, the stringent inspection that exposure is carried out for 24 hours in the environment of 40 DEG C of 90%RH It tests, but high-durability silver mirror of the present invention can pass through this stringent inspection.By with this kind of durability, silver can be used as Same environment lower automobile-used high-durability silver mirror used for a long time uses in general urban district and outside room.Equally , even across the mixed of the exposure between 5 years of the south east asia for being equal to the recorded high temperature and humidity of non-patent literature 2 After closing corrosive gas inspection, can also it maintain average reflectance 97% or more.For the heat resistance of such corrosive gas, Also it can be not construed as promoting the result of durability with heat treatment by the effect of membrane structure entirety.
As described above, by the membrane structure disclosed in the present invention, high-durability silver mirror can be made to have both in visible light High reflectance in broader region and excellent durability.It is set as substantially not by by the silverskin of the third layer of reflection layer Including the fine silver of impurity helps to realize high reflectance.
After film formation by the heat treatment between being carried out 30~90 minutes within the temperature range of 400~500 DEG C, can make High-durability silver mirror has the high reflectance in the broader region of visible light and the superior durable comprising heat resistance simultaneously Property.Also, by the combination of these effects, even can be as very strict heat-resisting in concentrating solar power generation Property examine in, or with coastal area be assume carries out high concentration saline immersion inspection or brine spray inspection in, or It is to be examined for a long time using the corrosion resistance gas required by the automobile-used optical goods carried out for hypothesis in general urban district In testing, silver can also maintain high-durability silver mirror of 97% or more average reflectance to use in visible light region.
Furthermore even if high-durability silver mirror of the invention is in the acceleration of the auto parts by JIS D0205 defineds Aggressivity detects the sunlight carbon arc lamp-based weathering tester of (resistance to optical activity) (in the environment of 83 DEG C, with the carbon of 6.8mW/cm2 Arc exposure 1080 hours is simultaneously carried out at the same time water sprinkling and examines) after, also confirm its can maintain 97% or more it is average anti- Penetrate rate.
Silver mirror with excellent durability that previous known techniques fail to reach can be realized by the present invention.Even across Various durabilities can also realize that average reflectance is 97% or more in the broader region of visible light after examining.It is used in addition to meeting In the inside of liquid crystal projection apparatus for the durability required by speculum except, even with concentrating solar generate electricity use Heat resistance required by condenser is examined or salt tolerant water retting is examined and brine spray is examined, or is used as auto parts Situation under required corrosion resistance gas examination or salt tolerant water retting examine and after brine spray examines, can also make height Durability silver mirror maintains 97% or more average reflectance.As a result, being used for concentrating solar power generation as that can be used as The concave mirror of the head up display of condenser or automobile utilizes, moreover it is possible to silver mirror that uses under more harsh environment and can expect There is wide purposes.
Brief Description Of Drawings
Fig. 1 is the schematic diagram of an example for the membrane structure for showing high-durability silver mirror of the present invention.
Fig. 2 is shown in an example of the membrane structure of high-durability silver mirror of the present invention, the thickness of ito film with it is average instead Penetrate the schematic diagram of the relationship of rate.
Fig. 3 is the schematic diagram for showing an example that can be used for the base material with inclined surface of the present invention.
Fig. 4 is the schematic diagram of the substrate dome for being configured at evaporation coating device for the base material for showing molded non-planar.
Specific implementation mode
Other than separately having special explanation, basic membrane structure be by glass substrate (10)/aluminium oxide (11)/nickel (12)/ Silver (13)/ITO (14)/aluminium oxide (151)/silica (152)/titanium oxide (153) (is referred to as the underlying membrane of the present invention later Structure) seven-layer structure that is formed.The film of these is to use vacuum deposition apparatus (Showa vacuum product SGC26WA) institute's shape At.It is then to use Jeol BS80020CPPS as plasma-based auxiliary device).
