Surface treatment method for polymer material substrate and manufacturing method for polymer material

Abstract

To provide a polymer material substrate surface treatment method and a polymer material production method which are able to realize high water repellency of a polymer material substrate of various surface chemical structures without introducing a chemical structure corresponding to a binder.SOLUTION: The polymer material substrate surface treatment method comprises reacting a vinyl compound represented by the general formula (1) defined by R-CH=CH2 with a surface of a polymer material substrate (excluding fabric substrates) under irradiation with ultraviolet rays, thereby imparting water repellency to the surface of the polymer material substrate. (In the formula, R represents an alkyl group having 6 or more carbon atoms.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for treating the surface of a polymeric material substrate and a method for producing a polymeric material. [Background technology]

[0002] As a method for imparting water repellency to the surface of a polymer material substrate, various methods of coating the surface of the polymer material substrate with a fluorine-containing compound are known. The inventors have also discovered a surface treatment method that exhibits water repellency by irradiating the surface with ultraviolet light in the presence of a fluorine-containing compound (Patent Document 1).

[0003] However, due to international regulations on fluorine-containing processing agents, there is a demand to switch to fluorine-free modification processes that use non-fluorine-based processing agents in consideration of the environment.

[0004] In addition, fluorine-free water-repellent treatment methods that use non-fluorine-based processing agents that have already been developed include an organic chemical method that uses the nucleophilic reaction of alkoxide ions (Non-Patent Document 1), a surface modification method that uses alkylborane (Patent Document 2), a method that uses photosurface modification (Patent Documents 3 and 4), and a method that uses a silane coupling reaction (Patent Document 5). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6011852 [Patent Document 2] Special Publication No. 2019-518119 [Patent Document 3] Special Publication No. 2019-532008 [Patent Document 4] Japanese Patent Application Publication No. 2019-099786 [Patent Document 5] Japanese Patent Application Publication No. 2020-029468 [Non-patent literature]

[0006] [Non-Patent Document 1] JH Lee, SH Park, SH Kim, Polymers, 12, 178 (2020) Summary of the Invention [Problem to be solved by the invention]

[0007] However, these fluorine-free water-repellent treatment methods have the following problems: the chemical treatment required to generate alkoxide ions is likely to cause side reactions (Non-Patent Document 1); alkylboranes, which are generally highly reactive and difficult to control, are used (Patent Document 2); the chemical structure of the substrate surface is limited to hydroxyl groups and the like due to the reaction with the treatment chemicals (Patent Documents 3 and 5); and the chemical structures of both the substrate and the treatment chemicals must be precisely controlled (Patent Document 4). For these reasons, it has been difficult to perform water-repellent treatment without introducing a chemical structure equivalent to a binder or without restricting the surface chemical structure of polymer material substrates.

[0008] The present invention has been made in view of the above circumstances, and provides a surface treatment method for a polymer material substrate, and a method for producing a polymer material, which can impart high water repellency to polymer material substrates having various surface chemical structures without introducing a chemical structure equivalent to a binder. [Means for solving the problem]

[0009] The present inventors have discovered that by irradiating the surface of polymer material substrates having various surface chemical structures with ultraviolet light, a hydrocarbon-based agent having a vinyl group can be chemically bonded to the surface, thereby making it possible to develop high water repellency, and have completed the present invention. That is, the present invention provides the following techniques.

[0010] [1] A surface treatment method for a polymer material substrate (excluding fabric substrates), comprising contacting the surface of the polymer material substrate with a vinyl compound represented by the following general formula (1) and irradiating the surface with ultraviolet light, thereby imparting water repellency to the surface of the polymer material substrate: R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.) [2] The surface treatment method for a polymer material substrate according to [1], wherein R is an alkyl group having 6 to 20 carbon atoms. [3] The surface treatment method for a polymer material substrate according to [1] or [2], wherein the ultraviolet light has a wavelength of 150 to 400 nm. [4] The illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW / cm 2 The method for treating the surface of a polymer material substrate according to any one of [1] to [3], wherein ultraviolet light is irradiated so that the surface of the polymer material substrate becomes [5] A method for producing a polymer material, comprising the steps of contacting a surface of a polymer material substrate (excluding fabric substrates) with a vinyl compound represented by the following general formula (1) and irradiating it with ultraviolet light: R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.) [6] The method for producing a polymer material according to [5], wherein R is an alkyl group having 6 to 20 carbon atoms. [7] The method for producing a polymer material according to [5] or [6], wherein the ultraviolet light has a wavelength of 150 to 400 nm. [8] The illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW / cm 2 The method for producing a polymer material according to any one of [5] to [7], wherein ultraviolet light is irradiated so that the polymer material becomes [Effects of the Invention]

