JP2004231970A - Surface modification method, water-repellent polymer material obtained by the method and clothing, paper and rubber using the material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface modification method surely imparting water repellency by treating the surface of a synthetic or natural polymer material, to provide a polymer material obtained by the method, and to provide clothing, paper and rubber using the material. <P>SOLUTION: The method comprises treating a synthetic or natural polymer with a gas containing fluorine gas and an inert gas to impart water repellency, wherein, as the synthetic or natural polymer material, a material having ≤1.6 specific gravity and containing neither ether bond, carbonate bond, amide bond nor urethane bond is selected so as to make the contact angle to water and of the treated by the method ≥10° larger than that of the untreated. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a surface modification method for making a synthetic or natural polymer material water-repellent, a surface-modified synthetic or natural polymer material, and clothing, paper and rubber using the same.

  BACKGROUND ART Conventionally, a surface treatment method for a synthetic polymer and a natural polymer material which is subjected to a surface treatment on a synthetic polymer and a natural polymer material to make it water-repellent has been studied.

For example, as a water repellent treatment method, there is a surface treatment method for a molded rubber material disclosed in Patent Document 1 below. In this method, a molded rubber material is held at a temperature of about 10 to 150 [deg.] C. in a flow of a fluorine gas or a mixed gas of a fluorine gas and an inert carrier gas to make the surface of the molded rubber water-repellent.
JP-A-56-126146

  However, even with these conventional water-repellent treatments, water-repellent functions may not be efficiently provided.

  Therefore, the present invention provides a surface modification method capable of surface-treating a synthetic or natural polymer material to reliably impart water repellency, a water-repellent polymer material by the method, and clothing, paper, and the like using the same. The purpose is to provide rubber.

  The surface modification method for imparting water repellency to a synthetic or natural polymer material according to the present invention for solving the above-mentioned problems is performed by treating a synthetic or natural polymer material with a gas containing a fluorine gas and an inert gas. A surface modification method for imparting aqueous properties, wherein a material having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond is selected as the synthetic or natural polymer material. By doing so, the contact angle with water after the treatment is increased by 10 ° or more than before the treatment. Preferably, the concentration of the fluorine gas is 5 to 95 Vol%.

  Further, the synthetic polymer material is preferably a material selected from a thermosetting resin, a thermoplastic resin, and a rubber-like polymer. The natural polymer material is preferably a material selected from natural rubber, cellulose, cellulose ester, cotton, silk, and flax.

  The present invention is a polymer material having a water-repellent surface, and can be used as clothing, paper, and rubber.

  Examples of the synthetic polymer material used in the present invention include phenol resins, xylene resins, thermosetting resins such as epoxy resins, polyethylene, polyethylene chloride, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, polypropylene, Polymethylpentene, polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, acrylonitrile-chlorinated polyethylene-styrene (ACS) resin, methyl methacrylate resin, methacrylstyrene copolymer resin, chloride Vinyl resin, vinyl chloride vinyl acetate copolymer resin, vinyl chloride vinylidene chloride copolymer resin, vinyl chloride acrylate copolymer resin, vinyl methacrylic acid copolymer resin, vinyl chloride acrylonitrile copolymer resin, ethylene chloride Cycloalkenyl copolymer resin, propylene-vinyl chloride copolymer resin, vinyl acetate resin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polysulfone, ethylene-tetrafluoroethylene copolymer resin, thermoplastic resins such as polybutylene can be exemplified.

  Examples of the rubbery polymer include butadiene styrene copolymer (styrene butadiene rubber), butadiene acrylonitrile copolymer (nitrile rubber), butyl rubber, polyisobutylene, chlorosulfonated polyethylene, polybutadiene (butadiene rubber), chloroprene rubber, Examples thereof include ethylene propylene rubber and acrylic rubber.

  Examples of the natural polymer include natural rubber, cellulose, cellulose ester, cotton, silk, flax and the like.

