Patent Application
20150017409
This invention relates to a composite member containing an oxide glass formed as a layer on a base material containing a resin or a rubber.
There is a wide range of organic compounds, and organic compounds have characteristics in that their functions, physical characteristics and the like are easier to control depending on purpose and they are lighter and easier to form at a relatively low temperature compared with other materials; however, they have defects such as the low gas barrier property, absorbency, odor-absorbing property, deterioration by the irradiation with ultraviolet rays and low mechanical strength (softness). On the other hand, glass is excellent in mechanical strength and chemical stability compared with organic compounds and it is possible to add various functions; however, glass has defects in that glass is heavy and weak to impact and breaks easily. Therefore, various composite materials combining an organic compound and glass have been invented to comprehend each other's defects.
As laminates of glass, an oxide or a nitride and an organic polymer (such as a gas barrier sheet), many laminates obtained by forming a thin film of an oxide or a nitride on an organic polymer film such as polyester or polyamide by a method such as sputtering, vapor deposition, CVD or sol-gel method have been proposed.
PTL1 discloses a gas barrier laminate in which a barrier layer comprising a metal or an inorganic compound and an organic layer comprising an organic compound have been sequentially laminated on at least one surface of a polymer film and in which the barrier layer has been formed using vacuum vapor deposition method.
When a laminate is produced by vapor deposition method, sputtering method and CVD method described above, there are problems in that a small amount of gas may still permeate because only a film with a thickness of dozens of nanometers can be generally formed and the film is not completely dense.
An object of this invention is to improve the gas barrier property.
In order to solve the above problems, this invention is characterized by a composite member containing an oxide glass formed as a layer densely on a base material containing a resin or a rubber, in which the oxide glass is bonded to the base material by irradiating the oxide glass with an electromagnetic wave and softening and fluidizing the oxide glass.
Further, this invention is characterized by containing a step of coating an oxide glass powder on a base material containing a resin or a rubber, a step of applying an electromagnetic wave and a step of forming a layered and dense coated film on the base material by softening and fluidizing the oxide glass powder, and characterized in that the oxide glass contains a transition metal oxide and has a transition point of 330° C. or lower.
According to this invention, the gas barrier property can be improved.
This invention is explained below.
Schematic cross-sectional views of the composite members of the embodiments in this invention are shown in
However, in case of an oxide glass which does not absorb an electromagnetic wave or an oxide glass which is softened and fluidized only by a high-power electromagnetic wave, there are sometimes problems in that a layered and dense oxide glass cannot be formed or the thermal damage to the base material containing a resin or a rubber is significant. As the electromagnetic wave 3, a laser having a wavelength in the range of 400 to 1100 nm and a microwave having a wavelength in the range of 0.1 to 1000 mm are effective. If the wavelength of the laser is less than 400 nm, there is a possibility that the resin or the rubber contained in the base material 1 deteriorates. On the other hand, with the wavelength exceeding 1100 nm, the oxide glass may not show excellent softness and fluidity or the resin or the rubber contained in the base material 1 may become hot and melt if a tiny amount of water is included in the resin or the rubber. With the irradiation with a microwave having a wavelength in the range of 0.1 to 1000 mm, the oxide glass obtains semiconductor-like conductivity, and thus the oxide glass can absorb the electromagnetic wave thereof and can be softened and fluidized as with the irradiation with the laser above. Accordingly, the oxide glass can be solidly bonded and adhered to the base material 1. The source of the microwave is not particularly limited and those of 2.45 GHz band and the like which are used for a known microwave for domestic use and the like can be used.
