JP4958136B2 - Hybrid of polyethylene glycol and copper (II) oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means capable of exhibiting characteristics of copper (II) oxide, by mixing the copper (II) oxide into polyethylene glycol, while keeping excellent flexing properties and transparency of the polyethylene glycol, and to provide a hybrid capable of being applied to a glass base, a polymeric resin base, etc., by a single layer, without being required to be laminated, and having ultraviolet ray cutting properties and heat ray cutting properties. <P>SOLUTION: The hybrid of the polyethylene glycol and the copper (II) oxide, the hybrid having the ultraviolet ray cutting properties and the heat ray cutting properties, and a method for producing the hybrid by a sol-gel process are provided, respectively. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a hybrid of polyethylene glycol and copper (II) oxide. The present invention also relates to the hybrid having ultraviolet cut ability and heat ray cut ability. The present invention further relates to a method for producing the hybrid by a sol-gel method.

  Since polyethylene glycol is excellent in chemical resistance, flexibility, tensile strength, and transparency, it is widely used as a packaging film for foods and pharmaceuticals. Further, copper (II) oxide is useful as an additive because of its use as a pigment and paint, and also has heat ray cutting properties, but it is inferior in flexibility.

  Therefore, in order to meet the demands for UV-cutting properties and heat ray-cutting properties in food and pharmaceutical packaging films and organic glass, etc., polyethylene glycol containing copper oxide (II) is used as a packaging film. It is conceivable to use it by laminating it on a polymer resin substrate, organic glass substrate, etc., but the refractive index of both is greatly different, so the excellent flexibility and transparency of polyethylene glycol is maintained. However, it is not easy to contain copper (II) oxide.

There has also been proposed a heat ray cut filter in which an ITO film, which is a metal oxide film, and a dielectric film are formed on a translucent glass substrate, but the metal oxide film and the dielectric film are laminated on the substrate. For this reason, problems such as peeling occur, which is not satisfactory (see Patent Document 1). In addition, there are cases where metal oxides exhibit a strong oxidizing action when exposed to ultraviolet rays such as sunlight, and there is a problem of weather resistance such as deterioration of a polymer resin substrate or an organic glass substrate.
Japanese Patent Laid-Open No. 7-74667

  An object of the present invention is to provide a means for containing copper oxide (II) while maintaining the excellent flexibility and transparency of polyethylene glycol and exhibiting the characteristics of copper oxide (II), and a glass substrate, It is an object of the present invention to provide a hybrid having an ultraviolet ray cutting property and a heat ray cutting property which can be applied as a single layer without being laminated on a polymer resin substrate.

  By considering copper oxide (II), which is a metal oxide, as one monomer, the present inventors have attempted to directly react with polyethylene glycol, which is a kind of polymer resin that has been conventionally used as a substrate constituent material, When a hybrid of polyethylene glycol and copper oxide (II) (hereinafter referred to as “hybrid” is sometimes referred to as “hybrid film”, which is a typical application form) by a sol-gel method) It has been found that both characteristics of copper (II) oxide can be maintained, and the optical characteristics and physical properties of the film are extremely excellent.

  In other words, polyethylene glycol, which is excellent in transparency and flexibility, is combined with copper oxide (II) that has both UV-cut and heat-ray-cut properties while maintaining the excellent transparency and flexibility of polyethylene glycol (hybrid). Thus, it has been found that the problem of the present invention of imparting UV-cutting properties and heat ray-cutting properties to polyethylene glycol can be solved by preparing a hybrid film of polyethylene glycol and copper (II) oxide by a sol-gel method. .

  The hybrid film of polyethylene glycol and copper (II) oxide obtained according to the present invention is excellent in both optical properties and physical properties, but in particular, what is conventionally laminated on a glass substrate or a polymer resin substrate is an ultraviolet shielding layer. If it is, if it was ultraviolet-cut property and it was limited to heat-ray cut property if it was a heat ray shielding layer, it is worth noting that the hybrid film of this invention has transparency, ultraviolet-ray cut property, and heat ray-cut property.

  According to the sol-gel method, a hybrid film in which polyethylene glycol, which is an organic polymer, and copper (II) oxide, which is a metal oxide, are combined at a so-called molecular level, that is, nanometer order can be obtained. Both are considered to be integrated by covalent bond or Coulomb force bond. The obtained hybrid film has an integrated single-layer structure, but substantially shields ultraviolet rays in the entire region of 400 nm or less and near infrared rays in the vicinity of 850 to 1020 nm (generally referred to as “heat rays”). have.

  The amount of the copper (II) oxide to be complexed is preferably 0.6 to 30% by weight based on polyethylene glycol, more preferably 3 to 14% by weight based on polyethylene glycol.

  The thickness of the transparent hybrid film is preferably 50 to 500 μm, more preferably 100 to 300 μm.

