JPS5981161A - Selective light transmitting film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to selectively transparent (light here refers to all visible light, including ultraviolet and infrared light) or conductive multilayer sheet materials. More particularly, the present invention relates to a selectively transparent or electrically conductive film and a pre-layerable, self-sustaining, flexible laminate structure made using the same.

BACKGROUND ART In recent years, selective light transmitting films, such as heat ray reflective films and solar control films, have been actively researched and developed in order to save energy for heating and cooling by applying them to windows of buildings. U.S. Patent No. 4i166,876, U.S. Patent No. 4,2
No. 26,910 and No. 4,234,654 disclose such selective light transmitting films.

Furthermore, in U.S. Pat. No. 3,718,535, a flexible plastic film is prepared in a safety glass mold (i.e., by forming a laminate between hard transparent insulating plates such as glass or polymethyl methacrylate). Windows, aircraft canopy.

It is pointed out that it is known that windbreaks can significantly increase the crushing resistance of glass and the like. Furthermore, it has been proposed to make a safety glass type boxing device by making the safety glass type structure electrically conductive by applying a film having a conductive metal thin film on one or both sides.

U.S. Patent No. 3.7 '18,535, U.S. Patent No. 3.8 i
No. 6.201, No. 3.962,488 and No. 4.1117,661 contain such safety glass molds 1.
A d removal device is disclosed. Further, British Patent Publication No. 1,586,889 and Japanese Unexamined Patent Publication No. 56-32352 propose using a heat ray reflective film to form a safety glass type structure.

By the way, there is no way to create a functional safety glass structure by laminating a functional film with functions such as heat ray reflection ability, solar control ability, or light guiding ability in a safety glass structure. It is necessary that the presence of the film does not reduce the crushing resistance, and furthermore it is necessary that the appearance is not impaired thereby.

As a result of intensive research to achieve the above object, the present inventors have found that by reducing the thickness of the functional film, the glass-type structure can be safely broken even in the presence of the functional film. It was found that the resistance did not decrease and the fit was improved when applied to curved laminated glass. However, when the thickness of the base film was reduced, TfE
Wrinkles occur in the film in the Jj adult, which deteriorates the transparency of the safety glass type structure and causes distortion of the reflected image.
It was found that the appearance became abrupt, thus reducing the commercial value of the 4'1# adults. Therefore, the present inventors conducted various studies in order to obtain a functional film that does not cause this deterioration in appearance, and as a result, they arrived at the present invention.

SUMMARY OF THE INVENTION According to the present invention, a self-contained selectively transparent or conductive film (hereinafter often referred to as arsenide film) is obtained; namely: (1) a transparent polymeric film having a thickness of less than 125 μm; and (2) a selectively transparent or conductive thin film supported on one or both sides of the support film, and the thermal shrinkage rate of the functionalized film satisfies the following formula: 4.4 ≧E≧0.00028 X (d −128)”
d<125 Additionally, the present invention provides a preformed self-supporting material that is defined in two dimensions (i.e., length and width substantially greater than thickness) and is transparent when the outer surface is flat and free of irregularities. A flexible fiit161 structure is obtained and its composition is as follows: (1) The selectively transparent or conductive film described above (
(i.e., a functionalized film), and (11) a film having a thickness of o, 001, which is attached to the surface of the selectively transparent or conductive thin film on the support film, and the blank surface opposite to this attachment surface is the outer surface. The laminated structure is sandwiched between hard transparent layers and further laminated to form a safety glass type structure.

The selectively transparent or conductive film of the present invention has the property of shrinking upon application of heat, whether via a preformed self-supporting flexible laminate structure or individually. The safety glass 7 also promises good crush resistance and an excellent appearance when used in the production of mold structures.

The preformed self-supporting flexible laminate structure of the present invention promises the above-mentioned advantages and is a very convenient intermediate step in the production of safety glass-type constructions. .

The various advantages of the present invention will become more apparent from the following detailed description and accompanying figures (not to scale); FIG. FIG. 2 is a cross-sectional view of a preformed self-supporting potable area Ai1 structure made in accordance with one embodiment of the present invention.