＜ Examples 1 to 8 ＞
It after warm water cleaning glass substrate (10), is placed in vacuum deposition apparatus, until being vented to vacuum degree 0.9mPa.And And plasma-based is carried out to the surface of glass substrate (10) using the oxygen for reaction gas and is cleaned, then, vacuum degree (back pressure) is adjusted Whole is 3mPa.In the film forming of the oxidation film (11) (such as pellumina) of first layer, oxygen is imported, with the item recorded in table 1 Part is formed a film.It is similarly formed a film later with the condition recorded in table 1 by the follow-up second layer, and in glass substrate (10) On sequentially form the film of No.1~No.8.In table 1, " VD " of thin film-forming method field is the meaning of general vacuum evaporation, is made It is formed a film with electron gun evaporation evaporation material." PAD " is then the meaning being deposited using plasma-based auxiliary device, is that auxiliary uses Promote the ion gun of evaporation material ionization.Plasma-based auxiliary current at this time is recorded as PA electric currents.Furthermore the 4th layer of ito film Film forming (14) carried out under argon atmosphere, the film forming of nickel (12) and silver-colored (13) does not all import any gas, other than these The film forming of material carry out in oxygen atmosphere.O is noted down under the situation to form a film under oxygen atmosphere2Gas flow, and in argon Atmosphere is enclosed notes down argon flow amount under the situation of lower film forming, when controlling pressure when forming a film, records its pressure.Film forming terminates Afterwards, it is taken out from vacuum deposition apparatus, is put into control temperature in 450 DEG C of stove, carries out heat treatment in 60 minutes.
【Table 1】
It, will be as seven samples (embodiment 1~reality made by embodiment using the membrance casting condition for being shown in table 1 Apply example 7) membrane structure be shown in table 2.In Examples 1 to 4, the quadravalence until the film thickness of ito film (14) is transformed to 3~10nm The object of section, and keep the film thickness of other layers all identical.The film of first layer as embodiment 5 and 6 uses silicon dioxide film respectively Replace the pellumina for Examples 1 to 4 with oxidation titanium film.In this case, silicon dioxide film and oxidation titanium film Membrance casting condition on the basis of the membrance casting condition of the pellumina (11) of the first layer in table 1.In embodiment 7, as the second layer Structure replace nickel film using copper film.
【Table 2】
1~comparative example of ＜ comparative examples, 8 ＞
It is assessed to compare with embodiment and the membrane structure of produced comparative example is shown in table 3.Compare In example 1, without using the oxidation film as first layer, but in the membrane structure for directly forming nickel film on glass substrate (10).Compare Example 2 and comparative example 3 are the membrane structure without using the 4th layer of ito film (14) in the present invention.In comparative example 4 and comparative example 5, By taking the ito film (14) for forming nickel film or copper film to replace the 4th layer in the present invention as an example, film thickness is about 1nm.Comparative example 6 is to make It is used as the membrane structure of the film of the metal of the second layer in the present invention with chromium film.Comparative example 7 is 2 revealed film knot of patent document Structure, comparative example 8 are 4 revealed membrane structure of patent document.Furthermore in the making of comparative example 8, as patent document 4 is remembered It carries, the metal film as the second layer uses the nickel-chromium alloy for the chromium for containing 15wt% as evaporation material, with the film forming of nickel film Condition on the basis of condition forms nickel-chrome film.
【Table 3】
The investigation result of the relationship of the ito film thickness and average reflectance that play a significant role in the present invention is shown in Fig. 2. This, membrane structure identical with 1~embodiment of embodiment 4 is used as basic mode structure, is 3nm by the Thickness Variation of ITO (14) Until~15nm, later, with 450 DEG C of heat treated rear measurements for carrying out reflectivity in 60 minutes.In figure, the two-lines of line chart are Carry out after two groups of experiment as a result, the two is all same tendency.According to this as a result, being averaged to reach 97% or more Reflectivity judges that the film thickness as ito film (14) has in 12nm or less.