In addition, in the composite member of this invention, the average thickness of each layer of the oxide glass is preferably 50 μm or less. When this average thickness is 50 μm or less, the oxide glass can be excellently softened and fluidized. The softening and fluidizing mechanism of the oxide glass is as follows: the surface part of the oxide glass irradiated with the electromagnetic wave first starts to be softened and fluidized; the heat thereof transfers in the depth (thickness) direction; and the electromagnetic-wave-irradiated part is softened and fluidized as a whole. Therefore, if the thickness of the oxide glass is large, it becomes difficult to efficiently and evenly soften and fluidize in the electromagnetic-wave-irradiation direction. The particularly effective average thickness range of the oxide glass was 3 to 20 μm. When the average thickness was 20 μm or less, the oxide glass could be easily softened and fluidized with the irradiation with the electromagnetic wave and a composite member in which a layered and dense oxide glass was formed was easy to obtain. However, when the average thickness was less than 3 μm, the thickness was so small that an even layered film was difficult to obtain although the oxide glass was softened and fluidized.
Moreover, the oxide glass in the composite member of this invention preferably contains a transition metal oxide and has a transition point of 330° C. or lower. When a transition metal oxide is contained, the oxide glass absorbs the above electromagnetic wave and thus becomes easier to soften and fluidize. Further, when the transition point is 330° C. or lower, the softening and fluidization are achieved at a low temperature and the film can be easily formed on the base material. A more specific example of the oxide glass is an oxide glass containing vanadium oxide, tellurium oxide and phosphorus oxide in which, in terms of the following oxides, the total amount of V2O5, TeO2 and P2O5 is 70 to 95% by mass and V2O5>TeO2≧P2O5 (% by mass). When V2O5 as a transition metal oxide is contained most, the electromagnetic wave is easily absorbed. TeO2 and P2O5 are contained for glass formation and P2O5 is more effective than TeO2 for glass formation while TeO2 is more effective than P2O5 for softening and fluidizing at a lower temperature. As a result, it is more effective that both are contained and the relation is TeO2P2O5 as % by mass. Further, it is effective that the total amount of V2O5, TeO2 and P2O5 is 70 to 95% by mass and the softening and fluidization by the irradiation with the electromagnetic wave become not so easy if the total amount is less than 70% by mass. On the other hand, if the total amount exceeds 95% by mass, the reliability such as moisture resistance and water resistance tends to deteriorate. In this regard, in this invention, when the amount is described to be 70 to 95% by mass for example, it means that the amount is 70% by mass or more and 95% by mass or less.
Further, it is desirable that the above oxide glass contains one or more kinds of iron oxide, tungsten oxide, molybdenum oxide, manganese oxide, antimony oxide, bismuth oxide, barium oxide, potassium oxide and zinc oxide in addition to vanadium oxide, tellurium oxide and phosphorus oxide. By containing these oxides, the reliability such as moisture resistance and water resistance can be improved and the tendency towards the crystallization can be lowered. The most effective glass compositional range is, in terms of the following oxides, 35 to 55% by mass of V2O5, 15 to 35% by mass of TeO2, 4 to 20% by mass of P2O5 and 5 to 30% by mass of one or more kinds of Fe2O3, WO3, MoO3, MnO2, Sb2O3, Bi2O3, BaO, K2O and ZnO. If the amount of V2O5 is less than 35% by mass, the softening and fluidization by the irradiation with the electromagnetic wave become not so easy. On the other hand, if the amount exceeds 55% by mass, the reliability such as moisture resistance and water resistance deteriorates. If the amount of TeO2 is less than 15% by mass, the tendency towards the crystallization becomes significant, the transition point increases and the reliability such as moisture resistance and water resistance deteriorates. On the other hand, if the amount exceeds 35% by mass, although the temperature can be lowered, the softening and fluidization by the irradiation with the electromagnetic wave become difficult. If the amount of P2O5 is less than 4% by mass, the tendency towards the crystallization becomes significant and the softening and fluidization by the irradiation with the electromagnetic wave become difficult. On the other hand, if the amount exceeds 20% by mass, the transition point increases and the softening and fluidization become not so easy even when the electromagnetic wave is applied. Furthermore, the reliability such as moisture resistance and water resistance deteriorates. If the amount of one or more kinds of Fe2O3, WO3, MoO3, MnO2, Sb2O3, Bi2O3, BaO, K2O and ZnO is less than 5% by mass, the effects for improving the reliability such as moisture resistance and water resistance, decreasing the tendency towards the crystallization and the like are hardly obtained. On the other hand, if the amount exceeds 30% by mass, these effects rather affect adversely and the softening and fluidization become not so easy even when the electromagnetic wave is applied.