FIG. 1 shows a selectively transparent or electrically conductive thin film 2 attached to the surface of the support film. The thin film 2 shown in FIG. 1 is of a two-layer type consisting of a metal layer 3 and a dielectric layer 4.

Many proposals have been made regarding selective light transmitting thin films or conductive thin films. W in the old days in 1953,
Vacuum 3 by H. Colbert et al.

This can be traced back to the sandwich structure in which a metal is sandwiched between aluminum oxide layers, which was proposed in 375. Since then, various structures have been developed, not only the sandwich structure described above but also a single metal layer or a combination of a metal layer and a dielectric layer. A type has been proposed.

In addition, a metal oxide layer such as indium, tin, or oxide can be used as a thin film that transmits selective light by itself, or as a conductive film. Various proposals have been made.

The thickness of these coatings generally ranges from 50A to 5,00A.
It is 0A. The present invention generally encompasses all such types of selectively transparent or 2# conductive coatings. However, according to our research, the following are desirable; for example: gold, silver, silk, aluminum.

Examples include a thin film of nickel, chromium, palladium, tin, alloys thereof, or mixtures thereof, or a thin film of these metals with a dielectric layer on one or both sides. Such dielectric layers include, for example, titanium oxide, bismuth oxide, zinc sulfide, tungsten oxide,
Indium oxide, zirconium oxide, silicon oxide, etc. are praised. Furthermore, one side or both sides of the above-mentioned gold J, 4 wI, thickness 5X ~ of KTi, Zr, St, C, etc.
A 50X protective layer can also be provided.

When the selective light-transmitting or conductive film is used for safety glass used in building windows, vehicle windows, etc., it can be used to improve the heat ray reflection ability of the window without losing the original brightness of the window. gold, silver, copper, and nickel.

Titanium oxide, bismuth oxide, tungsten oxide, indium oxide, zirconium oxide on one or both sides of a thin film of chromium metal or alloy.

A system in which one or more layers of a mixture selected from the group consisting of silicon oxide are laminated is preferably used. In particular, 41
: Safety glass used for vehicle windows must have a visible light transmittance of 70 coefficients or higher, and in addition to having a high degree of thermal sand reflection and light adjustment ability, it is also required to have a high degree of selective light transmittance.

For this purpose, 1141i or more selected from the group of titanium oxide, tungsten oxide, indium oxide, and zirconium oxide are coated on one or both sides of a thin film of gold hi selected from the group of silver, gold, and copper or an alloy thereof. A system in which I-fields of a mixture of the above are laminated is particularly preferably selected.

Among these, systems in which the metal layer of the above-mentioned systems is protected on one or both sides with a layer deposited in the form of titanium or zirconium are more preferably selected.

In the present invention, the selectively transparent or conductive coating described above is supported on a support film such as a transparent polymer film having specific properties, such as a polyethylene terephthanate film. The above-mentioned specific property means that the support film, when measured in the form of a functionalized film, satisfies the following formula in the relationship between its thickness and heat shrinkage rate: 4.4≧E≧0. 00028 X (d -128)!
d(125 A more preferable range for achieving the above effect is a range expressed by the following formula: 3.9≧E≧0.0O028X(d-130)'d(1
Safety glass-type structures made using selectively transparent or conductive films that satisfy the nine conditions listed in Section 2 of 25 exhibit the following surprising effects: (1) Because the functionalized film is thin. The crushing resistance decreases at ℃・.

(2) Because the functionalized film has a moderate heat shrinkage rate, the minute wrinkles that inevitably occur when creating a safety glass-type construct by combining an interlayer film and a hard transparent layer will be avoided in the construct. Under manufacturing conditions (for example, if the interlayer film is a polyvinyl butyral film, 90 to 150°C
, 5-20 kg/d, lo minutes to 1 hour) and disappear due to shrinkage of the functionalized film.

As mentioned above, one of the major features of the present invention is that the selectively transparent or conductive film has heat shrinkability, but if the heat shrinkage is too large, it will be too difficult to make a safety glass type laminate. Also, the aphrodisiacs will be greatly astringent, and the selective light transmittance or conductive coating will be destroyed.

