CA1198301A - Selectively light-transmitting laminated structure - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
This invention relates to a selectively light-transmitting laminated structure having various superior properties, which permits transmission of visible light and reflection of heat waves or infrared rays. Specifically, it relates to an improved selectively light-transmitting laminated structure which has improved resistance to light, heat, gases, etc., particularly showing remarkably improved resistance to heat degradation demonstrated by a degradation time of usually at least about 1,000 hours, and frequently more than about 5,000 hours, as a result of providing a layer deposited as a material selected from the group consisting of Ti, Zr, In, Si, C, Co and Ni on the surface of a heat wave-reflective silver-containing metallic layer.

Description

~9~ 7566-706 This invention relates to a selectively light transmitt-ing laminated structure having various superior properties, which permits transmission of visible light and reflection of heat ~aves or infrared rays. Specifically, it relates to an improved selec-tively light-transmitting laminated structure which has improved resistance to light, heat, gases, etc.. particularly showing re markably improved resistance to heat degradation demonstrated by a degradation time (as defined hereinbelow) of usually at least about 1,000 hours, and frequently more than about 5,000, a.s a result of providing a layer deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co on the surface of a heat wave~reflective silver-containing metallic layer.
More specifically, in one aspect this invention provides in a selectively light-transmitting laminated structure composed of (1) a substrate layer (A) of a transparent sheet-like structure,

(2) a heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 A on layer (A),

(3) a transparent thin layer (sl) having a high refractive in-dex between layers (A) and (D), the improvement wherein a thin layer(C~ having a thickness of 3 to 100 ~ and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co is provided in contact with layer (D), on that side of layer (D) which is remote from layer (A). In another aspect the invention provides in a selectively light-transmitting laminated structure composed of (1) a substrate layer (A) of a transparent sheet~like structure, ~g8~3Y3~

(2) a heat wave~reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 A on layer (A), (3) a transparen-t thin layer (B2) having a high refractive index on layer (D), the improvement wherein a thin layer (C) having a thickness of 3 to 100 A and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co is provided in contact with layer (D), on that side of layer (D) which is remo-te from layer (A).
In yet another aspect the invention provides in a selectively light-transmitting laminated structure composed of (1) a substrate layer (A~ of a transparent sheet-like struc-ture, (2) a heat wave~reflective layer (D~ of a silver-containing metal having a thickness of 50 to 300 A on layer (A), (3) a transparent thin layer (Bl~ having a high refractive index between layers (A) and (D~, and a transparent thin layer (B2) having a high refractive index on layer (D), the improvement where-in a thin layer (C) having a thickness of 3 to 100 A and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co is provided in contact with layer (D), on that side of layer (D) which is remote from layer (A).

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A great nurnber of suggestions about a heat wave-reflective or elec-trically conductive laminated structure or the like have been made in many pa-tent documents including UO~O Patents NosO 3698946~ 3962488~
4017661 and 4020~89~ 3apanese Laid-Open Patent Publica-tion NoO 66841/76~ British Paten-t No. 1307642 French Patent No. 2043002, Belgian Patent No. 693528~ ~anadian Patent NoO 840513~ west German O~S NosO 28133947 2828576 and European Patent Application NoO 80302985a Selectively light-transmitting layers are useful as transparent thermal insulating layers because they are transparen-t to light in -the visible region but have the ability to reflect infrared light (including near infrared light)n Accordingly, they can be used in solar energy collectors ~water heaters), power genera-tion by solar energyS wi~dow portions of greenhouses and window portions of refrigerated and cooled showcasesO
In particular, thes~ layers will gain increas-ing importance because of their ability to act as trans-parent heat insulating windows which utilize solar energ~and prevent dissipation of energy in modern buildings in which the windows occupy a larg~ proportion of the wall surfacer ~hey are also important as films for green-houses in agriculture which are used in cultivating 2~ vegetables and fruits.
Thus, the selectively light-transmitting layers are important from the standpoint of the utilization of solar energy, and it is desired in the art to provide large quantities of such films of uniform quality and high performance at low cost~
K~own transparent thin layers of electrically conduative metal disclosed in the above-mentioned patent documents and elasewhere include (i) -thin layer of metals such as gold, copper, silver, and palladium, (ii) thin layer of compound semiconductors such as indium oxide, tin oxide and copper iodide, and (iii) thin layer of electrically conductive metals such as gold, silver, r)~

copper and palladlum which are made selectively trans-parent over a certain wa~elength regionO Indi~n oxide or tin oxide layer having a thickness of several thousand Angstroms and laminates of metallic layer and transparent conductive layer are known to be selectively transparent and have a high ability -to reflec-t infrared radia-tion~
However, transparent electrically conductive film or selectively lig'nt-transmitting film having superior per-formances have not been produced commercially at low costO
The above-cited west German O~S l~o. 281339L~
discloses a -transparent, electrically conductive lamina-ted structure composed of (A) a transparent solid substrate, (B) a thin layer of an oxide of titanium in ~ontact with said substrate (A).
(C) a thin layer of an electrically conductive metal in contact with said layer (B), (D) a thin layer of an oxide of -titarlium in con-tact with said ]ayer (C), and (~) optionally, a transparent top layer in contact with said layer (D), characterized in that (i) said substrate (A) is a film-forming synthetic resin layer, and (ii3 said layer (B) is a layer of an oxide of titanium derived from a layer of an organic titanium compound and containing an organic residual moiety of said organic titanium compoundO
In this patent documentj a uni-tary thin metal layer containing both silver and copper is recommended as a preferred species of the -thin layer (C) of elec-tri-cally conductive metal. In particular, the use of layer (C) composed of Ag and Cu wi-th a Cu conten-t of 1 -to 30%
35 by weight based on the -total weight of Ag and Cu is re~
commendedO
The weYt German O~S 2828576 recommends the use ~9~3.;3~3~.

of a thin layer of a metal selected from gold, silver, copper, aluminum, and mixtures or alloys of at least two of these.
European Patent Application Publication No. 0007224 recommends a heat wave-reflective or electrically conductive lamin-ated structure composed of (A) a shaped solid substrate, (B) a transparent thin layer having a high refractive index in contact with said substrate (A), (C) a transparent heat wave-reflective layer of an electri~
cally condu~tive metal in contact with said layer ~B), and (D) optionally, a transparent thin layer having a high refrac-tive index (D'~ in contact with said layer (C) and transparent top layer (D") in contact with said transparent thin layer (D');
characterized in that said layer (C) is a layer composed of Ag and Au in which the amount of Au is 3 to 30% by weight based on the total weight o~ Ag and Au.
To the best of the knowledge of the present inventors, however, none of the prior literature discloses a heat wave-reflec~
tive or electrically conductive laminated structure having a layer which,is deposited on a heat wave-reflective Ag-containing metallic layer in contact therewith, as a material selected from the group consisting of Ti, Zr, Si, In, C and Co.
The present inventors noted that a selectively light-transmitting laminated structure having a transparent thin layer with a high refractive index provided on a heat wave-reflective Ag-containing metallic layer in contact therewith, such as the one i3~3~

