JP2005118493A - Plasma-polymerized sugar membrane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sugar membrane having physical and chemical characteristics materializing a membrane of sugars such as glucose and industrially practically using it without impairing its hydrophilicity and biocompatibility as original functions of the sugars. <P>SOLUTION: This plasma-polymerized sugar membrane is so constituted that the membrane is formed by plasma enhancement of the sugars of one kind or more out of monosaccharides and polysaccharides. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The invention of this application relates to a plasma polymerized saccharide film. More specifically, the invention of this application is a new plasma that has biocompatibility and hydrophilicity, and is useful for surface treatment, surface modification, etc. in various fields such as the medical, chemical, electrical, and electronic industries. The present invention relates to a polymerized saccharide membrane.

  Various attempts have been made in the past to form various thin films by polymerizing and crosslinking these organic substances by exciting various organic substances in a plasma atmosphere, and these plasma-polymerized films have already been put into practical use. Some have.

  In any case, the plasma polymerized film has a three-dimensional structure that is highly cross-linked by plasma excitation that cannot be obtained by normal chemical reaction or thin film by applying polymer solution, or by vacuum deposition, CVD, etc. As a thin film with excellent adhesion to the substrate, ultra-thin film without pinholes with high density and denseness of the thin film, and a unique function derived from the organic material used as the target A characteristic thin film is formed (see Non-Patent Document 1, for example).

  The functions and applications of the plasma polymerized film with such characteristics are wide, such as surface protective film, insulating film, antireflection film, humidity sensor, biochemical sensor, separation film, biomaterial, VILI and other electronic devices. It covers a wide area.

  A wide variety of organic substances for forming plasma polymerized films have been targeted, including hydrocarbons such as ethylene, propylene, and fluorocarbons, oligomers or polymers thereof, silicon compounds, and polyethers. Substances having various functional groups such as compounds have also been targeted.

  On the other hand, the importance of glucose and other saccharides has attracted attention as a biological constituent, but it has not been attempted to make these saccharides thin, and it is almost assumed that they will be developed as plasma polymerized membranes. Not even been.

  With respect to a thin film of saccharides such as glucose, there are great expectations for treatment or modification of the surface of an artificial organ, for example, by taking advantage of the hydrophilicity and biocompatibility characteristic of saccharides. However, in actuality, a chemical reaction must be performed in a thin film by a normal chemical method, and the chemical structure of the thin film formed in that case changes considerably, such as hydrophilicity and characteristics such as glucose. Biocompatibility is impaired. In addition, it is difficult to form a thin film by physical coating or vapor deposition in a gas phase, and the substance is not a thin film but is a state in which granular glucose is placed on a substrate. Thin-film glucose and the like easily dissolve in water and are not suitable for surface treatment / modification of various materials.

From the location of such problems, conventionally, it has hardly been assumed that a thin film of sugar such as glucose is formed by plasma polymerization.
“Chemical Dictionary” (Tokyo Kagaku Doujin), page 2028 (1989.10.20)

  Therefore, the invention of this application has realized the realization of thinning of saccharides such as glucose based on the above background and the location of problems, and impairs hydrophilicity and biocompatibility as the original functions of saccharides. The object is to provide a new thin film having physical and chemical properties that can be practically used in the industry without any trouble.

  The invention of this application provides a plasma polymerized saccharide film characterized in that, first, a saccharide formed by plasma excitation of a saccharide, and secondly, There is provided a plasma polymerized saccharide film characterized by being one or more of monosaccharides and polysaccharides.

  The invention of this application provides, in a third aspect, the above-mentioned plasma polymerized saccharide film, which is a hydrophilic film having a contact angle of 20 ° or less, and fourth, a cross-cut adhesion test. A plasma polymerized saccharide film having a value of 10 is provided.

  According to the invention of this application as described above, glucose is thinned while maintaining the hydrophilic and biocompatible functions of saccharides such as glucose, and further has no solubility in a solvent such as water, and the surface of the material is treated. A thin film is provided that achieves hydrophilicity and biocompatibility of the material surface by modification. This thin film is a new thin film that has never been seen before.

  The invention of this application has the features as described above, and an embodiment thereof will be described below.

  The plasma polymerized saccharide film of the invention of this application can be based on a conventionally known method and apparatus for forming the thin film. In plasma polymerization, a saccharide substance is excited as a high-frequency excitation plasma to form a thin film on a substrate. In this case, the generation and introduction of plasma may be various, including a substrate facing type and a high-frequency antenna method, In any case, a so-called glow discharge plasma is generated, and a saccharide is excited by this plasma to form a thin film. For example, thin film formation by low-temperature plasma in a vacuum vacuum chamber is considered as a typical method, but an atmospheric pressure glow discharge plasma method may be adopted.

As for the mode for forming a thin film, for example, in a low temperature plasma method, an inert gas such as argon (Ar) or helium (He) is preferably introduced under a vacuum at a pressure of 1 × 10 ⁻¹ Pa or less. Then, a glow discharge plasma is generated and evaporated, or a saccharide introduced in a gaseous state is excited by the plasma to form a film on the substrate. It may be considered to introduce oxygen or hydrogen together with the inert gas, for example. In any case, the physical properties of the formed saccharide thin film can be controlled by controlling the high frequency power for plasma generation, the composition and supply of the introduced gas, or the temperature of the substrate.