Such selectively transparent or conductive films may include, for example,
U.S. Pat. No. 946, No. 3
, No. 962,488, No. 4,017,661, @
No. 4,166,876.

British Patent No. 4,234,654, British Patent No. 1,230,4
No. 25, No. 1,364.712, European Patent Publication (E
european patent publication
n) applying the metal layer and/or by physical vapor deposition and/or mixed coating methods as disclosed in A635906;
Alternatively, it can be manufactured by forming dielectric layers in an appropriate combination.

At this time, since the support film has heat shrinkability, it is necessary to protect the support film from being exposed to high temperatures for a long period of time during or after production of the functionalized film.

The preferred film configuration described above is a preferred embodiment of the present invention also from the viewpoint of ease of manufacture.

Although there are no limitations on the use of the selective light transmitting or conductive film obtained by the present invention, the 4F characteristics suggest that
It is particularly suitable for use in expansion windows such as those disclosed in '548 and safety glazier constructions such as those described above, particularly the latter construction. In order to make a safety glass type tank assembly using the above film, the above film/interlayer film and the hard transparent layer may be combined independently, but for convenience of manufacturing, the above film/film may be used in advance Preferably, the preformed self-supporting flexible laminate structure is formed by laminating and integrating the interlayer film and the interlayer film. The second aspect of the present invention, namely the preformed self-supporting flexible laminate structure, will now be described.

FIG. 2 shows a selectively transparent or conductive film 5,
The film 10.10' is shown attached to the selectively transparent or conductive thin film 7 (1!l) of the support film 6.

Although the embodiment shown in FIG. 2 is one embodiment of the present invention and shows a more multilayered system, it goes without saying that the present invention is not limited to this. The selectively transparent or conductive film 5 shown in FIG. 2 has a selectively transparent or conductive thin film 7 made of a metal layer 8 and a dielectric layer 9 on the support film 6 described above. The selectively transparent or conductive film 5 is sandwiched between interlayer films 10 and 10' on both sides. An adhesive layer 11 is provided between the interlayer film 10' and the support film 6 to ensure adhesion therebetween.

As the interlayer film, those conventionally known in the safety glass art, such as the polyvinyl butyral film disclosed in U.S. Pat. No. 3,718,535, can be used. Usually, the thickness is 0.01 nm to 1 nm, more preferably 0.1 nm to 0.9 ynm.

It is preferable that this l-space film has a low heat shrinkage rate, and it is also preferable that the heat shrinkage rate is low in either of the two orthogonal directions.

The preferable range of heat shrinkage is in the longitudinal direction.

In both horizontal directions, it is only about xo% at most,
More preferably, it is at most 5 inches, particularly preferably 3 inches or less.

Commercially available interlayer films, such as polyvinyl butyral films, have a fairly large unidirectional heat shrinkage.
Moreover, it has non-uniformity in that it undergoes thermal expansion in the direction perpendicular to it (-°C.), so it is not preferable to use the momme as it is in the present invention.

When a polyvinyl butyral film is used in the present invention, it must be heat-treated in advance to improve its properties so that it satisfies the above conditions.

Furthermore, when polyvinyl butyral film is used as an interlayer film for safety glass, both sides are necessarily embossed to give it a patterned appearance, for example. However, when the interlayer film used in the present invention, such as a polyvinyl butyral film, is used to make a safety glass type host, one or both sides attached to a selectively transparent or conductive thin film are selectively transparent or conductive. In principle, it is preferable that the surface be flat and free from irregularities before being integrated with the film.

If it is not flat, the roughness of the interlayer film surface will adversely affect the selective light transmission or conductive thin film and detract from the appearance of the ultimately formed safety glass type structure.

If the film is flat and has no irregularities, the two films can be laminated under high temperature and pressure. This has the advantage that the adhesion at the interface increases when

As shown in FIG. 2, the present invention includes a preferable embodiment in which a selectively transparent or conductive film is sandwiched between a first interlayer film IO and a second interlayer film 10'. Preferably, a suitable adhesive layer 11 is provided between the high-temperature film 10' and the support film 6.