[0011] According to the present invention, there are provided a surface treatment method for a polymer material substrate and a method for producing a polymer material, which can impart high water repellency to polymer material substrates having various surface chemical structures without introducing a chemical structure equivalent to a binder. [Brief explanation of the drawings]

[0012] [Figure 1] 1 shows XPS spectra of a polymer material substrate before surface treatment in Experimental Example 1 and a polymer material after surface treatment by reaction with 1-octadecene. [Figure 2] 1 shows C1s spectra of a polymer material substrate before surface treatment in Experimental Example 1 and a polymer material after surface treatment by reaction with 1-octadecene. [Figure 3] 1 shows XPS spectra of a polymer material substrate before surface treatment in Experimental Example 2 and a polymer material after surface treatment by reaction with 1-octadecene. [Figure 4] 1 shows C1s spectra of a polymer material substrate before surface treatment in Experimental Example 2 and a polymer material after surface treatment by reaction with 1-octadecene. [Figure 5] This shows the ultraviolet-visible light transmission spectra of a polymer material substrate made of film-like polyethylene terephthalate before surface treatment and after surface alkylation treatment by reacting with 1-octadecene. [Figure 6] 1 shows the ultraviolet-visible light transmission spectra of a polymer material substrate made of film-like polyethylene terephthalate before surface treatment and after surface alkylation treatment by reacting with 1-tetradecene. [Figure 7] These are FT-IR difference spectra measured by the ATR method before and after the surface treatment of various polymer materials, obtained by applying a 1-octadecene solution to the polymer materials and then irradiating them with a xenon excimer lamp. DETAILED DESCRIPTION OF THE INVENTION

[0013] <Surface treatment method for polymer material substrate> A surface treatment method for a polymer material substrate according to one embodiment of the present invention is a surface treatment method for a polymer material substrate, which comprises contacting the surface of a polymer material substrate (excluding fabric substrates) with a vinyl compound represented by the following general formula (1) and irradiating the surface with ultraviolet light, thereby imparting water repellency to the surface of the polymer material substrate. R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

[0014] In the surface treatment method for a polymer material substrate according to this embodiment, substrates made of various general-purpose polymers and functional polymers can be used as the polymer material substrate. The shape of the polymer material substrate is not limited, and a wide range of shapes, including plate, film, powder, and pellet shapes, can be used. However, fabric substrates are excluded. In this specification, the polymer material before surface treatment is sometimes referred to as the polymer material substrate, and the one after surface treatment is sometimes referred to as the polymer material.

[0015] In the surface treatment method for a polymer material substrate according to this embodiment, R is preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 20 carbon atoms, even more preferably an alkyl group having 10 to 20 carbon atoms, and particularly preferably an alkyl group having 12 to 18 carbon atoms. The alkyl group may be linear, branched, or cyclic, and is preferably linear. It is more preferable that R is a linear alkyl group having 12 to 18 carbon atoms.

[0016] In the surface treatment method for a polymer substrate according to this embodiment, known ultraviolet light sources can be used. Examples include low-pressure mercury lamps, high-pressure mercury lamps, ArF or XeCl excimer lasers, excimer lamps, etc. Thus, the present invention can utilize light over a wide range of wavelengths.

[0017] In the surface treatment method for a polymer substrate according to the present embodiment, the vinyl compound is irradiated with ultraviolet light to chemically bond the alkyl group to an element derived from the polymer substrate on the surface of the polymer substrate by electron transfer from the vinyl group to the polymer substrate. The wavelength of the ultraviolet light is preferably 150 nm to 400 nm, more preferably 170 nm to 300 nm.

[0018] To increase the efficiency of the reaction, it is preferable to irradiate with ultraviolet light having a wavelength of 200 nm or less.

[0019] In the surface treatment method for a polymer material substrate according to this embodiment, the illuminance reaching the polymer material substrate is 0.1 to 100 mW / cm 2 It is preferable to irradiate with ultraviolet light so that the temperature becomes 100°C. The irradiation time may be about 1 minute to 6 hours, and is preferably about 1 minute to 30 minutes. These conditions are preferred ranges, and are not necessarily limited to these.

[0020] In the surface treatment method for a polymer material substrate according to this embodiment, the vinyl compound represented by general formula (1) can be brought into contact with the surface of the polymer material substrate (excluding fabric substrates) by either a dry process or a wet process, such as bringing the vinyl compound into contact with the polymer material substrate as a liquid, spraying or applying a solution of the vinyl compound onto the polymer material substrate, immersing the polymer material substrate in a solution of the vinyl compound and then drying it, or introducing the vinyl compound into a reaction vessel as a gas in the presence of the polymer material substrate.