  The saccharide may be evaporated in the vacuum chamber by means of resistance heating, induction heating, electron beam radiation or the like, or may be introduced into the vacuum chamber in the vaporized gas state as described above.

  The saccharide as a raw material has the following formula

It may be various substances such as glucose as saccharides represented by the formula, or various kinds of polysaccharides including disaccharides and trisaccharides. Of course, these may be used in combination. Selection may be made according to the properties and functions of the thin film to be formed.

  As the thin film of the invention of this application, a thin film with good hydrophilicity having a contact angle of 20 ° or less is provided. Moreover, a water-insoluble thin film is realized.

  Further, in the cross-cut adhesion test, an extremely thin adhesive film having a value of “10” is obtained. Depending on the film forming conditions, a material to be peeled may be formed. This can be applied as a peeled state.

  Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.

  As the thin film forming apparatus, the one having the configuration shown in FIG. 1 was used. The reference numerals in the figure indicate the following.

AFG: High frequency power supply IM: Matching box S: Substrate U: Upper electrode M: Monomer L: Lower electrode Ar: Argon gas RP: Rotary pump In this apparatus, as a raw material monomer (M) on the glass surface as the substrate (S) A plasma polymerized film of glucose was formed. The inside of the apparatus was evacuated to 5 × 10 ⁻² Pa, and argon (Ar) was introduced at 10 ml / min. The temperature of the glass substrate was 25 ° C.

  The characteristics of the formed glucose plasma polymerized film were evaluated by changing the power of the high-frequency power source.

  Table 1 shows the change in the abundance ratio of C (carbon) and O (oxygen) by ESCA (XPS: X-ray photoelectron spectroscopy). FIG. 2 shows the thin film in the case of glucose and 10 W and 50 W. An IR spectrum is shown.

  It can be seen that the degree of polymerization and cross-linking of glucose molecules are becoming higher with the increase in power.

  Table 2 shows the contact angle of the formed thin film, and it can be seen that the glucose thin film formed by plasma polymerization has good hydrophilicity at less than 50 W. Moreover, although the raw material glucose itself is readily soluble in water, it was confirmed that the plasma-polymerized thin film is insoluble in water due to cross-linking between glucose molecules.

  Table 3 also shows the results of the cross-cut adhesion test, which shows that excellent adhesion is obtained.

  FIG. 3 shows the state of platelet adhesion on the formed thin film.

  The result of contacting red blood cells with a thin film is shown, and it can be seen that a thin film at 10 W is superior in biocompatibility to a thin film formed at 50 W. In addition, it is confirmed that even a 50 W thin film has better biocompatibility than conventional materials.

  As described in detail above, according to the invention of this application, a thin film that is hydrophilic, insoluble in water, excellent in biocompatibility, and excellent in film adhesion is provided.

  Because of these characteristics, the plasma polymerized saccharide membrane of the invention of this application can be used for surface treatment / modification of biotechnology materials using biological materials or cells. Cells may be destroyed by the shape and properties of the surface of the material, and materials that do not affect the cells are currently used. The plasma polymerized saccharide membrane of the invention of this application is It is possible to easily hydrophilize the surface of a material and modify it to have excellent biocompatibility, which will expand the range of materials used for biotechnology research and contribute to the development of the biotechnology field. It is.

  In addition, since it is easy to coat with water, is a hydrophilic thin film, and is excellent in biocompatibility, it can be used for surface treatment and modification of artificial organs and pacemakers used for transplantation and the like. In the materials for artificial organs and pacemakers used so far, the compatibility with the living body including surface treatment and modification had to be specially considered. By using it, it will be possible to develop without worrying about the material of the material, it will expand the range of choice of material use in the medical field, and it will be possible to save human lives that have been lost so far .

  In recent years, research on microreactors that perform chemical reactions in the micro region has been actively conducted because chemical reactions have a high impact on the environment. However, the materials used for the microreactor are limited, and the surface is hardly studied. However, the plasma polymerized saccharide membrane of the invention of this application can easily process and modify the surface of materials on the micro order, and contributes to widening the scope of microreactor research.

  Furthermore, anti-fogging is desired for various material surfaces by hydrophilization and water repellency. The plasma-polymerized saccharide film of the invention of this application is very hydrophilic, has a high antifogging effect, and enables the formation of an antifogging film on various material surfaces.

  As mentioned above, it is possible to impart hydrophilicity and biocompatibility to the surface of the material regardless of the material and shape of the material. It contributes enough.

It is the schematic which showed the structure of the film-forming apparatus in an Example. It is the figure which showed IR spectrum. It is the figure shown about adhesion of platelets.

Claims (4)

  A plasma polymerized saccharide film characterized by being a thin film formed by plasma excitation of saccharides.   The plasma-polymerized saccharide film according to claim 1, wherein the saccharide is one or more of monosaccharides and polysaccharides.   The plasma-polymerized saccharide film according to claim 1 or 2, wherein the film is a hydrophilic film having a contact angle of 20 ° or less. 4. The plasma-polymerized saccharide film according to claim 1, wherein the cross-cut adhesion test value is 10.

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