mentioned above, undergoes degradation in perEormance by the influ-ences of heat, light, environmen-tal gases, etc...
Their investigations made in an attempt to overcome this technical difficulty with ease and at low cost have led to the discovery that by providing a thin layer deposited as a material selected from the group consisting of Ti, Zr, Si, In, C and Co on, or both on and beneath, the heat wave-reflective layer of a silver-containing metal, the above technical difficulty due presumably to the surface diffusion of Ag in the heat wave-reflective Ag contain-ing metallic layer which is caused by environmental ~actors suchas heat, light, and gases can be overcome, and a selective:Ly light-transmitting laminated structure having markedly improved environ-mental durability can be produced.
The thin layer of such a material may be formed on -the heat wave-reflective Ag-containing metallic layer by known means such as vacuum deposition and sputtering. It has been found that the material forming this layer should be deposited under conditions which do not convert it to its oxide or other compound as much as possible, and specifically, the thin layer should be deposited as a material selected from the group consisting of Ti, %r, Si, In, C
and Co.
Accordingly, there can be provided a selectively light-transmitting laminated structure which shows various superior properties, and above all, a markedly high resistance to heat degra-dation demonstrated by a degradation time of at least about 1,000 hours, and frequently more than about 5,000 hours, the degradation time being defined as the time which elapses until the infrared 3~3~l reflectance at a wavelength of 9~8 or 10 microns of a sample de-creases to 85% thereof in a degradation test at 90 C.
It is an object of this invention therefore to provide a selectively light-transmitting laminated structure having vari~us improved and superior properties.
The above and other objects and advantages of this invention will become more apparent from the following description.
A laminated structure in accordance with this inventlon is composed of (1) a substrate layer ~A) of a transparent sheet-like structure, (2) a heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 ~ on layer (A), (3~ a transparent thin layer (Bl) having a high refractive index between layers (A) and (D~, and a thin layer (C~ having a thickness of 3 to 100 A and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co in contact with layer (D), on that side of layer (D~ which is remote from layer (A~.
Another laminated structure in accordance wi~h this invention is composed of (1~ a substrate layer ~A~ of a transparent sheet like struc-ture, (2~ a heat wave-reflective layer (D~ of a silver-containing metal having a thickness of 50 to 300 A on layer (A~, (3~ a transparent thin layer (B2~ having a high refractive index on layer (D~, and a thin layer (C~ having a thicknesc of 3 to 100 A and deposited as a material selected from the group consisting '~?g ~38~

of Ti, Zr, In, Si, C and Co in contact with layer (D), on that side of layer (D) which is remote ~rom layer (A).
Yet another laminated structure in accordance with this invention is composed of (1) a substrate layer (A) of a transparent sheet-like struc-ture, (2) a heat wave-reflective layer (D) oE a silver-containing metal having a thickness of 50 to 300 A on layer (A), (3) a transparent thin layer (Bl) having a high refractive index between layer (A) and (D), a transparent thin layer (B2) having a high refractive index on layer (D) and a thin layer (C) having a thickness of 3 to 100 A and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co, in contact with layer (D), on that side of layer (D) which is remote from layer (A).
In one embodiment, an additional layer (C~ may also be formed beneath the layer (D), i.e. on that side of layer (D) which is not remote from layer (A), in contact with layer (D).
One preferred structure has the following layers:
(1~ a substrate layer (A~ of a transparent sheet-like structure;
(2) a heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 A;
(3) a single layer (C) deposited as elemental titanium (Ti) and having a thickness of 25 to 100 A, or said layer (C) on each side of layer (D), said layers (C) having a minimum total thickness of 10 A and a maximum total thickness of 100 A;

- 5b -~L~98~

(4~ at least one transparent thin layer (B~ having a thickness of 50 to 500 A and a high refractive index, said layers being in contact with each other in the order: tA)-(B)-(D~-~C~, (A)-(B)-(D)-(C)-(B), (A)-(D)-(C)-(Bl,(A)-(B)-(C~-(D)-(C), ~A)-(C)-(D)-(C)-(B) or (A)-(B)-(C) -(D~-(C)-(B) and (5~ optionally, a transparent top layer (E~.
Another preferred structure has the following layers:

~8'3~L

(1) a substrate ].ayer (A) of a transparent sheet-like structure;
(2) a heat wave-reElective layer (D) of a silver-containing metal having a thickness of 50 to 300 A;
(~) a layer (C) deposi-ted as elemen-tal zirconium (zr) or elemen-tal carbon and having a thickness of 25 to 100 A, or said layer (C) on each side of layer (D), said layer (C) having a m;nimllm total thickness of 10 A and a maximum total thickness of 100 A;
(~) at least one transparent thin layer (B) having a thickness of 50 to 500 A and a high refractive index, said layers being in contac-t with each other in the order: (A)-(B)-(D)-(C), (A)-(B)-(D)-(C)-(B), (A)-(D)-(C)-(B), (A)-(B)-(C)-(D)-(C), (A)-(C)-(D)-(C)-(B) or (A)-(B)-(C)-(D)-(C)-(B); and (5) optionally, a transparent top layer (E) .
~he substrate layer (A) may be a layer of a shaped solid substra-te made of an organic material, an inorganic material or a combination of -these.
In the present invention, -the te.rm "transparent shee-t-like structure" is meant to include such shapes as films, sheets and plates, and the term "transparent"
also includes a coloured and transparen-t state.
In the substrate layer (A), the organic material is preferably an organic synthetic resin. Specific examples of the resin include theYmoplastic resins such as polyethylene terephthalate, polyethylene naphthalate, poly-carbona-te, acrylic resin, ABS resin, polystyrene, polyace-tal, polyethylene, polypropylene, polyamides, and fluorocarbon resins; thermosetting resins such as epoxy resins, diallyl phthalate resins, silicon resins, unsaturated poly-ester resins, phenolic resins and urea resins; and solvent-soluble resins such as polyvinyl alcohol, polyacrylonitrile, polyurethane, arom~atic - 6a -polyamides, and polyimidesO 'rhese are in -the form of homopolymers or copolymers and may be used ei-ther singly or as a mixture.
The shaped solid substr~te made of an inorganic material rnay, for example, be a shaped article of a vitreous material such as soda glass, borosilicate glass and silicate glass, a metal oxide such as alumina, silica, magnesi~ and zirconia, and semiconductors such as galli~lm-arsenic, indium-phosphorus, silicon and 10 germaniumO
r~he heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 -to 300 A may be a layer of Ag7 or bo-th Ag and ~nother me-tal or metal compound. 5xamples of -the metal or metal compounds which may be presen-t together with Ag are Au, Cu, Al, In, Zn~ and Sn, above all Au and ~u, and -the compounds there-of. For ex~lpie, the layer (D) of the Ag-con-taining metal may be a layer of Ag, a layer of Ag con-taining up to 30% by weight of ~u, a layer of Ag containing up to 20 30/0 by weight of Au~ a layer of Ag con-taining both up to 30,~ by ~Jeight of Cu and up to 30,~ by weight of ~u. I'he ligh-t resistance of the selec-tively ]ight-transmi-tting laminated structure in accordance with this invention may be improved by including Ool -to 30/0 by weight, pre-25 ferably 0~3 to 15% by weight, of ~u in Ago ~he heat resis-tance of -the lamin~ted structure of this invention can be improved by including 3 -to 30~0 by weight of Au in Ago ~he hea-t wave-reflective layer (D) of a silver-containing metal has a thickness of 50 to 300 A, prefer-ably 70 to 200 Ao If the thickness of -the layer (D) is too small below 50 A~ the infrared reflectance and heat resistance of the laminated struc-ture -tend -to be reduced.
If the thickness of the layer (D) is too large beyond 300 A, -the visible light transmittance of -the laminated s-tructure decreases so that it is no longer fea~ible in practical applications.