As such an adhesive layer, those well known to those skilled in the art can be used, such as metals such as titanium oxide or zirconium oxide obtained by coating and hydrolyzing a fully bent alkoxide such as tetrabutyl handanate or tetrabutoxy zirconate. It is better to use a thin layer of oxide. The thickness of the adhesive layer is usually 50X to 1.0
00X, preferably 100X to 500X.

The surface of the second interlayer film on the supporting film side does not necessarily need to be flat before forming the self-supporting flexible laminate structure, but it is better to have it flat and without any unevenness for better contact. It is preferable in terms of improvement.

By the above method, the interface between the first interlayer film and the selectively transparent or conductive thin film! Both the fitting force and the interfacial adhesive force between the second interlayer film and the support film can be significantly increased. Adhesion strength is 20. V/cIIL or higher, particularly preferably at least 509/crr
It is L.

Thus, preferred configurations of the preformed self-supporting flexible laminate structure of the present invention include the following.

(1) PVB/PET/l&titanium chloride/Ag-Cu
/Titanium nide/PVB (2) PVB /Titanium oxide/PET/Ti/
Ag-Cu/Ti/Titanium oxide/PVB (31P V Il /Titanium oxide 7P E T/Ag
-Au/Mixture of zirconium oxide and silicon oxide/PVB
(41PVB/Titanium oxide/PET/indi
um tin oxide /Ag / indium
tin oxble / PV B (51PV
B / titanium oxide / f' ET / Au /le
Titanium chloride/VB *deposited as weight The preformed self-supporting flexible laminate structure described above is generally deposited onto the selectively transparent or conductive film at a relatively low temperature e.g. 20°C to 100°C It can be obtained by pressing an interlayer film such as a polyvinyl butyral film.

It can also be obtained by forming an interlayer film such as a polyvinyl butyral film using an extruder, overlaying it on a selectively transparent or conductive film, and embossing the outer surface if necessary.

1 in the longitudinal direction and in the perpendicular direction, respectively, onto the support film sample with the selectively transparent thin film.

Mark at intervals of a. Next, the sample was placed in a heating furnace for 120 minutes.
After keeping it at ℃ for 30 minutes, take it out from the furnace and let it cool to room temperature.
Measure m and find the heat shrinkage rate E using the following formula: 1iff an interlayer film on a polyethylene terephthalate sheet whose surface has been treated with silicone oil in advance.
i, and on top of this, L in the vertical direction and in the direction perpendicular to it, respectively.
Mark at l, CIn intervals. Next, the polyethylene terephthalate sheet with this interlayer film placed on it was placed in a heating furnace and heated at 70°C for 30 minutes, then taken out from the furnace and allowed to cool to room temperature, and the interval after heating Lσ of the mark made before heating was determined. Double-width ICFI to calculate the heat shrinkage rate using the formula
L, a piece of the laminated structure with a length of 10 cWL was tested using a tensile tester (A
STMD-882-67). The end of the support film of the structure is fixed, and the end of the interlayer film is pulled in the opposite direction from the support film fixing point at a speed of K 2 cm/sec to determine the adhesive force (J//) between the support film and the interlayer film. crn).

Example 1 A biaxially stretched polyethylene terephthalate film with a thickness of 100 μm was used as a substrate, and on it a titanium layer with a thickness of IOA as the first layer, a silver-copper alloy layer with a thickness of 120A as the 21st (4) layer, and a 120A silver-copper alloy layer as the third layer. A titanium layer of A and a titanium oxide layer of 200A as a fourth layer were sequentially laminated to produce a selective light transmitting and electrically conductive film.

The polyethylene terephthalate film used here as a substrate had a 200A titanium oxide layer attached to one side in advance, and the first to fourth layers described above were laminated on the opposite side.

The titanium oxide layer contains tetrabutyl titanate in a ratio of 5:ff1
A solution containing J11, consisting of 2 parts of n-hexane and 1 part of n-butanol was applied using a bar coater and dried at 70° C. for 5 minutes to form a sample. Further, the fourth titanium oxide layer was also formed by the same method.