The composite member of this invention shown in
The composite member of this invention can be applied as a window of a house or a car; when slurry containing a powder of the oxide glass is spray-coated or paste thereof is print-coated on one surface or both surfaces of a transparent resin base plate, the oxide glass powder is softened and fluidized by applying a laser having a wavelength in the range of 400 to 1100 nm and a fired coated film having an average thickness of 3 to 20 μm is formed on the resin base plate. A glass plate, which has high reliability, has been conventionally used for such a window; however, there were problems in that a glass plate was heavy and dangerous when it broke. By this invention, a window which is light and does not break easily can be provided. In addition, because the oxide glass is formed as a layer densely in the window of this invention, the moisture absorption and deterioration by ultraviolet rays of the resin base plate hardly occur and the surface hardness can be also improved, thereby ensuring the reliability comparable to that of a glass base plate. Moreover, this invention can be also developed into a base material of a solar battery module or an image display device, when it is formed as described above on a transparent resin base plate or resin film, and it becomes possible to provide a solar battery module and an image display device which are light and have high reliability.
Further, in this invention, it is possible to coat a coating material containing an oxide glass powder on the surface of a fiber-reinforced blade used for a wind power generator, soften and fluidize the oxide glass powder by applying a laser having a wavelength in the range of 400 to 1100 nm, and form a fired coated film having an average thickness of 10 to 50 μm on the surface of the blade. Thus, it is possible to provide a blade for a wind power generator with high reliability in which the moisture absorption and the deterioration by ultraviolet rays of the blade are prevented and the blade is not likely to be scratched due to the hard coating of the oxide glass.
In addition, in this invention, it is possible to spray-coat slurry containing an oxide glass powder or print-coat paste thereof on inner surfaces or outer surfaces of a cap and a base plate made of a rein, soften and fluidize the oxide glass powder by applying a laser having a wavelength in the range of 400 to 1100 nm, form a fired coated film having an average thickness of 3 to 20 provide an element on the base plate, put a cap, and irradiate the periphery with the laser for sealing. Thus, it is possible to develop this invention into a package electronic component which requires high gas barrier property.
Further, in this invention, it is possible to spray- or print-coat slurry or paste containing a powder of the above oxide glass on the surface of a resin panel provided in a food storage such as a refrigerator, soften and fluidize the oxide glass powder by applying a laser having a wavelength in the range of 400 to 1100 nm, and form a fired coated film having an average thickness of 3 to 20 μm. Thus, it is possible to provide a panel for a food storage which is unlikely to absorb moisture and odor.
Although the method for producing the oxide glass of this invention is not particularly limited, the oxide glass can be produced by introducing the materials, in which all oxides as raw materials have been incorporated and mixed, in a platinum crucible, heating to 900 to 950° C. in an electric furnace with a rate of temperature increase of 5 to 10° C./minute and keeping for several hours. During the materials are kept, it is desirable to stir the materials in order to obtain homogeneous glass. When the crucible is taken out from the electric furnace, it is desirable to pour the oxide glass into a graphite mold or onto a stainless plate which has been previously heated to around 150° C. in order to prevent the water adsorption of the oxide glass surface.