For the membrane structure of embodiment and comparative example, the various durabilities for implementing to be shown in table 4 are examined.It has such as the following It examines：The adherence for adhesive tape stripping of JIS H8502 defineds examines, the heat-resisting inspection required by solar cell manufacturer It tests, the constant temperature and humidity required by solar cell manufacturer and auto parts manufacturer is examined and saline immersion is examined, automobile zero Corrosion check etc. required by part manufacturer.It is examined other than the brine for implementing general condition examines A as saline immersion, and And also implement to require the brine of tightened up condition to examine B from a part.Corrosion check is in addition on the basis of JIS H8502 Corrosion check A also implements to correspond to the corrosion check B corresponding to actual exposed recorded in non-patent literature 2.
【Table 4】
The result of these inspections is arranged, table 5 is shown in about embodiment, table 6 is shown in about comparative example. Zero mark in the result bar of the inspection A of table 5 and table 6 indicates that film stripping does not occur in adherence inspection.× mark is then Indicate film stripping.Others annotation is then shown in the marge of table 6.
【Table 5】
【Table 6】
Without mark：40deg. average reflectances
*：300 DEG C of 100 a part of film stripping of time ＆
※：Most white grains occur in film surface, a black grain ＆ parts change colour
△：A film surface part becomes white
By the above content, the embodiment of the present invention 1 shows 97% or more in all inspections implemented Average reflectance learns it with excellent durability and high reflectance.Embodiment 2,3,4 compared with Example 1, only the 4th layer Ito film (14) film thickness it is different, it is believed that be that ito film thickness rate embodiment 1 also wants thick reason, so leading in the same manner as in Example 1 Cross all inspections.In the adherence implemented to make provision against emergencies is examined, film is not stripped, brine examine A with And brine examine B after, confirm be still maintained at 97% or more high reflectance.Although embodiment 5, the structure of embodiment 6 are The pellumina of layer, learns these based on being replaced in 1~embodiment of embodiment 4 using silicon dioxide film or oxidation titanium film Even if oxidation film under the situation used as first layer, examine A, examine D and examine E result have with embodiment 1~ The same durability of embodiment 4.Although the structure of embodiment 7 is substituted in second in 1~embodiment of embodiment 4 using copper film The nickel film of the film of the metal of layer, equally confirms and shows excellent durability.But in embodiment 5,6 and 7, only exist B (resistance to hot inspection) is examined to observe the reduction of 3~6% or so reflectivity later.It follows that being carried out from the viewpoint of heat resistance Judge, the oxidation film as first layer is preferable with pellumina, and the metal film as the second layer is then that nickel film is preferable.
According to the inspection result in comparative example content below is become apparent from.Comparative example 1 is not in glass substrate (10) example of pellumina (11) is formed on, therefore lacks adherence, is removed when adherence is examined.Comparative example 2 And comparative example 3 is the example for not forming the ito film (14) in the present invention, its film surface deteriorates after resistance to hot inspection, and It observes and many white grains or black grain occurs, in addition also observe the discoloration of film.Comparative example 4 and comparative example 5 are to form thickness Nickel film or the copper film of 1nm is spent to replace the example of the ito film (14) in the present invention, even so thin film thickness, Yin Qiping Durability inspection is not carried out in 97% reason below in equal reflectivity.Although comparative example 6 is to replace embodiment using chromium film Structure in 1~embodiment 4 as the nickel film of the film of the metal of the second layer, due to being dropped to through Overheating Treatment back reflection rate 93.3%, therefore and durability inspection is not carried out.Although being come using the above-mentioned nickel with face-centered-cubic crystal structure and copper Excellent durability is shown in 1~embodiment of embodiment 8 of the film of metal as the second layer, but is learnt with body-centered cubic knot The chromium of the crystal structure of structure body can be such that reflectivity drops under the situation used as the film of the metal of the second layer, by heat treatment It is low.Comparative example 7 is silver mirror of 2 revealed membrane structure of patent document, and the oxygen of film thickness thickness is although used as basic film Change aluminium film (11), learns for corrosion experiment B, although high reflectivity is able to maintain that, by the caudacoria of resistance to hot inspection short It will deteriorate within time, a part of film can peel off.Comparative example 8 is silver mirror of 4 revealed membrane structure of patent document, with The membrane structure of the present invention is compared, and has no to form ito film (14), it is nickel-chromium alloy that the film of the metal as the second layer, which is formed by, Film, the film thickness that other films are formed are respectively more of the invention thick.The result of various inspections, it is thus understood that A, salt are examined for brine Water examines B, and although it is possible to maintain high reflectivity, brine to examine the reflectivity after B to decline to a great extent, be unable to maintain that 97% Reflectivity decline after reflectivity and resistance to hot inspection is slightly larger, and drops to 97% or less.