  Here, in a synthetic or natural polymer material having a specific gravity of 1.6 or less, the diffusion of fluorine gas in the material is extremely good and easily spreads to the reaction site of the surface-modified material. For this reason, the surface of the surface-modified product is easily modified. On the other hand, if the specific gravity is larger than 1.6, the crystal structure of a synthetic or natural polymer material has been developed, so that diffusion of fluorine gas is not easy, so that the function of surface modification is hardly exhibited.

  Further, those having an ether bond, a carbonate bond, an amide bond, or a urethane bond are not preferred because they are easily decomposed by contact with fluorine gas and it becomes difficult to impart a water repellent function. The ether bond, carbonate bond, amide bond, and urethane bond on the surface of the synthetic or natural polymer material are each bonded using a Fourier transform infrared spectrophotometer (FT-IR) 5300 type manufactured by JASCO Corporation. Was measured.

  Hereinafter, a surface modification method for making these synthetic polymer materials or natural polymer materials water-repellent will be described.

  When imparting water repellency, a synthetic or natural polymer material is placed in a processing vessel, and the pressure in the processing vessel is reduced to several hundred Pa or less. Next, the atmosphere is replaced with an inert gas. Here, the inert gas refers to a nitrogen gas, a helium gas, an argon gas, or the like. Thereafter, the fluorine gas is introduced into the container so as to be 5 to 95 vol%. The treatment time for contact with the fluorine gas is 1 second to 10 days, preferably 10 minutes to several hours. The processing temperature is 0 to 200 ° C, preferably room temperature to 100 ° C.

In addition, the term “water repellency” as used in the present invention refers to the synthesis or water repellency of a synthetic or natural polymer material after water repellency treatment with fluorine gas, which is greater than the contact angle (θ) of water with respect to water. It is defined that the contact angle (θ ₁ ) of the natural polymer material to water becomes larger by 10 ° or more, and the relationship between θ and θ ₁ can be expressed as in Equation 1.
θ ₁ −θ ≧ 10 ° (Equation 1)

  Here, the contact angle with water was measured by using a G-1 type device manufactured by Elma, cutting a polymer material having a thickness of 1 mm into 10 × 20 (mm), and applying a diameter of 0.5 mm to one sample. Water droplets of the same order were formed with 10 syringes, the contact angles of each were measured with the above-mentioned device, and the average value was obtained. This operation was repeated 10 times, and the average value was used as the measured value of the contact angle of one sample.

  The specific gravity was measured by the Pycnometer method among the methods for measuring the density and specific gravity of plastic-non-foamed plastic (JIS K7112 (1999)).

  When making these synthetic polymer materials or natural polymer materials water-repellent, the method of bringing them into contact with a fluorine gas or a mixed gas containing a fluorine gas is, as described above, a batch method in which a treatment container is installed for each treatment product. In addition to the formula processing method, a continuous processing method may be used. The continuous treatment method is a method in which a synthetic polymer material or a natural polymer material is passed through fluorine gas or a mixed gas containing fluorine gas and brought into contact therewith.

  Here, the fluorine gas used in the present invention is usually obtained by electrolysis of hydrogen fluoride. It is also possible to directly use the fluorine gas obtained by such electrolysis for the treatment. It is also possible to use fluorine gas filled in a cylinder.

  It is very important to replace the atmosphere in the processing container before introducing the fluorine gas.If this order is reversed, the function of water repellency will not be exhibited, or the substrate will be decomposed and burned. There is.

  As described above, the surface of a synthetic polymer material or a natural polymer material can be made water-repellent without impairing the strength, chemical resistance, and heat resistance of the material. By modifying the surface in this way, each can be used for clothing, paper, rubber, and the like.

  Note that it is possible to partially make the surface of a synthetic polymer material or a natural polymer material water repellent by partially masking and treating the surface with water repellency. This makes it possible to use a synthetic polymer material or a natural polymer material having different characteristics on the front and back surfaces, or a synthetic polymer material or a natural polymer material whose characteristics are inclined.