The resin or the rubber in this invention is not particularly limited, and both crystalline and amorphous ones can be used and not only one kind but also a combination of several kinds can be used. For example, polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyvinyl acetate, ABS resin, AS resin, acrylic resin, phenolic resin, polyacetal resin, polyimide, polycarbonate, modified polyphenylene ether (PPE), polybutylene terephthalate (PBT), polyarylate, polysulfone, polyphenylene sulfide, polyetheretherketone, polyimide resin, fluorine resin, polyamide-imide, polyetheretherketone, epoxy resin, polyester, polyvinyl ester, fluorine-containing rubber, silicone rubber, acrylic rubber and the like can be used. However, because the oxide glass is softened and fluidized by the irradiation with the electromagnetic wave while it is in contact with the resin or the rubber, the heatproof temperature of the resin or the rubber is preferably as high as possible. If the heatproof temperature of the resin is significantly lower than the transition point of the oxide glass, there is a risk that the resin or the rubber burns due to the oxide glass heated by the irradiation with the electromagnetic wave.
From the above, the composite member of this invention and a product using it maintain the advantages of an organic compound, such as the lightness and the formability at a low temperature, and can also compensate the defects such as the low gas barrier property, absorbency, odor-absorbing property, deterioration by the irradiation with ultraviolet rays and low mechanical strength (softness).
Further details are explained below using Examples. However, this invention is not limited by the descriptions of the Examples mentioned here and the Examples can be appropriately combined.
In this Example, using a polycarbonate base plate as the base material and, in terms of the following oxides, 47V2O5-30TeO2-13P2O5-10Fe2O2 (% by mass) as the oxide glass, a test of the electromagnetic wave irradiation was conducted. As the electromagnetic wave, semiconductor lasers having wavelengths of about 400 nm, 600 nm and 800 nm were used.
The oxide glass was produced by incorporating and mixing certain amounts of reagents V2O5, TeO2, P2O5 and Fe2O3 manufactured by Kojundo Chemical Laboratory Co., Ltd. in a total amount of 200 g, introducing the mixture into a platinum crucible, heating to 900 to 950° C. in an electric furnace with a rate of temperature increase of 5 to 10° C./minute and melting. In order to obtain homogeneous glass, the mixture was kept at this temperature for one to two hours while it was stirred. Then, the crucible was taken out and the glass was poured onto a stainless plate which had been previously heated to about 150° C.
The glass poured onto the stainless plate was pulverized into a powder having an average particle diameter (D50) of less than 20 μm, and the transition point (Tg), the sag point (Mg), the softening point (Ts) and the crystallization temperature (Tcry) were measured by conducting differential thermal analysis (DTA) up to 550° C. with a rate of temperature increase of 5° C./minute. In this regard, an alumina (Al2O3) powder was used as the standard sample. A typical DTA curve of the oxide glass is shown in
The moisture resistance of the oxide glass made from 47V2O5-30TeO2-13P2O5-10Fe2O3 (% by mass) was excellent. The moisture resistance was evaluated under the condition of the temperature of 85° C. and the humidity of 85% for seven days. A prismatic column of 4×4×20 mm was used as the evaluation sample and the sample was evaluated as “A” when no change in the appearance was observed or as “C” when change was observed. The oxide glass above was “A”.