In order to which the environment for evaluating high-durability silver mirror 1 of the present invention using semiconductor or resin as the situation of base material is resistance to Long property, weatherability, abrasion performance etc. other than the various inspections recorded in table 4, and are implemented to be recorded in the various durable of table 7 Property examine.It examines L and examines the inspection of M accurate according to the ISO09211 specifications formulated as the optically coated method of inspection Then, the JISB7080 reformulated out：It tests based on 2015.For examining sand erasing rubber specified in M, such as It is the homogeneous mixture of rubber and grinding agent described in the specification.
【Table 7】
＜ embodiments 8,9,10 and comparative example 9,10 ＞
It produces in addition to corrosion resistance, also especially with the membrane structure being appropriate in the purposes of requirement good wear consumption High-durability silver mirror 1, implement examine A, examine K, examine L and examine M simultaneously evaluated.As embodiment and compare The membrane structure that example is evaluated is shown in table 8.It is the basic membrane structure of the present invention until the layer 7 on glass substrate (10), Embodiment 8,9,10 and comparative example 9,10 are all identical.In embodiment 8, on the oxidation titanium film (153) of layer 7, as resistance to Abrasion film is formed with the magnesium fluoride film that thickness is 120nm.In embodiment 9, two that thickness is 20nm are formed on magnesium fluoride film Silicon oxide film (not shown).Embodiment 10 is formed with the water-repellent oil-repellent that thickness is 3nm on the silicon dioxide film (not shown) Film (not shown).On the other hand, comparative example 9 is formed with the fluorination that thickness is 25nm on the oxidation titanium film (153) of layer 7 Magnesium film.In addition, comparative example 10 is then formed with the silicon dioxide film that thickness is 20nm as abrasion performance film, it is formed with thickness above Degree is the water-repellent oil-repellent film (not shown) of 3nm.
The membrance casting condition of each layer is as recorded in table 1.The membrance casting condition for the magnesium fluoride film not being recorded in table 1 is to make Be evaporation source use magnesium fluoride, indoor pressure (back pressure) will be deposited and be evacuated to after 0.9mPa or less, using electron beam into Row vapor deposition.In addition, as water-repellent oil-repellent film, then use the commercially available vapor deposition for containing dipping fluorine-containing organic silicon compound use particle as Evaporation source (as an example of such as SURFCLEAR of Canon Optron corporations is), is similarly deposited using electronic beam method.
