TWI629180B - Water-vapor barrier laminates - Google Patents

Abstract

A water vapor barrier laminate comprising a substrate and at least one water vapor barrier film. The water vapor barrier film includes an organic-inorganic layer unit and an aluminum oxide layer unit. The organic-inorganic layer unit is obtained by hydrolytic condensation of an organic decane and metal source modification, and comprises a first organic-inorganic layer disposed on the surface of the substrate. An aluminum oxide layer unit is disposed on the first organic-inorganic layer, comprising a layer of a first reactive sputtered aluminum oxide layer, a second reactive sputtered aluminum oxide layer, and a first non-reactive sputtering layer An aluminum oxide layer and a second non-reactive, sputtered aluminum oxide layer. The moisture barrier layer has an excellent water vapor barrier effect and a high light transmittance.

Description

Water vapor barrier laminate

The invention relates to a water gas barrier laminate, in particular to a water vapor barrier comprising at least one organic-inorganic layer, two layers of reactive sputtered alumina layer, and two layers of non-reactive sputtered alumina layer. Barrier layer.

Water-blocking packaging technology is widely used in food, drug storage and electronic products. According to recent statistics from the World Packaging Organization (WPO), packaging costs worldwide have reached 5.6 trillion US dollars. As electronic products change with each passing day, heavy glass substrates are gradually replaced by soft, thin, flexible and highly flexible soft plastic substrates, such as electronic paper, dye-sensitized solar cells (DSSCs), and organic solar cells (OPV). And related developments such as organic light-emitting diodes (OLEDs) are imperative. However, such products have doubts about reliability. The components of organic solar cells or organic light-emitting diodes have highly sensitive organic materials and easily oxidized cathode metals. The moisture in the air penetrates through the flexible plastic substrate. The inside of the component will cause deterioration and aging of the above materials. Therefore, in order to prolong the service life of the product, it is necessary to use a water vapor barrier film to block the penetration of moisture into the interior of the component, thereby preventing the component from being inside. Degradation of organic materials and aging of cathode metals. In addition, the water vapor barrier film needs to have high light transmission properties in commercial applications.

Accordingly, it is an object of the present invention to provide a water vapor barrier laminate.

Thus, the water vapor barrier laminate of the present invention comprises: a substrate; and at least one water vapor barrier film comprising: an organic-inorganic layer unit, which is obtained by hydrolysis and condensation of an organic germane and upgrading of a metal source. a first organic-inorganic layer disposed on a surface of the substrate, and an aluminum oxide layer unit disposed on the first organic-inorganic layer, comprising a layer of first reactive sputtered alumina disposed in a stack a layer, a second reactive sputtered aluminum oxide layer, a first non-reactive sputtered aluminum oxide layer, and a second non-reactive sputtered aluminum oxide layer.

The effect of the invention is that the moisture barrier layer penetrates the first organic-inorganic layer, the first reactive sputtered aluminum oxide layer, the second reactive sputtered aluminum oxide layer, and the first non-reactive sputtering oxidation The interaction of the aluminum layer and the second non-reactive sputtered aluminum oxide layer provides the water vapor barrier laminate with excellent water vapor barrier effect and high light transmittance.

The details of the present invention are described below: Preferably, in one embodiment of the moisture barrier layer, the first non-reactive sputtered aluminum oxide layer is sequentially formed on the surface of the first organic-inorganic layer opposite to the substrate. a first reactive sputtered aluminum oxide layer, a second non-reactive sputtered aluminum oxide layer, and a second reactive sputtered aluminum oxide layer.

Preferably, in another embodiment of the water vapor barrier laminate, the organic-inorganic layer unit of the water gas barrier laminate according to the paragraph [0007] further comprises a second organic-inorganic layer. The surface of the second reactive sputtered aluminum oxide layer is disposed.

Preferably, in another embodiment of the water vapor barrier laminate, the organic-inorganic layer unit of the water gas barrier laminate according to the paragraph [0007] further comprises a second organic-inorganic layer. And disposed between the first reactive sputtered aluminum oxide layer and the second non-reactive sputtered aluminum oxide layer.

Preferably, in another embodiment of the water vapor barrier laminate, the organic-inorganic layer unit of the water gas barrier laminate according to [0009] further comprises a third organic-inorganic layer. The surface of the second reactive sputtered aluminum oxide layer is disposed.