The optical characteristics of the oxide glass made from 47V2O5-30TeO2-13P2O5-10Fe2O3 (% by mass) were evaluated by the transmittance using an ultraviolet and visible spectrophotometer. As the evaluation sample, paste for printing was produced by pulverizing the oxide glass produced into a powder having an average particle diameter (D50) of 2 μm or less with a jet mill, introducing a solvent in which a 4% resin binder was dissolved to the glass powder and mixing. Here, ethyl cellulose was used as the resin binder and butyl carbitol acetate was used as the solvent. This paste was coated on glass slides by screen-printing, dried at 150° C. and then fired in the atmosphere at 400° C. As the firing temperature profile, a two-step profile was used and the resin binder was volatilized and removed by first heating to 350° C. with a rate of temperature increase of 10° C./minute and keeping for 30 minutes. Then, by heating to 400° C. also with a rate of temperature increase of 10° C. and keeping for 10 minutes, fired coated films of the oxide glass were obtained. The viscosity of the paste and the printing method were controlled so that the average thicknesses of the fired coated films became about 5 μm, 10 μm and 20 μm. Regarding the fired coated films formed on the glass slides, transmittance curves in the wavelength range of 300 to 2000 nm were measured using an ultraviolet and visible spectrophotometer. In this regard, the transmittance curve of the glass slide only was subtracted as the base line so as to obtain the transmittance curves as close to those of the fired coated films of the oxide glass only as possible. The transmittance curves of the oxide glass made from 47V2O5-30TeO2-13P2O5-10Fe2O3 (% by mass) regarding various thicknesses are shown in
Using the above sample for optical evaluation, the electrical resistance of the fired coated film of the oxide glass made from 47V2O5-30TeO2-13P2O5-10Fe2O3 (% by mass) was measured. The measurement was conducted at room temperature by a four-terminal method; the specific resistance was 5.3×106 Ω·cm and semiconductor-like conductivity was observed.
In the test of the electromagnetic wave irradiation, the oxide glass was pulverized into a powder having an average particle diameter (D50) of 2 μm or less with a jet mill and used as described above. By introducing a solvent in which a 1% resin binder was dissolved to the glass powder and mixing, slurry for spraying was produced. Here, ethyl cellulose was used as the resin binder and butyl carbitol acetate was used as the solvent. This slurry was evenly sprayed on a polycarbonate base plate and dried at about 70° C. Then, semiconductor lasers having wavelengths of about 400 nm, 600 nm and 800 nm were each applied. Regarding the irradiation method, by moving the heads of the lasers, the composite member shown in
Next, the composite member shown in
Next, the composite member shown in
As in Example 1, the oxide glass made from 47V2O5-30TeO2-13P2O5-10Fe2O3 (% by mass) was formed on base plates and films of polyimide, polyamide-imide, polyarylate, polysulfone, epoxy resin, fluorine resin, fluorine-containing rubber, silicone rubber and acrylic rubber, instead of the polycarbonate base plate, and the composite members as shown in
Next, a fluorine resin base plate on which slurry of the oxide glass was coated and dried was irradiated with a microwave of 2.45 GHz band (wavelength: 125 mm) using a μReactor manufactured by Shikoku Instrumentation CO., Inc. and the composite member of
Layers of the oxide glass made from 47V2O5-30TeO2-13P2O5-10Fe2O3 (% by mass) having different thicknesses were formed on a polyimide film having a thickness of 25 μm as in Example 1, and composite members as shown in
In Comparative Example a, in which the polyimide film alone was used, the moisture vapor transmission rate was high. On the other hand, with the polyimide films of Comparative Examples b and c in which a SiO2 film was formed by sputtering method or sol-gel method, the moisture vapor transmission rates were decreased but the gas barrier property was not excellent. It is thought that this is because of the small thicknesses. In addition, it is thought that, because Comparative Example c was not completely mineralized and an organic material was contained a little, the moisture vapor transmission rate thereof was higher than that of Comparative Example b.
In comparison to Comparative Examples a, b and c, the moisture vapor transmission rates could be significantly decreased in Examples A, B, C and D. In particular, in Examples B, C and D, in which the average thicknesses of the oxide glass were 3 μm or more, the moisture vapor transmission rate was hardly observed and it can be said that the gas barrier property was almost perfect. It is thought that such excellent gas barrier property was obtained because the oxide glass was softened and fluidized by the irradiation with the electromagnetic wave and bonded and adhered to the polyimide film as an even and dense layer. It is thought that the gas barrier property of Example A was inferior to those of Examples B, C and D because the homogeneity deteriorated due to the smaller average thickness. Even if the average thickness is small, it is certain that the gas barrier property improves when a dense layer can be evenly formed. For this, it is effective to decrease the particle diameter of the oxide glass powder.