Known means can be used to form the thin Ag-containing metallic layer (D). E'or example, there can be used a vacuum deposi-tion method, a cathode sputtering method, a plasma flame spraying method, a vapor phase plating method, an electroless plating method, an electroplating method, a chemical coating method, and combinations of these methods.
The layer (C) having a thickness of 3 to 100 A and deposi-ted as a material selected from the group consisting of Ti, Zr, Si, In, C and Co, which is the important feature of the selectively light-transmitting laminated structure of this invention, is formed on the layer (D), or both on and beneath the layer (D), in contact there~ith by means known per se, such as vacuum deposition and cathode sputtering.
At least at this time, the above material is deposited under such conditions that it is not converted as much as possible to its oxide or another compound. A minor degree of oxidation, for example the formation of TiOX where x is less that 1.3, prefer-ably not more than 1, in the case of Ti, may be permissible. It is preferred to choose conditions so that partial oxidation beyond this degree or complete oxidation may not take place. The same can be said with respect to the other materials constituting the layer C. The allowable degree of partial oxidation is for example, MOX where M is a metal and x is less than about 1Ø
The layer (C) deposited as a material selected from the group consisting of Ti, Zr, Si, In, C and Co ~including, of course, a mixture of two or more of these materials) may further contaln a very small amount o:E another metal or metal compound.
The layer (C1 has a thickness of 3 to ll0 ~, preferably l0 to 50 ~. The thickness of the layer C is properly varied depending upon the material which constitute the layer (C), and whether it is provided only on the layer (D) or both on and beneath the layer (D). For example, when the layer (C) is provided only on the layer (Dl in contact therewith, its minimum thickness is preferably 25 ~, especîally 30 ~. When the layer (C) is provided both on and beneath the layer (D) in contact therewith, the total .ninimum thickness of the two layers (C) is preferably l0 ~, especi-ally 15 ~. The thickness of the layer (C1 may also be chosen de-pending upon the type of the material constituting the layer (C).
For example, in the first-mentioned case/ the thickness of the layer (C) may be at least 30 A for Ti, and at leas-t 25 ~ for Si, Co, In, Zr and C. In the latter case, the total thickness may, for example, be at least l0 A for Ti, Si and Zr.
If the thickness of the layer (C~ is too small beyond the above-specified range, there is little effect of improving the durability of the laminated structure. On the other hand, if it is too large beyond l00 A, the transmittance of the laminated structure in the visible region decreases markedly so that the resulting laminated structure is not sufficiently selectively light-transmit-tln~.
When the layer (C) is provided both on and beneath the layer (D), it brings about the advantage that each layer (C~ may have a smaller thickness.

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3~

In the present invention, the transparent thin layer (Bl) and/or ~s2) having a high refractive index is a layer of an oxide of a metal preferably selected from the group consisting of Ti, In, Zn, Sn, Y, Er, Zr, Ce, Ta, Ge and Hf (including mixtures of two or more of thesel, or a layer of ZnS. The refractive index of the layer (Bl) or (B21 is, for example, at least 1.6, preferably at least 1.8, especially preferably at least 2.0, a~d its visible light transmittance is at least 50%, preferably at least 75%.
A thin layer of an oxide of titanium is especially pre-ferred as the layer (B11 and/or (B2).
The thickness of the layer (Bl~ or (B2~ is - 9a -,~

'3~3~

preferably 50 to 500 A~ especially preferab1.y 1~0 to 400 Ao Thicknesses outside -the specified range tend to ca-use a reduc-tion in the visible light transmittqnce o~ the laminated structureO ~he transparent thin lAyer (:B1) and/or (B2) cqn be formed by known means such as sput-tering, ion pla-ting, vacuum deposi~tion, we-t-method co~t-ing, etc.
~ he wet-method c03ting is a process which com-prises co~-ting a solution of c~ metal alcohol?te, etcO, and hydrolyzing -the coa~ing to form a me-tal oxide layer.
For the purpose of this invention, there can be used orgqnometallic compounds7 for example organoti-tana-te compounds such as te~trabutoxy titanate, organozirconate compounds such as ~te~trabutoxyzirconate, organoaluminum compounds such as aluminum tri-sec-bu~toxide, aIld organo-germanium corrlpounds such qs tetr.~butoxy germanium, may be used as a material for forming the metal oxide layerO
These compounds can be used in this invention because the alkoxy group bonded to -the metql atom can be ester-interchanged or polycondensed by known methodsO ~everal.kinds of metal alkoxi~es may be used as mixed or poly-condensed, and in this case, -the metal alkoxides may ha~ve di~ferent metal atoms from each other.
~or example, in the case of organo-ti-tanq-tes taken up as an example of the metal alkoxide, -the alkyl group may, for example, be e~thyl, propyl, isopropyl, butyl, 2-e-thylhexyl7 stearyl, etcO, and a condensate obtained by condensing two or more of -these tetraalkyl titanates may also be usedO Or as stated above, metal alkoxides of difterent meta]s, such as aluminurn, tri-sec-bu-toxide, aluminum tri-iso-propoxide~ te-trabutoxy zirconate and tetrabu-toxy germaniurn may be used as con-densed or mixedO
An organic silicate compound which by itself can only give a film having a low refr~ctive index, such as monomethyltrirnethoxysilane or monoethyl-triP-thoxysilqne, may be mixed in a proportion such tha-t the refractive index of -the en-tire rne-tal oxide layer does no-t decrease beyond 1 D 6O
The layer rnay be formed by dilu-ting the me-tal alkoxide compound or its condensation produc-t or i-ts mixture in a suitable solvent, coa-ting the resulting solution, and drying -the coated layer so as -to ind-uce polymerizationO The solvent used for -this purpose mus-t mee-t certain requirements for solubili-ty in rre-tal alko-xides, boiling points and inertness (the property of not inhibiti~g the crosslinking of the me-tal alkoxides by condensation)O Examples of the solvent include hydro-carbons such as n-heptane and cyclohexane, hydrocarbon mixtures such as ligroin, solven-t naphtha, petroleum benzine and petroleum ether, and mixtures of theseO
Addition of a ca-talyst may be effective in order to promote the formation of a transparent layer having a high refrac-tive index. The ca-talyst may be any which promo-tes the hy~rolysis and condensation of the metal alkoxide, and includes, for example, sodium acetate, potassium ace-ta-te and metal naphthenateS. The mixing of different kinds of me-tal alkoxides is an ef-fective means as the addition of a silicon alkoxide is effec-tive for curing of a titanium alkoxideO
The provision of at least one of -the layers (Bl) and (B2) is essential in -the selectively light--transmitting laminated structure of -this invention. The lamina-ted structure does not necessarily contains only one combination of the layer D and the layer or layers (C), and -two or more such combinations may exis-t in the lamina-ted struct-ure of the inven-tion.
The laminated s-truc-ture of -this invention maJ
fur-ther include a transparent -top layer (~) as an op--tional layer~ The top layer (E) serves -to improve -the surface hardness, light resistance7 gas resis-tance, water resistance, etcD of -the structureD 5xamples of materials which can be used to forrn this -top layer (E) incl-ude organic ma-terials, for example acrylic resins _ 12 -such as polymethyl me-thacryla~e resin, polyacrylonitrile resin, polymethacrylonit.rile resin, polyolefin resins such as polypropylene, silicon resins such as a polymer derived from ethyl silicate, polyes-ter resins, fluorine-containing resins, and inorganic substances such assilicon oxide.
The top layer (E) can be formed by known means such as coating, film-larr.ination and vapor depositionO
T'ne -thickness of -the -top layer (3~ may be chosen properly9 and is, for example, 0O05 to 10 microns, preferably 0 1 to 5 micronsO An underlayer may be provided beneath the top layer in order to improve adhesion~ etcO
The lamina-ted struc-ture of -this invention con-s-tructed as described hereinabove has excellen-t durabi-lity, and can be used advantageously in a wide range of applications for heat wave-reflec-tion by din-t of its hea-t wave-reflecting property, and also in a broad range of electronics applications by din-t of its elec-trical conductivi-tyO
For example, the selective light-transmit-ting laminated structure of this inven-tion may be used as a selectively light~transmi-tting material for the effective utilization of sunlight, and/or as an energy saving ma-terial by u-tilizing i-ts thermal insula-ting proper-tyO
Moreover, it may be used as a -transparen-t electrode for liquid crystal displays, electroluminescence~ a pho-to-conduc-tive photosensitive rraterial, an antistatic layer, and a panel heater by u-tilizing its electro~conductive proper-tyO
By controlling the thickness of the thin metal layer ~) of the A~-containing metal, the thickness of the thin layer (C), and the thickness of the layer (Bl) and/or (B2), and the me-thod of laminating them, the visible li~ht transmittance, surface resis-tance and infrared reflectance of the lar[linated s-tructure of the inven-tion can be freely chan.ged as requiredO
Typical uses of the lamina-ted s-tructure -thus ~ t~