Preferably, another embodiment of the moisture barrier layer is formed by sequentially forming a first reactive sputtered aluminum oxide layer on the surface of the first organic-inorganic layer opposite to the substrate. A non-reactive sputtered aluminum oxide layer, a second reactive sputtered aluminum oxide layer, and a second non-reactive sputtered aluminum oxide layer.

Preferably, in another embodiment of the water gas barrier laminate, the organic-inorganic layer unit of the water gas barrier laminate according to [0011] further comprises a layer A second organic-inorganic layer is disposed on a surface of the second non-reactive sputtered aluminum oxide layer.

Preferably, in another embodiment of the water vapor barrier laminate, the organic-inorganic layer unit of the water gas barrier laminate according to [0011] further comprises a second organic-inorganic layer. And disposed between the first non-reactive sputtered aluminum oxide layer and the second reactive sputtered aluminum oxide layer.

Preferably, in another embodiment of the water vapor barrier laminate, the organic-inorganic layer unit of the water gas barrier laminate according to [0013] further comprises a third organic-inorganic layer. The surface of the second non-reactive sputtered aluminum oxide layer is disposed.

Preferably, in each of the embodiments of the water vapor barrier laminate, two water vapor barrier films are included, and the first organic-inorganic layers of the water vapor barrier films are respectively disposed on the base On the opposite side of the material.

The material of the substrate is not particularly limited, and is not limited to, for example, a polyester resin, a polyacrylate resin, a polyolefin resin, a polycarbonate resin, or a polychlorinated resin. Ethylene, polyimide resin or polylactic acid. The polyester resin is, for example but not limited to, polyethylene terephthalate (PET), or polyethylene naphthalate (PEN). The polyacrylate resin is, for example but not limited to, polymethyl methacrylate (PMMA) or the like. The polyolefin resin is, for example but not limited to, polyethylene or polypropylene. go a step further The substrate is said to be a flexible substrate. The surface of the substrate may be selectively modified, and the modification is specifically performed by, for example, but not limited to, modifying the surface of the substrate with oxygen plasma. The thickness of the substrate is not particularly limited, such as, but not limited to, 25 to 250 μm.

The organic-inorganic layer unit is hydrolyzed and condensed by an organic decane, that is, a sol-gel method, and the obtained product is formed by upgrading a metal source. The organodecane is, for example but not limited to, 3-glycidoxypropyltrimethoxydecane, tetraethyl orthosilicate, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxy 3-mercaptopropyltrimethoxysilane or vinyltriethoxysilane, and the above organodecane can be used singly or in combination of two or more. The metal source may be, for example but not limited to, an aluminum source, a zirconium source or a titanium source, and the above metal sources may be used singly or in combination. Specific means for modifying the metal source, such as but not limited to, mixing alumina powder, zirconia powder, titanium oxide powder or a combination of the above with a product obtained by hydrolytic condensation of the organodecane; or containing an aluminum chelate, The zirconium-containing chelate compound, the titanium-containing chelate compound or a combination of the above is subjected to a miscible reaction with a product formed by hydrolysis condensation of the organodecane, wherein the aluminum-containing chelate compound is, for example but not limited to, aluminum acetylacetonate [aluminum acetylacetonate] , Al(acac) ₃ ], the zirconium-containing chelate compound such as, but not limited to, zirconium acetoacetate [tetrakis (2,4-pentanedionato) zirconium (IV), Zr(acac) ₄ ], the titanium-containing chelate compound, For example, but not limited to, titanium diisopropoxide bis (acetylacetonate).

Preferably, the first organic-inorganic layer of the organic-inorganic layer unit has a thickness ranging from 500 to 3000 nm. Preferably, the thickness of the second organic-inorganic layer of the organic-inorganic layer unit ranges from 500 to 3000 nm. Preferably, the third organic-inorganic layer of the organic-inorganic layer unit has a thickness ranging from 500 to 3000 nm.

The first organic-inorganic layer, the second organic-inorganic layer, and the third organic-inorganic layer may be the same or different from each other.

The first non-reactive sputtered aluminum oxide layer and the second non-reactive sputtered aluminum oxide layer are prepared, for example, but not limited to, by direct sputter deposition using an alumina target. The sputtering method for preparing the first and second non-reactive sputtered aluminum oxide layers is, for example but not limited to, radio frequency magnetron sputtering, and the power range used by the radio frequency magnetron sputtering method is, for example but not limited to, 80 to 150 watts. . Preferably, the first non-reactive sputtered aluminum oxide layer has a thickness ranging from 50 to 300 nm. Preferably, the second non-reactive sputtered aluminum oxide layer has a thickness ranging from 50 to 300 nm. And the first non-reactive sputtered aluminum oxide layer and the second non-reactive sputtered aluminum oxide layer may be the same or different.