【Table 8】
For the embodiment and comparative example shown by table 8, implements brine spray and examine and (examine K), after brine inspection Adhesive tape peel test (examining A), environment durability are examined and (examine L) and abrasion performance is examined and (examines M).Its result is shown In table 9.In brine spray inspection, there is not reflectivity to decline 1.0% or more person after being checked, embodiment and comparative example are all With excellent corrosion resistance.In addition, brine spray examine after, carry out adhesive tape peel test after as a result, in the sample of any one The stripping of film is not all observed in this, therefore there is excellent adherence.Next, being also inspection in environment durability inspection Front and back reflectivity changes are tested less than 1%, therefore there is excellent corrosion resistance.About abrasion performance examine, embodiment 8,9, In 10, even if abrasion performance is irradiated and is observed with light after examining, relative to not observing caused by wear pattern For the penetrating of light, the striped of thin light is observed in comparative example 9,10.That is, in comparative example 9,10, since abrasion are examined Silverskin (13) can be made to wear away, and lead to light penetrates generation.From learning above, it is used as abrasion performance by magnesium fluoride film is used Mould can be assigned with the good wear consumption for examining qualified level by sand erasing rubber.But made using magnesium fluoride monofilm It under situation for abrasion performance film, learns if film thickness is thin, (comparative example 9) can not be examined by sand erasing rubber.
【Table 9】
＜ embodiments 11,12 ＞
High-durability silver mirror 1 of the present invention is produced on the silicon substrate for semiconductor, and evaluates its durability.It will The membrane structure evaluated is shown in table 10.It is the basic membrane structure of the present invention until layer 7.In embodiment 11, layer 7 On be formed with the silicon dioxide film of thickness 20nm and be used as abrasion performance film.In embodiment 12, formed on silicon dioxide film There is the water-repellent oil-repellent film (not shown) of thickness 3nm.About this two embodiments, implement the knot that brine spray is examined and (examines K) Fruit is shown in table 11.Reflectivity after brine spray inspection, which is reduced, learns high-durability silver mirror 1 of the invention less than 1% i.e. Make that also there is excellent durability on a silicon substrate.
【Table 10】
【Table 11】
11~16 ＞ of ＜ embodiments 13~16 and comparative example
High-durability silver mirror 1 of the present invention is produced using resin base material, and carries out various durability evaluations.As tree It is cyclic olefin polymer (the Japanese ZEON limited liability companies system of thickness 2mm used in aliphatic radical materialAfter Referred to as COP).The evaluation result of the membrane structure of embodiment and comparative example that evaluation is completed is shown in table 12 and table 13。
【Table 12】
【Table 13】
Can be learnt from the point of view of the evaluation result of the various durabilities for high-durability silver mirror 1 being relevant on COP base materials with Under item.In embodiment 13~16, though basic membrane structure of the invention is with aluminium oxide (11)/nickel (12)/silver (13)/ITO (14) sequence of/aluminium oxide (151)/silica (152)/titanium oxide (153) is formed, in the pellumina for forming first layer (11) before, in advance to aoxidize silicon/silicon dioxide SiO on COP base materials2Sequence carry out basis of formation film (not shown).That is, with Membrane structure on glass baseplate or Si base materials is different, as first layer is not initially to form pellumina for COP base materials, must It must be as silica (SiO) film of first basal layer formation thickness 5nm (not shown) or so, as second base on it The plinth film silica (SiO (not shown) for forming 150~300nm of thickness or so2) film, it is subsequently formed pellumina (11). Through two layers of basal layer (not shown) constituted for being previously formed this oxidation silicon/silicon dioxide, even if using resin base material Also high-durability silver mirror 1 can be made with high reflectance and excellent durability.Furthermore the zero mark expression in table does not occur The corrosion or stripping of film, × mark are then to indicate there is the corrosion for observing film or stripping after being checked.
It learns by being previously formed two layers of basal layer constituted, the pellumina (11) being formed on basal layer Thickness about 5nm or so.In addition, also judging that energy skiving is formed in the thickness of the nickel film (12) under silverskin (13).Furthermore it is real It applies in example 13,15 and 16, the silicon dioxide film of thickness 20nm is formed with as abrasion performance film, embodiment 14 is in silicon dioxide film On be more formed with water-repellent oil-repellent film (not shown).