The 11th and 3rd layers are made of titanium metal target under argon gas pressure of 2. D while cooling the substrate film with -10"C refrigerant at OX 10""' Torr.
It was formed by C magnetron sputtering. In addition, the second silver-copper alloy layer uses a silver metal target containing 10% by weight of copper, and the substrate film is cooled with a refrigerant of -IQ'' (, D
It was formed by C magnetron sputtering.

The heat shrinkage rate of the laminated film thus obtained is in the transverse direction (T
D) 0.8 inch, longitudinal direction (MD) 0.8 inch.

Next, polyvinyl butyral sheets having a thickness of 0.38 μm were laminated on both sides of the laminated film to obtain a laminated structure.

The polyvinyl butyral used here has a heat shrinkage rate of MD
1. t%, TD 2. One side of the cup was completely flat and the other side was embossed. For the laminated wooden structure m1lk, the flattened surface and the laminated film were laminated.

In the laminated structure obtained in this way, the adhesive strength between the polyvinyl butyral sheet and the laminated film was a4o.
m/cm.

Subsequently, flat glass having a thickness of 2 μm was further laminated on both sides of the laminated structure, and the whole was placed in a rubber bag. The rubber bag was held horizontally and evacuated for 5 minutes, and then held at a temperature of 90° C. for 30 minutes. Remove the glass laminate sandwiching the laminate structure from the rubber bag and place it in an autoclave at a temperature of 1.
A laminated glass was produced by holding at 20° C. and a pressure of 4 kglcrl·G for about 3θ minutes.

The thus obtained laminated glass had a visible light transmittance of 73% and a solar energy transmittance of 58%.

In addition, a laminated window sample with good transparency and a uniform reflected image with no unevenness was obtained. Note that the curved laminated glass produced by laminating glass having a radius of curvature of 3crIL and a thickness of 2III+ on both sides of the above-mentioned laminated structure and operating in exactly the same manner as above had a good appearance as well. The heat shrinkage rate of a selectively transparent and conductive film obtained by using a polyethylene terephthalate film with a thickness of 12 μm instead of 100 μm is 'pl)
5.0%, MD 4.5%. A laminated glass produced using this laminated film using the same polyvinyl butyral sheet as in Example 1 and following the same procedure as in Example 1 did not show unevenness in the reflected image, but there were many small cracks in the sandwiched film. It was observed.

Comparative Example 2 The heat shrinkage rate of a selectively transparent and conductive film obtained by using a polyethylene terephthalate film with a thickness of 25 μm instead of 100 μm in Example 1 was TD 2
．． 0%, MD 1.6%. A laminated glass produced using this laminated film in exactly the same manner as in Example 1 had poor visibility and many irregularities occurred in the reflected image.

Comparative Example 3 In Example IVc, the thickness was 175 μm instead of 100 μm.
The heat shrinkage rate of the selective light transmitting and conductive film obtained using the polyethylene terephthalate film of m is TD
o, tchi, MD O, 01ch. A laminated glass produced using this laminated film in the same manner as in Example 1 had a visible light transmittance of 70% and a solar energy transmittance of 5.
It was 5chi. The laminated glass made of flat glass had a good appearance, but the appearance of the curved laminated glass made of glass with the same radius of curvature as in Example 1 had poor transparency.
Due to defects, one reflected image was distorted and many cracks were observed on the sandwiched film surface.

Example 2 As in Example 1, a titanium oxide layer made of tetrabutyl titanate and having a thickness of 300 A was formed on one side of a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm. On the other side of the polyethylene terephthalate film on which the titanium oxide layer is not formed, a titanium oxide layer with a thickness of 250X as a first layer, and a titanium oxide layer with a thickness of 250X as a second layer.
A 100A silver layer is added as a layer, and a 25A silver layer is added as a third layer.
A titanium oxide layer of 0A was formed to obtain a selectively transparent film.