ob-tained include a transparent elec-trical]y conduc-tive laminate in an an~tistatic or photoconductive photosen.siti~e layer, a transparent elec~trode for a solid display or panel il.lumina-tor such as a liquid cr~stal elec~tro-illumi-nator, a transparen-t panel heater as a hea-ter such as a defros-t hea-ter for -the windows of mo-tor vehicles, and a -transparent -thermal insulating lamina-te to be applied to -the glass portions of windowpanes of buildings, green~
houses and refrigerated and cooled showcases.
The selectively ligh-t-transmitting laminated structure of this inven-tion exhibits a visible light transmittance of at least 50% and an average infrared reflectance of at least 70/c, preferably a visible light transmit-tance of at least 60% and an average infrared reflectance of at leas-t 80%O
The following ~xamples illustrate the present invention more specificallyO
All par-ts in these examples are by weigh-t un-less otherwise specified.
The visible ligh-t transmit-tance and the average infrared reflectance of -the laminated s-truc-ture are determined by the following methodsO
Visible light -transmi-t-tance The tr~nsmittance in a visible region of 450 to 700 m~ is measuredO The product of -the transmittance and -the intensity of solar energy is calculated for every 50 mu increment in waveleng-th, and the summa-tion of -the products wi-th the above range is divided by -the total intensi-ty of solar energy a-t ~50 to 700 m~ The quotient obt~ined is defined as -the visible light transmit-tance (o/o) .Average infrared reflectance The infrared reflec-tance was measured by an infrared spectrophotometer (Model EPI-II, manufactured by Hitachi Limited) provided wi.th a reflec-tance meas1lring deviceO
The measuremen-t is carried out in an infrared waveleng-th region of 3 -to 25 I~.m. The energy radiated from ~ black body ~t 300 E (27 C) is rr~.easured for every On2 um incremen-t in wavel.ength, and the produc~t of the radia-tion energy and the infrared reflectance cor responding to -the respective wavelengths is calcula-ted for every 002 llmlincremen-t in waveleng~th~ The summa-tion of -the produc-ts is calculated within the wavelength region of 3 to 25 ~mO The summa-tion of the produc-ts is divided by -the total of the intensities of radiation energy is the wavelength region of 3 to 25 ~mO The quotien-t obtained represents -the average reflectance of -the energy (the wavelength region of 3 to 25 um) radiated from the black body at 300 K~
~he radiation energy in the region of 3 to 25 ~m corresponds to about 8~yG of the en-tire radiation energy of the black body at 300 ~
E~amples 1 to 3 and Comparative 3xamples 1 and 2 A titanium oxide layer having a thickness of 300 A (layer Bl), a layer of an alloy of silver ~-md copper (92% by weight of silv~r and 8% b-y weigh-t of copper) having a thickness of 150 A (layer D), a metallic titanium layer (layer C) and a ti.-tanium oxide layer hav-ing a thickness of 230 ~ (layer B2) were successively laminated to a biaxially oriented polyethylene tereph-thalate film having a light -transmittance of 86% and a -thickness of 50 microns to ob-tain a selec-tively light~
transmi-tting laminated s-truc-tureO
Each of the titanium oxi.de layer was formed by coating from a solution consisting of 3 parts of a tetra-~0 mer of -tetrabutyl titanate and 97 parts of isopropyl alcohol by means of a bar coater and heating -the coa-ted layer a-t 120C for ~ minutesO
The silver-copper alloy layer was formed by DC
sput-tering using a silver copper alloy consisting of 92%
by weigh-t of silver and 8% by weigh-t of copper as a target~
The metallic titanium layer (layer C deposited as Ti) was formed in each of the -thicknesses shown in Table 1 by vacuurn deposi-tion using elec-tron beam heatingO
'rhe selectively ligh-t-trqnsmi-tting laminated structure was pu-t into a hot air dryer kept at 90C to test it for resistQnce -~o .~ccelera-ted hea-t degradationO
The time (hours) which elapsed until the infrared reflec-tance (wavelength 10 microns) of the sample decreased to 85% of the initial. value w.~s defined ~s the degradation timeO
The resul~s of -the tes-t are shown in Table 1 toge-ther with the visible light transmit-tance and average infrared re~lectance before the testO
Comp-lrative ~xample 1 shows the same laminated structure except -that -the layer C W'lS omi-tted~

Table 1 Example Thic~ness ~isible Average Initial Degra-(~xO) or of the light infrared infrared da-tion Compara- metallic trans- reflect- reflec- time tive -ti-tanium mi-ttance ance tance at Example lay-er (C) 10 microns (C5xo ) (A) (%) (/) (/~) (hours) Ex~ 1 40 73 92 92 17 000 ~xO 2 50 73 92 92 1~100 Exo 3 84 70 92 92 1~ ~00 CExo 1 72 92 91 150 CEXD 2 150 L~7 92 92 The-resul-ts given in Table 1 show th~-t the laminated struc-ture has poor heat resistance when i-t does no-t con-tain -the layer C deposited as Ti, and the degra-da-tion -time is very short, ~nd that when -the thickness of the metallic ti-tanium layer exceeds 100 A, the lami-nated s-tructure is not suitable for pr~c-tical applica-tion because of the marked decrease in visible light tr~nsmittanceO