In this Example, the composition and characteristics of the oxide glass were studied. The compositions and characteristics of the oxide glass studied are shown in Table 2. As the glass raw materials, reagents V2O5, TeO2, P2O5, Fe2O3, WO3, MoO3, MnO2, Sb2O3, Bi2O3, BaCO3, K2CO3 and ZnO manufactured by Kojundo Chemical Laboratory Co., Ltd. were used and the oxide glass was produced as in Example 1. The transition point of the oxide glass produced was measured by DTA as in Example 1. Further, the water resistance was evaluated also as in Example 1. An oxide glass powder was pressed and formed by hand pressing; a titanium sapphire laser (wavelength: 808 nm), a YAG laser (wavelength: 1064 nm) and a microwave of 2.45 GHz band (wavelength: 125 mm) were each applied; and the softness and fluidity of the oxide glass produced was evaluated as “A” when the oxide glass could be fluidized, as “B” when it could be softened and as “C” when it could not be fluidized nor softened.
As it is seen from Examples G12, 14, 15, 17, 20-25, 27-30, 33, 35-37 and 39-48 in Table 2, the samples with excellent moisture resistance satisfied the relation V2O5>TeO2≧P2O5 (% by mass) and the total amounts of the oxides were 70% by mass or more and 95% by mass or less. Here, the transition points of the oxide glass were 330° C. or lower and the moisture resistance properties were also excellent. Furthermore, the softness and fluidity properties by the irradiation with the electromagnetic waves such as the lasers and the microwave were also excellent and it is possible to produce the composite members shown in
In this Example, the potential as a window was studied. Using a polycarbonate base plate having a thickness of 3 mm as a transparent resin base plate, the oxide glass of G41 shown in Table 2 was formed on one surface or both surfaces thereof as in Example 1 in such a way that the average thickness became around 5 to 10 μm, and the composite member for a window as shown in
In this Example, the potential as a solar battery module was studied. Using a polycarbonate base plate having a thickness of 3 mm as a transparent resin base plate as in Example 5, the oxide glass of G41 shown in Table 2 was formed on one surface thereof as in Example 1 in such a way that the average thickness became around 3 μm, and the composite member for a solar battery module base plate as shown in
In this Example, the potential as an image display device was studied. A flexible organic light-emitting diode (OLED) display was produced as the image display device. A schematic cross-sectional view of the OLED display produced is shown in
The OLED display produced was set in wet air at the temperature of 50° C. and the relative humidity of 90% and connected to an alternating-current source of 100 V 400 Hz, and the brightness thereof was measured by lighting it up continuously for 500 hours. The change of the brightness over time was measured but the brightness was scarcely decreased, and the composite member of this invention can be developed into an image display device such as an OLED display.
In this Example, the potential as a blade for a wind power generator was studied. A schematic cross-sectional view of the blade for a wind power generator produced is shown in
In this Example, the potential as a package electronic component was studied. A schematic cross-sectional view of the package electronic component produced is shown in
In this Example, the potential as a resin panel or the like provided in a food storage such as a refrigerator was studied. An acrylic resin was used as the resin panel. The oxide glass G48 in Table 2 was formed on this resin panel as in Example 1 by the irradiation with an electromagnetic wave in such a way that the average thickness became around 10 μm. A semiconductor laser having a wavelength of about 800 nm was used for the electromagnetic wave irradiation. An odor absorption test of the acrylic resin panel on which G48 was formed was conducted. Odor was absorbed in case of the acrylic resin panel only while the acrylic resin panel on which G48 was formed did not absorb odor, and thus it was found that the panel can be developed into a panel for a food storage such as a refrigerator. Further, from this finding, it goes without saying that the development into a bath-tub, a toilet and the like is also expected. A toilet constituted by a resin or the like may be produced.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-282622 | Dec 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2012/080119 | 11/21/2012 | WO | 00 |