The first reactive alumina layer and the second reactive sputtered alumina layer are prepared by, for example but not limited to, using an aluminum target and introducing oxygen to cause oxygen to react with the aluminum target to deposit alumina. The sputtering method for preparing the first and second reactive sputtered aluminum oxide layers is, for example but not limited to, pulsed DC magnetron sputtering, and the power range used by the pulsed DC magnetron sputtering method is, for example but not limited to, 50 to 80. watt. Preferably, the first reactive sputtering The thickness of the aluminum oxide layer ranges from 50 to 300 nm. Preferably, the second reactive sputtered aluminum oxide layer has a thickness ranging from 50 to 300 nm. And the first reactive sputtered aluminum oxide layer and the second reactive sputtered aluminum oxide layer may be the same or different.

1‧‧‧Substrate

2‧‧‧Water and Gas Barrier Film

3‧‧‧Organic-inorganic layer unit

31‧‧‧First organic-inorganic layer

32‧‧‧Second organic-inorganic layer

33‧‧‧ Third organic-inorganic layer

4‧‧‧ Alumina layer unit

41‧‧‧First non-reactive sputtered alumina layer

42‧‧‧Second non-reactive sputtered aluminum oxide layer

43‧‧‧First reactive sputtered alumina layer

44‧‧‧Second reactive sputtered alumina layer

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: Figure 1 is a schematic view of a first embodiment of a water vapor barrier laminate of the present invention; 3 is a schematic view of a second embodiment of a water vapor barrier laminate of the present invention; and FIG. 4 is a schematic view of a fourth embodiment of the water vapor barrier laminate of the present invention; Figure 5 is a schematic view showing a fifth embodiment of the water vapor barrier laminate of the present invention; Figure 6 is a schematic view showing a sixth embodiment of the water vapor barrier laminate of the present invention; and Figure 7 is a schematic diagram of the water vapor barrier laminate of the present invention. 7 is a schematic view of an eighth embodiment of a water vapor barrier laminate of the present invention; FIG. 9 is a schematic view of a ninth embodiment of the water vapor barrier laminate of the present invention; FIG. 11 is a schematic view showing an eleventh embodiment of the water gas barrier laminate of the present invention; and FIG. 12 is a twelfth embodiment of the water vapor barrier laminate of the present invention. Schematic diagram of an example; FIG. 13 is a tenth embodiment of the water vapor barrier laminate of the present invention Schematic of an embodiment; FIG. 14 is a schematic view of a fourteenth embodiment of the present invention, water vapor barrier layer assembly; Figure 15 is a schematic view showing a fifteenth embodiment of the water vapor barrier laminate of the present invention; and Figure 16 is a schematic view showing a sixteenth embodiment of the water vapor barrier laminate of the present invention.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

Before the present invention is described in detail, it should be noted that in the following description, similar elements are denoted by the same reference numerals.

Referring to Figure 1, a first embodiment of a water vapor barrier laminate of the present invention comprises a substrate 1 and a moisture barrier film 2. The water vapor barrier film 2 includes an organic-inorganic layer unit 3 and an aluminum oxide layer unit 4. The organic-inorganic layer unit 3 contains a first organic-inorganic layer 31 disposed on the surface of the substrate 1. The aluminum oxide layer unit 4 is disposed on the first organic-inorganic layer 31, and the aluminum oxide layer unit 4 is formed on the surface of the first organic-inorganic layer 31 opposite to the surface of the substrate 1 A non-reactive sputtered aluminum oxide layer 41, a first reactive sputtered aluminum oxide layer 43, a second non-reactive sputtered aluminum oxide layer 42, and a second reactive sputtered aluminum oxide layer 44. The first organic-inorganic layer 31 is capable of modifying the surface of the substrate 1, thereby reducing the extrinsic defects of the aluminum oxide layer unit 4, and avoiding the phenomenon of moisture hysteresis, and enabling the water vapor barrier film 2 has better mechanical flexibility.