~g~

Examples 4 and 5 and Comparative Examples ~ and 4 A selec-tively ligh-t--t;rarlsmitting l~in,a-ted structure was made in subs-tan-tially the same waty as in Example 1 by laminating a -titanium oxide layer (B1) hav-ing ~ thickness of 300 ~, a layer (D) of an alloy ofsilver an~l copper having a thickness of 150 A, a metallic -titanium layer (C) of each of the thicknesses shown in l'able 2 and a ti-tanium oxide layer (B~) having a thick-ness of 280 ~ successively -to a biaxially oriented poly-ethylene terephthala-te film (layer A).
Each of t'he titanium oxide layers Bl and B2 was forrned by lQw-tempera-tl~re sput-tering using a target molded from a comIQercially available titanium dioxide powder of high purityO A vacuum vessel was evacuated to a high vacuum (5 x 10-6 -torr), and argon gas was intro-duced to a pressure of ~ x 10 3 -torrO Sput-tering was performed in a high freq-uency elec-tric f`ield in the vessel~ The ou-tput of the high frequency sputtering was 500 W, and the distance be-tween the substra-te and the target was adjusted -to 10 cm. ~he titanium oxide layer Rl was formed by performing -the spu-ttering for 20 minutes, and the titani~n oxide layer B2, by performing the sput-tering for 18 m~inu-tesO
~able 2 summarizes t'ne visible light transmit-tance, the average infrared reflectance, -the ini-tial infrared reflectance (10 microns) and the degradation time of the laminated structure in relation to the thickness of the metallic titanium layer C10 ~ J~

T~ble 2 Exarnple Thickness Visible ~verage Initial Degra-(Exo) or of the light infrared i~.frared dation Compara- metallic trans- reflec- re~'lec- time tive titanium mittance tance tance a-t Example layer C 10 microns (CEx~ ) (0~,) (o/,) (0~) (hours) 5xo L~ ~0 73 91 92 1,000 ~x~ 5 78 71 92 91 1,500 ~xO 3 0 73 92 92 120 CExo 4140 L~6 92 9~ _ The results given in Table 2 demons-trate that the laminated structure has poor heat resistance when it does not contain the metallic titanium layer C, and when the thickness of the met~llic titanium layer ex-ceeds 100 ~ the visible ligh-t transmit-tance of the l~minated structure decreases drastically.
Examples 6 and 7 and Comparative ~amples 5 and 6 In a laminated structure obtained by providing a titanium oxide layer (Bl) having a -thickness of` 300 A, a layer (D) of an alloy of silver and copper having a thickness of 150 A (silver 9Z~/c by weight) and a titanium oxide layer (B2) he,ving a -thickness of 280 ~ successively on a biaxially orien-ted polye-thylene terephthalate film (layer A), each of the v~rious metallic titanium layers (C) deposited as Ti was forrned between the silver-copper alloy layer (D) and the titanium oxide layer (Bl) or (B2)o The various proper-ties of the resulting laminated struc-tures were determined, and -the resul-ts are shown in ~able 3O
The titanium oxide l,~yers Bl and B2 were formed ei-ther by -the TBT rmethod from -the tetramer of te-trabutyl titan~te as in ~xamples 1 to 3, or by the sput-tering method as in Ex~nples 4 and 5O

The met~llic ti t~nilun layers C were forrned by vacuum deposi-tion using elec-tron beamsO

Table 3 Com Com-parative p--.rative Example 5 Example 6 ~xample 6 3xample 7 Method of forming sput-ter-sputter- TBT TBT
the Ti oxide ing ing layers Bl ~nd B2 Thick~ under ness of layer D 30 30 35 40 metallic Ti layer On 0 25 0 30 C (A) laye~ D
Visible light transmittance (%) 73 72 71 70 Average infrared reflectance (%) 92 93 92 9 Initial infrared reflectance at 92 93 91 92 10 microns (,~) Degrada-tion time (hours) 3 2,300 200 2,000 Examples 8 to 11 and Cornparative Examples 7 to 9 Example 7 was repeated excep t that a layer of -titanium oxide, zirconium oxide or tan-talum oxide formed by an ion pla-ting method was used as a reflection inhibit-ing layer instead of the titanium oxide film layer formed from the te-tramer of tetr~butyl titan~~te, and -the thick-ness of the layer C deposi-ted as metallic ti-tanium was ch~nged as shown in Table 40 The ion plati.ng was carried out under -the following conditionsO
Oxygen gas p~rtial pressure: 5 x 10 4 torr High-frequency power (13056 MHz) 200 W
The thickness of the reflection inhibiting layer was 300 A in all Examples and Comparative ExamplesO
The results ~re shown in Table 4~

Table 4 Exa7rlple T~igh_ Thic~rless Visible Average Initial Degrad -(Exo) or refractiveOI the Ti light infrared infrared tion time Comparative reflectionlayers C trans' reflec- reflec-Example inhibiting mittance tance tance ~t ( CExo ) 1 ~Iyers Bl 10 -microns and B2 (A) (o/~) (0/5) ( ,~) (hou~s) 3xo 8 Ti oxide 35 73 92 92 2000 Ex~. 9 Ti oxide 60 71 93 92 ~ 3000 ~x~, 10 Zr oxide 40 72 92 93 > 2000 Exo 11 Ta oxide 35 72 92 92 ~2000 C3x~ 7 Ti oxide 0 73 91 92 100 ~9 C3xo 8 Zr oxide 72 92 91 18C
C~xO 9 Ta oxide 0 72 91 92 200 _ 20 -Examples 1~ and 13 rlnd Compc,lr~tive 5x3.rnple~ :l.0 A -titaIliUm oxide layer having a thickness of ~00 ~ (layer Bl), a l,~yer of an alloy of silver ~nd copper having a thickness of 150 A (layer D), a silicon layer (C) deposited as Si and a -ti-tanium oxide film layer having a thickness of 2~0 ~ (layer B2) were successively l~minated to a biaxially orien-ted polyethylene tereph-thalate film having a light transmittance of 86/c and a a thickness of 50 rnicrons (layer A) to obtain ,~ selec--tively light-transmit-ting lamina-ted s-truct-uxeO
The ti-tanium oxide film layer Bl and B2 and the alloy layer D were formed as in Example 1~
The silicon l~yer C was formed in each of the thickness shown in Table 5 by vacuum deposition using electron beam heatingO
The results axe shown in 'lable 5O
Comparative 3xample ~ shows the same lamina-ted structure but not containing the silicon l~yer C~

Table 5 rExample 'rhickness Visible Average Ini-tial Degra-(Ex~) or of the light i.nfrared infrared dation Compara- silicon trans- reflec- reflec- time tivelayermit-tance tance -tance a-t Example(A)(/c~ (/~) 10 m )crolls (hours) Ex~ 1250 71 92 92 1,100 5x~ 1~70 70 92 92 1,500 CEx~10150 47 92 92 The resul-',s given in '~able 5 show that when ',:lre the thickness of the silicon layer exceeds 100 ~, the lamina-ted s-tructure is nct suitable for pxac-tical appli-cation becallse of -the extreme decrease of i-ts visible light transmittance.