Under the situation of Ranvier's membrane for not forming two-layer structure, the durability of silver mirror on COP base materials can be made to become It is insufficient.It learns in comparative example 11, the silicon dioxide layer film of thickness 100nm, comparative example is formed with as basic film (not shown) In 12, the SiO monofilms of thickness 100nm are formed with as basic film (not shown), although comparative example 14 not basis of formation film and It is that pellumina (11) is directly formed on COP base materials, all examples are examined through moisture-proof and (examine P) all in COP base material tables Face is abnormal, therefore can be allowed and film stripping formed thereon or reflectivity is greatly reduced.Although comparative example 13 is formed with two The Ranvier's membrane of layer structure, but do not formed under the situation of pellumina (11) above, it can be in COP base materials via moisture-proof inspection Surface is abnormal, via the stripping for also observing film after adhesive tape peel test (examining A).Comparative example 15 and comparative example 16 In, though be formed with the Ranvier's membrane of two-layer structure, though and form the membrane structure of pellumina (11) on it because second The thickness of the silicon dioxide film (not shown) of the Ranvier's membrane reason too thin in 50nm or less, due to being unable to fully prevent from coming from base material The corrosion of the silverskin (13) of side, and be unable to fully mitigate membrane stress, therefore also observe film stripping.
About embodiment 13, one hour is kept at -40 DEG C, instant heating is kept for one hour to 85 DEG C later, is followed with this Ring repeats 456 times to carry out after stringent thermal shock examines, according to be initially 95.8% reflectivity only drop to 94.5% can To learn, high-durability silver mirror 1 of the present invention on COP base materials has excellent thermal shock resistance.
Be not writing board shape base material on produce high-durability silver mirror 1, and carry out durability evaluation.With brass The object that the base material 20 that (copper-zinc alloy) is process is formed towards vertex B from rectangular bottom removal circular cone.Fig. 3 cuts open for it Face figure, A and C and the included angle A BC that B is constituted on bottom are θ.In the present embodiment, it is fabricated to the brass substrate of θ=50 °, in Inclined-plane ABC forms high-durability silverskin.That is, in this brass substrate 20, formed in from the inclined circular cone inclined-plane that ABC is constituted There is film.
Substrate holder (majority is referred to as substrate dome) for installing the base material for implementing vapor deposition among evaporation coating device is ball Face forms a film after arranging many base materials on the circumferencial direction of spherical surface or diametric(al).Also, the base material is in the shape of plane Under condition, no matter base material is installed on any position on the spherical surface of substrate holder, the thickness that film is formed by substrate plane also can It is almost the same.However, in the state that base material is not writing board shape, no matter base material is installed on towards which direction and base material The thickness of which position of holder, the vapor deposition on base material all can be different.Also, under the situation for forming multilayer film, due to each The accumulation of the thickness difference of the film of layer, it is not easy to obtain the optical characteristics (such as reflectivity) in accordance with design.
As shown in figure 4, four positions on substrate holder form a film from 25 ° of configuration glass substrates (10) of vertical plane Go out high-durability silver mirror 1 of the embodiment 17 and the embodiment 1 shown by table 2 shown by table 14.Embodiment 17 and embodiment 1 After being compared, in embodiment 17, for the silicon dioxide layer film that protective film is 20nm thickness, in embodiment 1 In, be formed with the three-layer protection film that is made of aluminium oxide (151)/silica (152)/titanium oxide (153) with as wear-resisting Consume the silicon dioxide film of film.In addition, the thickness of silverskin (13) is formed as thicker 500nm in embodiment 17.
【Table 14】
To configure high-durability silver mirror 1 of embodiment 17 and embodiment 1 on four positions shown by Fig. 4 into The measurement of row average reflectance, and its measurement is shown in table 15.It learns relative in embodiment 1, according to substrate branch Position and direction on frame and so that reflectivity is had big variation, be used as silicon dioxide layer in the thickness for thickening silverskin (13) In the embodiment 17 of protective film, is not influenced by the position on substrate holder and realized high reflectance.