The first organic-inorganic layer 31 in the first embodiment will be described in detail below, first. The non-reactive sputtered alumina layer 41, the second non-reactive sputtered alumina layer 42, the first reactive sputtered alumina layer 43, and the second reactive sputtered alumina layer 44 are prepared in the following manner:

(Step 1) Preparation of the first organic-inorganic layer 31: 1.805 g of methanol (manufactured by ANCCORE, purity 99.9%) was mixed with 2.559 g of deionized water, followed by hydrochloric acid (manufactured by ACROS, concentration 37) %) Adjust the pH to 1.2 to obtain a first component. 8.000 g of 3-glycidoxypropyl trimethoxy decane (manufactured by ALDRICH, purity 98%), 7.051 g of tetraethoxy decane (manufactured by ACROS, purity 98%), and The amount of 65 wt% of n-butanol (manufactured by ACROS, the purity is 99%, the total amount of n-butanol to be added is such that the final product has a solid content of 25 wt%), and the magnet is stirred for 20 minutes to obtain a second. Component. The third component is added dropwise to the second component to obtain a third component, and the third component is continuously stirred at room temperature (25 ° C) for 20 minutes, followed by refluxing at 80 ° C for 90 minutes, and then at room temperature. Cooling (25 ° C) gave a product. To the product was added 0.220 g of aluminum acetoacetate (manufactured by ACROS, purity: 97%), 0.165 g of zirconium acetonide (manufacturer TCI, purity: 97%), and stirred to make acetam aluminum acetate and acetamidine. After dissolving the acetone zirconium, the remaining 35 wt% of n-butanol was added and stirring was continued at normal temperature (25 ° C) for 20 minutes, followed by a mixture of hydrochloric acid and n-butanol (hydrochloric acid: n-butanol ratio of 1:1). Adjust the pH to 2.0 to obtain a white water solution. Then the water white solution is at room temperature (25 °C) Stirring for 2 days gave a clear and transparent solution, which is the material for the first organic-inorganic layer.

The surface of the substrate 1 (material is polyethylene terephthalate, the manufacturer's model is CH2A6 of Nanya Plastic Co., Ltd., thickness 100 μm) was cleaned using high-pressure air. The first organic-inorganic layer material was extruded on the surface of the substrate 1 using a syringe [the injection head was equipped with a syringe filter (Syring 0.22 μm filter)], followed by a coating bar (manufacturer model number was RDS No. 4) The material for the first organic-inorganic layer was applied flat on the surface of the substrate 1. The substrate 1 to which the material for the first organic-inorganic layer has been coated is placed in an aluminum pan and the aluminum pan is covered with aluminum foil, and the aluminum pan is placed in an oven and baked in a plurality of stages: 60 ° C first Bake for 15 minutes, bake at 80 ° C for 30 minutes, and finally bake at 105 ° C for 90 minutes. After the baking is completed, the first organic-inorganic layer 31 is formed on the substrate 1, and a first laminate is obtained.

(Step 2) Preparation of First Non-Reactive Sputtered Alumina Layer 41

The sputtering target is made of alumina (the manufacturer is Kaidasen Industrial Co., Ltd., the purity is 99.9%, the size is 2吋 in diameter, and the thickness is 3mm). The power supply is an RF power supply. First, the surface of the first organic-inorganic layer 31 of the first laminate is cleaned with high-pressure air, and the first laminate is fixed on a glass sheet and placed in a magnetron sputtering device (the manufacturer is Gao Dun Co., Ltd.) Company, model R-24K08-SPUTTERING) cavity. First, the background pressure of the chamber is pumped to 3×10 ^-6 torr, and then argon gas is introduced to control the working pressure of the chamber to be 1 mtorr. The sputtering conditions were set as follows: the rotation speed of the turntable was 20 rpm, and the power was 150 W. Then, the surface of the target is cleaned for 10 to 15 minutes until the parameters are stabilized, and sputtering is started. The sputtering time is 48 minutes, that is, the first non-form is formed on the first organic-inorganic layer 31 of the first laminate. The reactive aluminum oxide layer 41 (thickness: 100 nm) was sputtered to obtain a second laminate.