3~

Examples 14 and 15 and Compara-ti.ve 5xamples 11 and 12 In substan-tially -the same way as in ~xample 1, a selectively light-transmitting laminated s-tructure was made by lamina-ting a titanium oxide layer B1 having a thickness of 300 ~, a layer D of silver having a -thick-ness of 150 A, a titanium la~er C de~osited as ti-taniurn of each of the various thicknesses shown in ~able 6, and a titanium oxide layer B2 having a thickness of 280 1~
successively to a biaxially oriented polyethylene ~tere-phthala-te film (layer A)o The titanium oxide film layers Bl and B2 were formed in the same way as in Examples lo ~ he resul-ts are shown in ~able 6.

Table 6 Exam~le .hickness Visible Average Initial Degra-(Exo) or of -the light infrared i.nfrared da-tion Compara- titanium trans- reflec- refelec- -time tivelay~r mittance -tance -tance a-t Example 10 microns (CEx,)~A) (/~) (%) (o/) (hours) ~xO 1~ 30 72 91 92 1,200 Exo 15 65 69 92 91 1,800 CExo 11 0 73 92 92 1.80 C~ 12 1~0 46 92 93 ~ he results shown in ~able 6 demonstrate -that -the l.aminated structure has poor heat resistance when it does not contain the ti-tanil~ layer C, and that when -the thickness of the ti-tanium layer C exceeds 100 ~, the visible ligh-t transmi-ttance of the lamina-ted structure decreases drastically.
Examples 16 and 17 In a laminated structure obtained by laminat-ing a titanium oxide layer Bl having a thiGkness of 300 ~, a layer D of an alloy of silver and ~old having a thickness of 150 .OA (92% by weight of silver) and a titanium oxide layer :B2 having a thickness of 280 ~
successively to a biaxially oriented polyethylene tere-phthalate film (layer A), a sil.icon layer G having each of the t~icknesses shown in ~able 7 was formed between the silver-gol-l alloy layer D and each of the titanium oxide film layers Bl ancl B2O ~he results are shown in ~able 7~
The titanium oxide film layers Bl and B2 were formed ei-ther by the TBT method or by the spu-ttering me-thod as in Ex~mples 12 and 13 and 5xamples 14 and 15, respectivelyO
The silicon layer C was formed by vacuum depositing using electron be~ms.

~able 7 æxample 16 hJxample 1 Method of forming the ~i oxide layers Bl and B2 sputtering B~B
~hickness of under ~o 25 tht? Si layer layer C
(A) on layer C 25 ~Q
Visible light trans-~: mittance (%) 7 7 Average infrared reflectance (%) 93 93 Initial infrared reflec--tance at 10 microns (%) 9~ 92 Degradation time (hours) 2,400 2,000 Examples 18 to 21 Example 12 was repeated except -that a layer of titanium oxide, zirconium oxide or -tan-talum oxide formed by an ion pla-ting method was used as a reflec-tion inhibi-tl.ng layer ins-tead of -the titanium oxide layer prepared from the tetramer of tetrabutyl ti-tanate, and -the thick-ness of th~ silicon metal layer was changed as shown in ~able 8O

~3~

rhe ion pla-ting was perforrne(l under -the same conditions as in Example 3O
~ he results are shown in 'rable 8.

Table 8 5x- High-re- Thick- Visible Average Ini-tial Degra-ample fractive ness ligh-t infrared infrared dation laye~S Bl of the trans- reflec- reflect- time B2 layer mittance -tance ance at microns (A) (%) (~/) (0/o) (hours) 13 ~ri oxide 35 73 92 92 1,000 19 Ti oxide60 71 93 92 1,800 Zr oxide35 72 92 93 1,000 21 Tz oxide40 71 92 92 1~000 ~xamples 22 to 24 and Comparative ~xample 13 A titanium oxide layer (B~) havin~ a -thickness of 300 A, a carbon layer (C), a layer (D) of an allvy of silver and copper (9~/~ by weight of silver and 8% by weight of copper) having a thickness of 150 A, a carbon layer (C) and a titanium oxide layer (B2) having a thick-ness of 280 A were laminated successively to a biaxially oriented polyethylene terephthalate film having a ligh-t transmittance of 36% and a thickness of 50 microns (layer A) to obtain a selectively light-transmitting laminated structureO
The ti-tanium oxi(~e layers Bl and B2 and the silver-copper alloy layers were formed in the same way as in Example 120 The layer ~ deposi-ted as carbon was formed by vacuum deposition using elec-tron beam heating, and its thickness was as shown in Table 9O
The results are shown in Table 9 3~9~

Table 9 ~xam le Thickness of Visible ~-verageInitial degra-( 3xo~ or the carbon light infrared infrared dation Compara- layer C ~ trans- reflect- reflect-time -tive ( ) mittance ance ance a-t Example under on 10 (C~x~) layer layer microns D D (~c) (%) (~c)(hours) f3x. 22 15 20 73 92 911,200 Exo 23 35 54 72 91 912,500 Exo 2L~ 65 7 68 91 92~LI~OOO
CExol3 130 120 45 92 92 ~ he results given in Table 9 demonstrate -that when the thickness of the carbon layer C exceeds 100 A, the visible light transmittance of -the laminate~l struc-ture d?creases drasticallyO
Examples 25 -to 27 and Comparative Example lL~
A titanium oxide layer (Bl) having a -thickness o~ 300 ~, a layer (D) of an alloy of silver and copper having a thickness of 150 A, a carbon layer C having the thickness shol~m in ~able 10, and titani~n oxide layer (B2) having a thickness of 280 A were laminated succes-sively to a biaxially oriented polyethylene terephthalate (layer A) in the same way as in ~xample 22 to make a selectively light-transmitting lamina-ted structureO
~he results ~re shown in Table 10~

Tab]e 10 Example 'rhickness ~isible Average Initial Degra-(Exo) or of the light infrared infrar(.?d dation Compara- carbon trans- reflect- reflect- time tivelayer C mi-ttance ance ance a-t .Example 10 microns (CExo)(~) (/c) (/~) (/) (hours) 5x~ 25 30 73 92 92 1 ~ 200 ~xo 2~i60 72 91 92 2~000 Ex. 27 70 71 92 92 3 ~ 900 CEx~ lL~140 4L1 92 92 ~ he resul-ts given in '~able 10 demons-tra-te t'nat the lami.natad structure has poor heat resistance when it does not con-tain the carbon layer C~ and that when the -thickness of the carbon layer C exc(-?eds 100 ~, the visible light transmittance of th? laminated layer decreases drasticallyO
Examples 28 to ~1 5xample 22 was rep?a-ted except -that a layer of titanium oxide, zirconium oxide or tantalum oxide formed by an ion plating me-thod was used as a reflection inhi~
biting layer instead o~ the -titanium oxide layer formed from the tetramer of tetrabutyl titana-te~ and the thick-ness of -the carbon l.ayer was chan~ed as shown in ~able ~ he ion plating was performed under the same condi-tions as in Example 8~
'~he resul-ts are shown in ~able 11.