A process diagram for obtaining the hybrid of the present invention is shown in FIG.
As shown in FIG. 1, first, 3-isocyanatopropyltriethoxysilane was added to polyethylene glycol having a number average molecular weight of 600 (hereinafter sometimes referred to as “PEG”), and 1 at 90 ° C. in a nitrogen gas atmosphere. The mixture is stirred for a day to obtain an ethoxysilane derivative-polyethylene glycol complex (ET-PEG). Ethyl alcohol is added to make a 20 wt% solution. To the solution is added a copper (II) ethoxide 20% by weight ethyl alcohol solution obtained by reacting copper (II) ethoxide, hydrochloric acid (2N) and ethyl alcohol, and the mixture is stirred for 10 minutes and dried for 7 days. Subsequently, it is vacuum-dried at 30 ° C. for 3 days to obtain a hybrid material of polyethylene glycol and copper (II) oxide (hereinafter sometimes referred to as “PEG / CuO hybrid”).
It was found that when the obtained PEG / CuO hybrid material is heat-treated, a high protective effect of ultraviolet rays and heat rays can be obtained even if the film thickness is reduced.

  Examples of the present invention will be described below.

2 to 4 show how the transmittance at each wavelength varies depending on the composite amount of copper (II) ethoxide. The horizontal axis represents wavelength (nm), and the vertical axis represents transmittance (%). FIG. 2 shows ultraviolet-visible (UV-VIS) spectrophotometric data in a wide area, FIG. 3 shows spectrophotometric data in the ultraviolet area, and FIG. 4 shows spectrophotometric data in the heat ray area.
2-4, the film thickness was 250 micrometers.

  As can be seen from FIG. 3, those containing no copper (II) oxide transmit ultraviolet rays, whereas when the composite amount of copper (II) ethoxide is 1% by weight or more, a region of 400 nm or less including ultraviolet rays is included. It turns out that it can cut completely.

  In addition, as can be seen from FIG. 4, in the heat ray region of 750 nm or more, those containing no copper (II) oxide transmit about 90% of the heat rays, whereas the composite amount of copper (II) ethoxide is 1% by weight. Then, it can be cut almost half, and when the composite amount of copper (II) ethoxide is 15% by weight or more, it can be seen that it can be cut almost completely.

FIG. 5 shows how the transmittance (%) at a wavelength of 900 nm varies depending on the thickness of the filmed PEG / CuO hybrid. The horizontal axis represents the film thickness (μm), and the vertical axis represents the transmittance (%) at a wavelength of 900 nm.
In FIG. 5, the composite amount of copper (II) ethoxide was 15% by weight.

  FIG. 6 shows how the transmittance (%) at a wavelength of 900 nm varies depending on the composite amount of copper (II) ethoxide and the thickness of the filmed PEG / CuO hybrid. The horizontal axis represents the composite amount (% by weight) of copper (II) ethoxide, and the vertical axis represents the film thickness (μm).

  From FIG. 5 and FIG. 6, if the composite amount of copper (II) ethoxide is about 1% by weight or more, the transmittance (%) at a wavelength of 900 nm is decreased even when the film thickness is 500 μm or less. It turns out that the transmittance | permeability (%) in wavelength 900nm falls further with the increase in thickness, and the effect of the heat ray cut of this invention is remarkable.

  In the step of FIG. 1, after vacuum drying at 30 ° C. for 3 days, heat treatment was further performed at 60 ° C. for 3 days (= 72 hours). The copper (II) ethoxide complex amount was 10% by weight, and the film thickness was 180 μm. FIG. 7 shows a broad region of UV-visible to see the effect obtained by the heat treatment by comparing with the case of the copper (II) ethoxide complex amount of 15% by weight and the film thickness of 250 μm in FIG. 2 (no heat treatment). (UV-VIS) shows spectrophotometric data.

  As can be seen from FIG. 7, in the heat ray region and the ultraviolet region near about 800 to 1000 nm, both hybrid materials are well protected. However, in the visible light region, the composite amount of copper (II) ethoxide is small, and even if the film thickness is thin, the heat-treated hybrid material has a wider visible light transmitting region and higher transmittance. I found out that In other words, it was found that the heat-treated hybrid material can reduce the amount of copper (II) ethoxide complex and reduce the thickness of the film, and can be a material rich in optical characteristics.

The process drawing which obtains the hybrid of this invention is shown. 1 shows wide area ultraviolet-visible (UV-VIS) spectrophotometric data. The spectrophotometric measurement data in the ultraviolet region are shown. The spectrophotometric measurement data of a heat ray area | region are shown. It shows how the transmittance (%) at a wavelength of 900 nm varies depending on the thickness of the filmed PEG / CuO hybrid. The figure shows how the transmittance (%) at a wavelength of 900 nm varies depending on the composite amount of copper (II) ethoxide and the thickness of the filmed PEG / CuO hybrid. Figure 2 shows a wide area ultraviolet-visible (UV-VIS) spectrophotometric data to see the effect obtained by heat treatment.

Claims (2)

A film for cutting ultraviolet rays and heat rays, comprising a hybrid material of polyethylene glycol and copper (II) oxide . The film according to claim 1, wherein the hybrid material is a material that is heat-treated after a hybrid of polyethylene glycol and copper (II) oxide is formed by a sol-gel method .

Images