(Step 3) Preparation of the first reactive sputtered alumina layer 43: The sputter target was an aluminum target (manufactured by Taiwan Graymont Co., Ltd., having a purity of 99.999%, a size of 2 Å, and a thickness of 6 mm). The power supply is a pulsed DC power supply (DC pulse). First cleaning the surface of the first non-reactive sputtered alumina layer 41 of the second laminate with high pressure air, and fixing the second laminate to a glass sheet, and placing a magnetron sputtering device (manufacturer The chamber of Gao Dun Co., Ltd., model R-24K08-SPUTTERING). First, the background pressure of the chamber is pumped to 3×10 ^-6 torr, and then argon gas is introduced to control the working pressure of the chamber to be 3 mtorr. The sputtering conditions were set as follows: power 50 W, turret rotation speed 20 rpm, pulse frequency 50 kHz, and pulse pause time 5 μs. Then clean the surface of the target for 10 to 15 minutes until the voltage is no longer floating, then pass oxygen [oxygen purity 99.999%, oxygen ratio O ₂ / (Ar + O ₂ ) = 2%], and wait in the cavity After the pressure is stabilized, it is equilibrated for 10 to 15 minutes until the voltage is no longer floating, and sputtering is started, and the sputtering time is 19 minutes, that is, the first reaction is formed on the first non-reactive sputtered alumina layer 41 of the second laminate. The aluminum oxide layer 43 (thickness: 100 nm) was sputtered to obtain a third laminate.

(Step 4) Preparation of Second Non-Reactive Sputtered Alumina Layer 42

Forming a second non-reactive sputtered alumina layer 42 on the first reactive sputtered alumina layer 43 of the third laminate in the same manner as the first non-reactive sputtered alumina layer 41 is obtained. The fourth layer is combined.

(Step 5) Preparation of Second Reactive Sputtered Alumina Layer 44

A second reactive sputtered alumina layer 44 is formed on the second non-reactive sputtered alumina layer 42 of the fourth laminate in the same manner as the first reactive sputtered alumina layer 43 is obtained. 1 water gas barrier laminate.

Referring to FIG. 2, a second embodiment of the water vapor barrier laminate of the present invention is different from the first embodiment in that the water vapor barrier laminate of the second embodiment comprises two water vapor barrier films. 2, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite surfaces of the substrate 1.

Referring to FIG. 3, a third embodiment of the water vapor barrier laminate of the present invention is different from the first embodiment in that the organic-inorganic layer unit 3 of the water vapor barrier film 2 of the third embodiment A second organic-inorganic layer 32 disposed on the surface of the second reactive sputtered alumina layer 44 opposite the second non-reactive sputtered alumina layer 42 is also included. The second organic-inorganic layer 32 has a function of protecting the aluminum oxide layer unit 4. The second organic-inorganic layer 32 is prepared in the same manner as the first organic-inorganic layer 31, and will not be described again.

Referring to FIG. 4, a fourth embodiment of the water vapor barrier laminate of the present invention is different from the third embodiment in that the water vapor barrier laminate of the fourth embodiment comprises Two water vapor barrier films 2, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite surfaces of the substrate 1.

Referring to FIG. 5, a fifth embodiment of the water vapor barrier laminate of the present invention is different from the first embodiment in that the organic-inorganic layer unit 3 of the water vapor barrier film 2 of the fifth embodiment is A second organic-inorganic layer 32 disposed between the first reactive sputtered alumina layer 43 and the second non-reactive sputtered alumina layer 42 is also included. The second organic-inorganic layer 32 has the function of protecting the first reactive sputtered aluminum oxide layer 43 and providing the water vapor barrier film 2 with better mechanical flexibility. The second organic-inorganic layer 32 is prepared in the same manner as the first organic-inorganic layer 31, and will not be described again.

Referring to FIG. 6, a sixth embodiment of the water vapor barrier laminate of the present invention is different from the fifth embodiment in that the water vapor barrier laminate of the sixth embodiment comprises two water vapor barrier films. 2, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite surfaces of the substrate 1.

Referring to FIG. 7, a seventh embodiment of the water vapor barrier laminate of the present invention is different from the fifth embodiment in that the organic-inorganic layer unit 3 of the water vapor barrier film 2 of the seventh embodiment Further, a third organic-inorganic layer 33 disposed on the surface of the second reactive sputtered alumina layer 44 opposite to the surface of the second non-reactive sputtered alumina layer 42 is further included. The third organic-inorganic layer 33 is prepared in the same manner as the first organic-inorganic layer 31, and will not be described again.