26 _ Table 11 ~xample ~x~mple Example ~xarnple High-refractive reflection inhibit- ri oxide Ti oxide Zr oxide 'ra oxide ing layers Bl and B2 Thickness of ~ri layer (A) 20 35 30 ~0 Thickn~ss of carbon layer (A) ~rO 5~ L~0 45 Visible light trans-mittance (%) 73 71 70 70 Average infrared reflectance (%) 92 92 92 92 Initial infrared reflectance at 10 92 92 91 92 micro.ns (~) Degradation time 1,600 2,400 2,000 1,800 Exa~,ples 32 to 34 and Comparative ~xamples 1~ and 16 A titanium oxide l~yer (Bl) having a -thickness 0~ ~00 A, a layer (D) of an alloy of silver and copper (95% by weigh-t of silvcr and 5% by weigh-t of copper) havi.ng a thickness of 150 ~ a metallic cobalt layer (C) deposited as Co and a titanium oxide film layer (B2) having a thickness of 280 ~ were successively laminated to a biaxially oriented polyethylene terephthalate film having a light transmittanc~ of 86% and a thickness of 50 microns (layer A) to ob-tain a selec-tively ligrht-transmitting laminated structureO
The -ti-tanium oxide layers Bl and B2 and the silver-copper alloy layer D were formed as in Example 1.
The metallic cobal-t layer C was formed in each of the thicknessessho~n in Table 12-~ vacuu~ deposi~ion using electron beam heating.
The results are shown in Table 120 Table 12 f~xample'~hickness Visible ~verageInitial Degra-(5x,) orof -the Co light infraredinfrared da-tion Compara-layer (C) trans- rr?flect-reflec-t- time tive rrlittance ance ance at ~xample 0 10 microns (C~xo) (h) (%) (~) (~Y~ (hours) Ex~, 32 30 73 91 92 1,000 Exo 33 50 73 92 92 1,100 Ex. 34 84 68 92 92 2,000 C~xO 15 71 92 91 180 CExo 16 150 47 92 92 The results given in Table 12 demons~trate -that the laminated structure has poor heat resistance when it does not cont~in -the metallic cobalt layer C, and that when the thickne ss of -the metallic cobal-t layer C exce-eds 100 ~, the visible light transmittance of the lami-nated structure drasticall~ decreasesO
~xamples 3'~ to 37 and Comparative 5xamples 17 and 18 Example 32 was repeated excep t tha-t metallic nickel was used instead of the metallic cobal-t~ The metallic nickel layer C was formed by -vacuum depo~ition using electron beam heatingO
The thickness of the metallic nickel layers and the results are shown in Table 130 r~
- 2~ -Table 13 5xampleThickness Visible Average Initial Deg~rcl-( ~xO) orof the light infrared infrared dati.on Compara-Ni layer trans- reflect- reflect- time tive mi-ttance ance ance at ~xample 0 10 microns x ) (~) (0~) (0~) (0/o) (.hours) Ex, 35 ~ 71 92 91 1,100 EXD 36 50 71 91 92 1, 600 Exo 37 80 67 92 92 3,000 CExo 17 72 92 91 150 CEx. 18150 44 92 92 The resul ts given in Tcable 13 demonstrate that the lamin~ted structure has poor heat resi.stance when it does not contain the metallic nickel layer C, and the degradation time is very short, and tha-t when -the -thick-ness of the me tallic nickel layer C exceeds 100 ~, the visible ligh-t transmittance of the lamina-ted structure decreases drastically to render it infeasible in prac-tical applicationO
Examples 38 to 41 ~nd Comparative .!3xamples 19 to 21 In substantially the same away as in 5xample 32, a titanium oxide layer (Bl) having a thickness of 300 A. a layer of an alloy of silver ~nd co-pper having a thickness of 150 A, a metallic cobalt or nickel layer C deposited as Co or Ni having each of the thicknesses shown in Table 14 and a titanium oxide layer B2 having a thickness of 280 ~ were successively lamina-ted to a biaxially oriented polye-thylene -terephthalate film (layer A) -to make a selectivelv light-transmit-ting lamin~ted structureO
The titanium oxide film layers Bl and B2 were :Eormed in the same way as in ~xamples 4 and 50 The resul-ts are shown in Table 140 ~able 1~l-3xample Metallic layer Visible Average Ini-tial Degra-( EXD ) or light infrared infrared dation Compar~- M ~ Th` k trans- reflect- reflec-t- time tivee~al neScs ~ mittance ance ~nce at Example 0 10 (C~xO) (A) micrc,ns (o/) (o/~) (/~) (hours) Ex~ 38Cobalt 40 71 91 921,400 EX. 39Cobal-t 78 68 92 912 ~ GOO
Xo 40Nickel 35 71 92 921 ~ 300 ~xa 41Nickel 60 70 92 921~ 800 CExo 19 ~ - 7 3 92 92110 C~X~ 20Cobalt140 4~ 92 93 CExo 21~ickel130 44 92 92 ~ rhe results shown in rrable 14 demonstrate -that the laminated s-tructure h~s poor heat resis-tance when i-t does not contain the metallic cobalt or nickel layer C, and tha-t when the -thickness of -the met~llic cobal-t or nickel layer C exceeds 100 A, the visible ligh-t trans-mittance of -the larlinated struc-ture decreases drastically, Examples 42 to 45 In a l~minated structur~ obtained by laminating a titanium oxide layer Bl having a thickness o~ 300 A, a layer D of an alloy of silver and copper (92/0 by weigh-t of silver), and a -titanium oxide layer B2 having a thickness of 280 A to a biaxi~lly orien-ted polye-thylene terephthalate film (layer A), a metallic cobalt or metallic nickel layer C was pro-vided between -the silver-copper alloy layer D and each of the ti-tanium oxide layers Bl and B2O
rhe -ti-~anium oxide film layers Bl and B2 were formed either by the rrBrr method as in Example 32 or by -the spu-ttering method as in Example 38.

~9~ J~

The metallic cobal-t layer and -the me-tallic nickel layer C were provided by vacuum deposition using electron beamsO
The resul-ts are shown in Table 15O

Table 15 Example 5xample. ~xample Example`
i 42 43 4L~ 45 Method of forming Sputter- Sputter- TBT ~BT
the Ti oxide layers ing ing Metallic layer on the 1ayer D
Metal Co Ni Co Ni Thickness (~) 30 35 30 35 Metallic layer under the la~er D
Metal Co Ni Co Ni Thickness (~ 50 50 45 5 Visible light transmittance (~O) 72 70 71 70 Average infrared reflectance (k) 92 92 92 92 Initial infrared reflectance at 10 microns (%) 92 92 91 92 Degradation -time (hours) 2~800 2,700 2,600 ~,000 ~xamples 46 to 49 and Comparative 5xamplss 22 to 24 ~ xample 32 was repeated except that a layer of titaniu~ oxide, zirconium oxide or tantalum oxide formed by an ion plating method was used as a reflection in-hibiting layer instead of the -titanium oxide layer pre-pared from the -tetramer of tetrabutyl titanate, and the thickness of the metallic cobal-t or me-tallic nickel layer was changed as sho~m in Table 16O
The ion p]ating was performed under -the same conditions as in Example 8 o The results are sho~ in Table 16 Table 16 Example ~igh- Metallic la~er Visible Average lnitial Degra-(Exo) or refractive m~tal thickness light infrared infrared dation Comparative reflection ~ trajns- reflect- reflect- time 3xample inhibiting mittance ance ance at (CExo ) layer 10 O microns (A)(%) (U/c) (~/o)(~ours) 3xo 46 Ti oxidd Co 40 73 92 921,400 Exo 47 Ti oxide Ni 50 71 93 921,800 Exo 48 Zr oxide Co 35 72 92 93l,OOC
~x~ 49 Ta oxide Co 35 71 92 9219 000 CEx. 22 Ti oxide - - 73 91 92 90 CExo 2~ Zr oxide - - 72 92 91180 C~
CExo 24 Ta oxide - - 72 91 92190 æ