【Table 15】
Next, using the brass substrate for being shown in Fig. 3, the membrane structure for three types that will be formed in its circular cone inclined-plane is shown In table 11, constant temperature and humidity inspection result will be implemented for these membrane structures and be shown in table 17.The difference of comparative example 17 and embodiment 18 Wei not form the membrane structure of ito film (14), the membrane structure of comparative example 18 do not formed on silverskin (13) ito film (14) with Protective film.
【Table 16】
【Table 17】
No. Embodiment 18 Comparative example 17 Comparative example 18
OH 94.6 96.4 97.5
20H 95.4 96.8 96.0
43H 95.1 96.2 94.9
185H 95.4 96.7 88.0
567H 95.1 96.2 77.8
1407H 95.5 95.2 76.4
Variable quantity
No. Embodiment 18 Comparative example 17 Comparative example 18
0H 0.0 0.0 0.0
20H 0.8 0.4 -1.5
43H 0.4 -0.1 -2.6
185H 0.7 0.3 -9.5
567H 0.5 -0.2 -19.6
1407H 0.9 -1.2 -21.0
Embodiment 18 is the silicon dioxide film for being formed with thickness 20nm as the protective layer in ito film (14), is unable to get The increasing reflecting effect of protective film although in addition learning the light absorption because of ito film, and makes average reflectance be maintained at 95% left side The right side, even if implementing 1000 hours or more constant temperature and moisture tests (experiment C), reflectivity will not reduce.On the other hand, not It forms ito film (14) and is formed in the comparative example 17 of silicon dioxide film, or on silverskin (13) not on silverskin (13) It is formed in the comparative example 18 of protective film, is found that while that the reflectivity at initial stage is high, but reflectivity can be made because of constant temperature and moisture test It is greatly reduced.
High-durability silver mirror 1 about embodiment 1 implements sunlight using the verifying attachment of JIS B7753 defineds Carbon arc formula weather-proof (sunshine carbon weather meter), which is examined, (examines I：Weatherability is promoted to examine).Test condition For：Blackboard temperature is 83 DEG C, in sunlight carbon arc irradiation in 60 minutes spray water within 12 minutes, and the above process repeats to implement 1080 hours.Inspection result is shown in table 18.
【Table 18】
Before inspection After inspection Difference
Embodiment 1 98.5 98.3 -0.1
It is learnt from result, high-durability silver mirror 1 of embodiment 1 has no causes reflectivity to drop because promoting weatherability to examine It is low, there is excellent weatherability.
【Symbol description】
1 high-durability silver mirror
10 glass substrates
11 aluminium oxide
12 nickel
13 silver medals
14 ITO
15 protective layers
16 abrasion performance films
20 brass substrates
151 aluminium oxide
152 silica
153 titanium oxide

Claims (3)

1. a kind of manufacturing method of high-durability silver mirror, wherein sequentially form the oxidation film as first layer on base material, make For the second layer film of metal selected from the metal with face-centered-cubic crystal structure, as third layer silverskin, As the 4th layer of ito film of the thickness in 3~12nm and the protective film as layer 5, it is further carried out at 400~500 DEG C Heat treatment in temperature range between 30~90 minutes, and the average reflectance of high-durability silver mirror is 97% or more.
2. a kind of manufacturing method of high-durability silver mirror, wherein sequentially form the oxidation film as first layer on base material, make For the second layer film of metal selected from the metal with face-centered-cubic crystal structure, as third layer silverskin, As the 4th layer of ito film of the thickness in 3~12nm and the protective film as layer 5, further in the protective film of the layer 5 On, silicon oxide film magnesium fluoride film or this two layers film as abrasion performance film is formed, further it is carried out at 400~ Heat treatment within the temperature range of 500 DEG C between 30~90 minutes, and the average reflectance of high-durability silver mirror is 97% More than.
3. the manufacturing method of high-durability silver mirror as claimed in claim 1 or 2, wherein the base material is glass baseplate or half Conductor substrate.
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