Referring to FIG. 8, an eighth embodiment of the water vapor barrier laminate of the present invention, The seventh embodiment is different in that the water gas barrier laminate of the eighth embodiment comprises two water vapor barrier films 2, and the first organic-inorganic layers of the water vapor barrier films 2 31 are respectively disposed on opposite faces of the substrate 1.

Referring to FIG. 9, a ninth embodiment of the water vapor barrier laminate of the present invention is different from the first embodiment in that the water vapor barrier laminate of the ninth embodiment is the first organic-inorganic The first reactive sputtered aluminum oxide layer 43, the first non-reactive sputtered aluminum oxide layer 41, and the second reactive sputtered aluminum oxide layer are sequentially formed on the surface of the substrate 31 opposite to the substrate 1. 44, and the second non-reactive sputtered aluminum oxide layer 42.

Referring to FIG. 10, a tenth embodiment of the water vapor barrier laminate of the present invention is different from the ninth embodiment in that the water vapor barrier laminate of the tenth embodiment comprises two water vapor barrier films. 2, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite surfaces of the substrate 1.

Referring to Fig. 11, an eleventh embodiment of the water vapor barrier laminate of the present invention is different from the ninth embodiment in the organic-inorganic layer of the water vapor barrier film 2 of the eleventh embodiment. Unit 3 also includes a second organic-inorganic layer 32 disposed on the surface of the second non-reactive sputtered alumina layer 42 opposite the second reactive sputtered alumina layer 44. The second organic-inorganic layer 32 is prepared in the same manner as the first organic-inorganic layer 31, and will not be described again.

Referring to FIG. 12, a twelfth embodiment of the water vapor barrier laminate of the present invention is different from the eleventh embodiment in the water vapor barrier of the twelfth embodiment. The laminate includes two water vapor barrier films 2, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite sides of the substrate 1.

Referring to FIG. 13, a thirteenth embodiment of the water vapor barrier laminate of the present invention is different from the ninth embodiment in the organic-inorganic layer of the water vapor barrier film 2 of the thirteenth embodiment. Unit 3 also includes a second organic-inorganic layer 32 disposed between the first non-reactive sputtered alumina layer 41 and the second reactive sputtered alumina layer 44. The second organic-inorganic layer 32 is prepared in the same manner as the first organic-inorganic layer 31, and will not be described again.

Referring to FIG. 14, a fourteenth embodiment of the water vapor barrier laminate of the present invention is different from the thirteenth embodiment in that the water vapor barrier laminate of the fourteenth embodiment comprises two water vapors. The barrier film 2 is provided, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite surfaces of the substrate 1.

Referring to FIG. 15, a fifteenth embodiment of the water vapor barrier laminate of the present invention is different from the thirteenth embodiment in that the organic-inorganic layer unit 3 of the fifteenth embodiment further comprises a layer setting. The third organic-inorganic layer 33 on the surface of the second non-reactive sputtered aluminum oxide layer 42 opposite to the second reactive sputtered aluminum oxide layer 44. The third organic-inorganic layer 33 is prepared in the same manner as the first organic-inorganic layer 31, and will not be described again.

Referring to FIG. 16, a sixteenth embodiment of the water vapor barrier laminate of the present invention is different from the fifteenth embodiment in the water vapor barrier of the sixteenth embodiment. The laminate includes two water vapor barrier films 2, and the first organic-inorganic layers 31 of the water vapor barrier films 2 are respectively disposed on opposite sides of the substrate 1.

Further, Comparative Examples 1 and 2 water vapor barrier laminates were provided. Comparative Examples 1 and 2 differed from the above examples in the difference in layer structure, and the preparation methods of the layers in Comparative Examples 1 and 2 were the same as those in the examples. Therefore, it will not be repeated here.

The water vapor barrier effect and the transmittance of the above respective examples and comparative examples were measured in accordance with the property evaluation methods described below, and the results are summarized in Tables 1 and 2.

1. Water Vapor Transmission Rate (WVTR)

The water vapor barrier laminate to be tested is placed in a sample tank of a moisture gas permeability meter (manufacturer model AQUATRAN ^® Model 2 G). When measuring, use a hygrometer (built in the water gas permeability meter) on one side of the sample tank to control the humidity and pass nitrogen gas. When the nitrogen gas carries water and gas permeates through the water gas barrier laminate to be tested, it reaches the other side. At the time, the Coulomb pentoxide pentoxide sensor is detected to detect the osmotic water content, thereby analyzing the water vapor transmission rate of the water vapor barrier laminate to be tested. Among them, the measurement conditions were as follows: the temperature was 37.8 ° C, the relative humidity was 90%, and the sample tank flow rate was set to 20 sccm.