Here, the first and third titanium oxide layers are formed by using titanium oxide as a target while cooling the substrate film with cold fN at 20° C. using an RF sputtering device at argon gas pressure of 2.0° C. The second silver layer was formed in the same manner as in Example 1.

[The heat shrinkage rate of the obtained laminated film is TDl, 8
%, MD was 2.0 yen.

Next, 1.0% by weight of Tlnuvin■ 32B (C1h) was applied to both sides of this laminated film in advance.
50 pieces of polyvinyl butyral sheet with a thickness of 0.38 μm kneaded with ultraviolet absorber (manufactured by a-Geig A, G)
A laminated structure was produced by laminating at ℃.

The heat shrinkage rate of polyvinyl butyral used here is MD
2.0 inches, TD 2.2%, and its flat side was bonded to the film, and the outermost surface of the laminated structure was embossed.

In the laminated structure produced in this way, the adhesive force between the film and the polyvinyl butyral sheet is a e
It was s 11/am.

Next, the laminated structure was sandwiched between flat glass plates having a thickness of 2 mm, and the laminated glass was prepared in the same manner as in Example 1. The laminated glass had a visible light transmittance of 75% and a solar energy transmittance of 65%. In addition, a good laminated window with good transparency and no distortion or irregularities in the reflected image was obtained.

Example 3 Indim tino using 2QTII stretched polyethylene terephthalate film with a thickness of 50 μm as a substrate
xide (containing 7.0% by weight of SnO) was laminated to a thickness of 3.50 OA by reactive sputtering to obtain a selective light transmitting film.

Indium tin oxide layer is oxygen gas,
The substrate film was formed by a DC sputtering apparatus at a pressure of 3.5 x 10''-3'l'' orr in the presence of a mixed gas of argon gas, nitrogen gas and hydrogen gas while being cooled with a 20° C. refrigerant. The heat shrinkage rate of the laminated film thus obtained was TD2.6, MD
2. It was o.

Next, a laminated glass produced using the same polyvinyl butyral sheet as in Example 1 and in exactly the same manner as in Example 1 had a visible light transmittance of 74 cm and a solar energy transmittance of 63 cm.

Furthermore, a laminated glass with good transparency and no unevenness in the reflected image was obtained. The adhesive strength of the interlayer film obtained by sandwiching polyvinyl butyral sheets was "J7/cm."

Example 4 A biaxially stretched polyethylene terephthalate film with a thickness of 50 μm was used as a substrate, and a first layer with a thickness of 10 μm was placed on it.
A 0X silver/gold alloy layer was further laminated with a 200X zircolumn oxide layer as a second layer to obtain a selective light transmitting and electrically conductive film.

Here, the silver/gold alloy layer was formed by DC sputtering in the same manner as in Example 1 using a target containing 20% by weight of gold. Zirconium oxide I- was obtained by applying a mixed solution of n-hexane and n-butanol containing 8.0 weight coefficient of tetrabutoxyzirconate using a bar coater and then drying it in a hot air dryer at 75°C for 5 minutes. .

The heat shrinkage rate of the laminated film thus obtained was TD2.3.
The MD score was 2.2 points.

Next, using this laminated film, a laminated structure was obtained in exactly the same manner as in Example 1, and a laminated glass was further produced in accordance with the method of Example 1.

The visible light transmittance of this laminated glass was 70%, and the solar energy transmittance was 62%.

Further, the transparency of the laminated glass was good, and no irregularities in the reflected image were observed.

[Brief explanation of drawings]

FIG. 1 is an example of a cross-sectional view of the functionalized film of the present invention. FIG. 2 is an example of a cross-sectional view of a preformed laminate + iS structure. 1362 Figure, 1 0.2

Claims (1)

[Claims] 1. (11) A support film made of a transparent polymer film having a thickness of less than about 125 μm; (2) A selectively transparent or conductive thin film supported on one or both sides of the support film. , and its thermal contraction rate E (%) and thickness d (μ
m) A selectively transparent or conductive film that satisfies the following formula: % formula %)
The selectively transparent or electrically conductive film according to claim 1, which is a polyethylene terephthalate film falling within the range of .