  In the present invention, a natural or synthetic polymer material having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond that inhibits the imparting of water repellency by gas containing fluorine gas is used. Since a selective treatment is performed, a water-repellent function can be easily provided.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

(Example 1)
As the thermoplastic resin, a low-density polyethylene having a specific gravity of 0.91 and not containing any of an ether bond, a carbonate bond, an amide bond, and a urethane bond is used. This is placed in a processing container, and the pressure is reduced to 100 Pa. After introducing and replacing the gas in the processing container, fluorine gas was introduced. The fluorine gas was introduced such that the gas mixture ratio in the processing container after introduction was 80 vol% of nitrogen gas and 20 vol% of fluorine gas. Thereafter, the material was reacted at 70 ° C. for 60 minutes to perform a water repellent treatment on the surface of the material.

(Example 2)
Except for using a chloroprene rubber having a specific gravity of 1.3 and containing no ether bond, carbonate bond, amide bond, or urethane bond as the rubber-like polymer material, the surface of the material was obtained in the same manner as in Example 1. Was subjected to a water-repellent treatment.

(Example 3)
A natural polymer material having a specific gravity of 1.5 and containing neither an ether bond, a carbonate bond, an amide bond, nor a urethane bond is used. The cotton is put into a treatment container, and the pressure is reduced to 100 Pa. Then, nitrogen gas is introduced. After replacing the gas in the processing container, fluorine gas was introduced. The fluorine gas was introduced such that the gas mixture ratio in the processing vessel after introduction was 95 vol% of nitrogen gas and 5 vol% of fluorine gas. Thereafter, the material was reacted at 20 ° C. (room temperature) for 10 minutes to perform a water-repellent treatment on the surface of the material.

(Comparative Example 1)
The same as in Example 1 using a thermoplastic resin having a specific gravity of 2.15 and a tetrafluoroethylene-perfluoroalkoxyethylene copolymer resin (PFA) containing neither an ether bond, a carbonate bond, an amide bond, nor a urethane bond. The surface of the material was subjected to a water-repellent treatment by a simple operation procedure.

(Comparative Example 2)
A polyurethane having a specific gravity of 1.21 and containing a urethane bond was used as the thermosetting resin, and the surface of the material was subjected to a water-repellent treatment in the same operation procedure as in Example 1.

(Comparative Example 3)
Using a polycarbonate having a specific gravity of 1.2 and containing a carbonate bond as a thermoplastic resin, the surface of the material was subjected to a water-repellent treatment in the same operation procedure as in Example 1.

  For the samples of Examples 1 to 3 and Comparative Examples 1 to 3, the types of synthetic or natural polymer materials, specific gravity, presence / absence of bonding that becomes an inhibitory factor for imparting water repellency function, processing conditions, contact angles, and the like are summarized. 1 is shown.

  As is clear from Table 1, a synthetic or natural polymer material having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond has water repellency by a gas containing fluorine gas. Can be easily applied.

  By providing water repellency, architectural materials (specifically, wallpaper, carpet, window material, sack paper) that are resistant to contamination, rubber caps with reduced permeability to oxygen and hydrocarbons, and no shrinkage without moisture absorption Clothing, oil-resistant paper and containers can be easily manufactured.

Claims (8)

  A surface modification method for imparting water repellency by treating a synthetic or natural polymer material with a gas containing fluorine gas and an inert gas, wherein the synthetic or natural polymer material has a specific gravity of 1.6 or less. A synthetic or natural polymer material that increases the contact angle with water after the treatment by 10 ° or more than before the treatment by selecting a material that does not contain any of an ether bond, a carbonate bond, an amide bond, and a urethane bond. Surface modification method.   The surface modification method according to claim 1, wherein the concentration of the fluorine gas is 5 to 95 Vol%.   The surface modification method according to claim 1, wherein the synthetic polymer material is a material selected from a thermosetting resin, a thermoplastic resin, and a rubber-like polymer.   The surface modification method according to claim 1, wherein the natural polymer material is a material selected from natural rubber, cellulose, cellulose ester, cotton, silk, and flax.   A water-repellent polymer material surface-treated by the method according to claim 1.   Clothing using the water-repellent polymer material according to claim 5.   A paper using the water-repellent polymer material according to claim 5. A rubber using the water-repellent polymer material according to claim 5.