2. Visible light transmittance (transmittance, T%)

The visible light transmittance of the water vapor barrier laminate to be tested was measured with a UV-VIS spectrometer (manufacturer model Agilent Cary 5000). The measurement method is detailed as follows: firstly, the UV-VIS spectrometer is subjected to all-light correction, and then the water-vapor barrier layer to be tested is placed. Place the measuring chamber of the UV-VIS spectrometer after the carrier. Among them, the measurement conditions are: wavelength 450~750nm.

Note: "P" represents a substrate; "O ₁ " represents a first organic-inorganic layer 31; "O ₂ " represents a second organic-inorganic layer 32; "O ₃ " represents a third organic-inorganic layer 33; "A ₁ " represents a first non-reactive sputtered alumina layer 41; "A ₂ " represents a second non-reactive sputtered alumina layer 42; "B ₁ " represents a first reactive sputtered alumina layer 43; "B ₂ ” represents a second reactive sputtered aluminum oxide layer 44.

The results of Tables 1 and 2 demonstrate that the water vapor barrier laminates of Examples 1 to 16 It has a low water vapor transmission rate and a visible light transmittance of more than 89%, which represents that the water vapor barrier laminates of Examples 1 to 16 have a better water vapor barrier effect and a high visible light transmittance. .

In summary, the water vapor barrier laminate of the present invention passes through the first organic-inorganic layer, the first reactive sputtered aluminum oxide layer, the second reactive sputtered aluminum oxide layer, and the first non-reactive sputtering oxidation. The aluminum layer and the second non-reactive sputtered aluminum oxide layer cooperate with each other, and the moisture barrier layer has an excellent water vapor barrier effect and a high light transmittance, so that the object of the present invention can be achieved.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

Claims (8)

A water vapor barrier laminate comprising: a substrate; and at least one water vapor barrier film comprising: an organic-inorganic layer unit, which is obtained by hydrolysis and condensation of an organic germane and metal source modification, and comprises a layer a first organic-inorganic layer disposed on a surface of the substrate, and an aluminum oxide layer unit disposed on the first organic-inorganic layer, comprising a layer of a first reactive sputtered aluminum oxide layer and a layer disposed in a stack a second reactive sputtered aluminum oxide layer, a first non-reactive sputtered aluminum oxide layer, and a second non-reactive sputtered aluminum oxide layer, wherein the organic-inorganic layer unit further comprises a second organic layer An inorganic layer, and the second organic-inorganic layer is disposed in the aluminum oxide layer unit. The water gas barrier laminate according to claim 1, wherein the first non-reactive sputtered alumina layer is sequentially formed on a surface of the first organic-inorganic layer opposite to the substrate, first A reactive sputtered aluminum oxide layer, a second non-reactive sputtered aluminum oxide layer, and a second reactive sputtered aluminum oxide layer. The moisture barrier laminate of claim 2, wherein the second organic-inorganic layer of the organic-inorganic layer unit is disposed on the first reactive sputtered aluminum oxide layer and the second non-reactive sputtering layer Between the layers of alumina. The water gas barrier laminate according to claim 3, wherein the organic-inorganic layer unit further comprises a third organic-inorganic layer disposed in the second reactivity The surface of the aluminum oxide layer is sputtered. The water vapor barrier laminate according to claim 1, wherein the first reactive sputtered alumina layer is formed on the surface of the first organic-inorganic layer opposite to the substrate, and the first non-reactive A sputtered aluminum oxide layer, a second reactive sputtered aluminum oxide layer, and a second non-reactive sputtered aluminum oxide layer. The moisture barrier laminate of claim 5, wherein the second organic-inorganic layer of the organic-inorganic layer unit is disposed on the first non-reactive sputtered alumina layer and the second reactive sputter Between the layers of alumina. The moisture barrier laminate according to claim 6, wherein the organic-inorganic layer unit further comprises a third organic-inorganic layer disposed on a surface of the second non-reactive sputtered alumina layer. The water gas barrier laminate according to any one of claims 1 to 7, comprising two water vapor barrier films, and the first organic-inorganic layers of the water vapor barrier films are respectively disposed on the water vapor barrier layer On opposite sides of the substrate.