3~

~xamples 50 to 57, A laminated s-truc-ture was produced in -the same way as in ~x~mple 7 except that the titani-um oxide layers obtained by -the TBrr method as the layers Bl and B2 were changed to zirconium oxide thin layers prepared from tetrabutoxy zirconate, and the layer D of an allov of si.lver and copper was changed -to a layer of silver alone, a silver-gold alloy or a silver-copper alloy having a thickness of 160 Ao ~he zirconium oxide layer was pro-vided by coa-t-ing from a solution consisting of 7 par-ts of tetrabutoxy ~irconate, ~0 parts of n-hexane, 20 parts of ligroin and 33 parts of n-butanol, and drying -the coating at 130C
for 5 minutesO
The silver layer, silver-gold alloy layer and silver-copper alloy layer were provided by DC sputtering using silver or a silver-gold alloy (90/. by weigh-t of silver and 10% by weight of gold) or a silver-copper alloy (92% by weight of silver and 8% by weight of copper) as a targetu r~he resu].ts are shown in ~able 170 ~able 17 ~xample Example Example Example Layer D Ag-Cu Ag Ag-Au Ag-Cu Metallic ti-tanium layer (-thickness ~) beneath the layer D 20 25 15 0 on the layer D 30 30 30 30 Visible trans-mittance (/c) 65 64 62 63 Average infrared reflectarlce (/0)92 93 92 92 Infrared reflectance ~fo) 92 92 92 91 Degradation -time (hours) 2,000 1,800>2,000 1,500 ~3~

Exarnples 54 to ~8 and Comparative :Exarnple 25 A laminated struc-ture was produced in the same way as in Exc~mple 7 except that the layers ~ and -the layers Bl and B2 were forme~ as shown in ~able 180 A
transparen-t top layer (E) having a thickness of 2 microns was formed on ~the surface of the laminated layer by wet-method coating from a solution of polyacrylo-nitrile in cyclohexaIlonen The properties of the resul-ting lamina-ted structures are shown in rable 18.

~9~

,~ o o o o o o c g o 8 ~ 8 8 r a~
~ ~ ~1 o ~ ~ ~ u~
d ~ A

~) I ~ U~
~D 4 ~ (D h co C~ (S\ 00 ~ Ci~
t I t~ c2 o r ~ a ~ o~ ~1 H h ~tS
~ I
a) D4 h ~ H c~~ C~ ~~ C~ C~ C~
aD t~ c~, c) ~
~ ~ aD S:~
<r,.rl h ~
o a~ c) ,D 4 U2 ~$ ~ O CO ~ ~ ~) rl ,~ r~ 4 ~ ;~; ~ Ll'~ ~ D ~ L
U2 ~0 ~ 4 ~rl~rl h-ri ~~ r~ 4 ~;
rl aD aD aD
~ 4 r~ 4 a~ o u\ ~ o Lr~ o o~ ~ r(~ ~ ~ Lr t~ , ~ ~s O O r~ ~1 U2 h d P l rd ~ r-la~ (D O 1~\ o o U\ 1 rl~ (D ~, OJ r~~J r~\ N`
,5~ rl aD ,~ ~S
F~ ~1 ~ ~ r-l a~ u2 u2u2 u2 t~ a~ o ~J aD a~ o ~1 ~
U~ U2 U2 U2 u2 ~, Q,` a~ o G` Q) C~
~ r~
,~ a~
a) Gi o ~1$ ~D ~Lr~ C0 r- ~ H ~ Lr~ Ll~ Ll~\ L(\ 1 ~ X 1 ~S ~
u r~ v ~ F~
6~ r~

~xarr~les ~9 and 60 ~ laminatecl structure was proclucecl in -the same way as in 3xarnple 7 except that the -thickness of the metallic titani.um layers C were changed as shown in ~able 190 rhe properties of the laminatecl struc-tures are shown in rable 19.

~able 19 Example Thickness of the Visible Infrared Degra-metallic titanium light reflec-t- da-tion layer C (A) -trans- ance -tirne beneath on t~le mittance the layer layer D D (o/O) (o/~) (hours) 59 ~0 55 70 92 > 3~000 7 67 92 ~51000

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In a selectively light-transmitting laminated structure composed of (1) a substrate layer (A) of a transparent sheet like struc-ture, (2) a heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 .ANG. on layer (A), (3) a transparent thin layer (B1) having a high refractive index between layers (A) and (D), the improvement wherein a thin layer (C) having a thickness of 3 to 100 .ANG. and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C
and Co is provided in contact with layer (D), on that side of layer (D) which is remote from layer (A).

2. In a selectively light-transmitting laminated structure composed of (1) a substrate layer (A) of a transparent sheet-like struc-ture, (2) a heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 .ANG. on layer (A), (3) a transparent thin layer (B2) having a high refractive index on layer (D), the improvement wherein a thin layer (C) having a thickness of 3 to 100 .ANG. and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co is provided in contact with layer (D), on that side of layer (3) which is remote from layer (A).

3. In a selectively light-transmitting laminated structure composed of (1) a substrate layer (A) of a transparent sheet-like struc-ture, (2) a heat wave-reflective layer (D) of a silver-containing metal having a thickness of 50 to 300 .ANG. on layer (A), (3) a transparent thin layer (B1) having a high refractive index between layers (A) and (D), and a transparent thin layer (B2) having a high refractive index on layer (D), the improvement where-in a thin layer (C) having a thickness of 3 to 100 .ANG. and deposited as a material selected from the group consisting of Ti, Zr, In, Si, C and Co is provided in contact with layer (D), on that side of layer (D) which is remote from layer (A).

4. The laminated structure of claim 1, 2 or 3 wherein a transparent top layer (E) is present.

5. The laminated structure of claim 1, 2 or 3 wherein an additional layer (C) is provided beneath the layer (D) in contact therewith.

6. The laminated structure of claim 1, 2 or 3 wherein the layer (D) is a layer of Ag, a layer of Ag containing up to 30% by weight of Cu, or a layer of Ag containing up to 30% by weight of Au.

7. The laminated structure of claim 1; 2 or 3 wherein one or both of the layers (B1) and (B2) is a layer of an oxide of a metal selected from the group consisting of Ti, In, Zn, Sn, Y, Er, Zr, Ce, Ta and Hf or a layer of Zns.

8. The laminated structure of claim 1, 2 or 3 wherein one or both of the layers (B1) and (B2) is a thin layer of an oxide of titanium derived from a layer of an organic titanium compound and containing an organic residual moiety of the organic titanium compound.

9. The laminated structure of claim 1, 2 or 3 wherein one or both of the layers (B1) and (B2) has a thickness of 50 to 500 .ANG..

10. The laminated structure of claim 1, 2 or 3 wherein the minimum thickness of the layer (C) is 25 .ANG..

11. The laminated structure of claim 1, 2 or 3 wherein an additional layer (C) is provided in contact with the layer (D) between layer (D) and layer (A) and the total minimum thickness of the two layers (C) is 10 .ANG..

12. The laminated structure of claim 1, 2 or 3 which has a visible light transmittance of at least 50% and an average in-frared reflectance of at least 70%.