[0021] In the surface treatment method for a polymer substrate according to this embodiment, the alkylation reaction proceeds easily at room temperature. This is one of the major features of the present invention. However, heating is not prohibited. Heating is also possible if necessary.

[0022] In this specification, room temperature refers to a temperature that is neither heated nor cooled from an external system. Room temperature may be 1 to 30°C, or may be 15 to 25°C.

[0023] The surface treatment method for a polymer material substrate according to this embodiment is a safe and simple reaction procedure that involves simply irradiating a polymer material substrate that has been brought into contact with a vinyl compound with ultraviolet light, thereby introducing alkyl groups onto the surface of the polymer material without causing deterioration of the substrate, thereby achieving the excellent effect of exhibiting high water repellency.

[0024] The surface treatment method of the polymer material substrate according to this embodiment does not require heat treatment during processing, which contributes to reducing energy consumption. Furthermore, high water repellency can be imparted without using fluorine- or silicone-containing surface treatment agents, which have been used in conventional surface treatments to impart water repellency to polymer material substrates, and without using a chemical structure equivalent to a crosslinking agent.

[0025] <Method of manufacturing polymer materials> The method for producing a polymer material according to this embodiment includes the steps of contacting a vinyl compound represented by the following general formula (1) and irradiating it with ultraviolet light. R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

[0026] The method for producing a polymer material according to this embodiment can provide a polymer material having a surface that is imparted with water repellency. The details of the method for producing a polymer material according to this embodiment are the same as those of the surface treatment method for a polymer material substrate described above. [Example]

[0027] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the examples shown below.

[0028] (X-ray photoelectron spectroscopy (XPS) analysis) X-ray photoelectron spectroscopy (XPS) equipment (ULVAC-PHI, ESCA5800, data analysis software: PHI MultiPak) TM ) was used to analyze the surface of the polymer material substrate before surface treatment and the surface of the polymer material after surface treatment under the following measurement conditions. This allows for analysis of elemental components and their bonding state from the surface to a depth of approximately 5 nm. X-ray source: Monochromatic AlKα, beam diameter 800 μmφ, output 100 W, measurement area: 800 μmφ measurement, sample tilt angle: 45°

[0029] In the XPS spectrum, the ratio of the peak area of ​​the carbon component in the binding energy range of 280 to 300 eV to the sum of the peak areas of all elemental components in the binding energy range of 0 to 1000 eV was determined as the carbon content.

[0030] The carbon-carbon bond content was calculated as the ratio of the peak area of ​​the carbon-carbon bond (CC) near 285.0 eV to the total area of ​​the peak area of ​​the carbon-carbon bond (CC) near 285.0 eV, the peak area of ​​the carbon-nitrogen bond (CN, CO, C-Cl) near 286.0 eV, and the peak area of ​​the carbon-oxygen bond (C=O) near 288 eV.

[0031] (Method for measuring water contact angle) The contact angle with water of the polymer material substrate before the surface treatment and the polymer material after the surface treatment was measured using a contact angle meter DMo-501 manufactured by Kyowa Interface Science Co., Ltd. The measurement temperature was room temperature, and the amount of water droplet was 2 μl.

[0032] (Method for measuring transmittance) The transmittance of the film-like sample in the wavelength range of 200 to 800 nm was measured using an ultraviolet-visible spectrophotometer (UV-3150 manufactured by Shimadzu Corporation).

[0033] (FT-IR measurement method using the ATR method) The polymer material substrate before and after surface treatment were measured using a JASCO FT / IR-680 Fourier transform infrared spectrophotometer equipped with an ATR unit (ATR500M, Ge prism). The measurement temperature was room temperature, and the measurement room environment was atmospheric. Using the analysis software provided with the instrument, a coefficient was set to cancel out the intensity of common peaks (such as C=O peaks), and the spectrum before surface treatment was subtracted from the spectrum after surface treatment to obtain an FT-IR difference spectrum.

[0034] (Experimental Example 1) A 2.3 g / L hexane solution of 1-octadecene was applied to the surface of various 1 mm thick plate-shaped polymer substrates (polyethylene, polypropylene, PMMA, polyvinyl chloride, ABS resin, polycarbonate, nylon 6) and irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of the ultraviolet irradiation was 172 nm.

[0035] The surface-treated polymer material was then washed with hexane and dried under reduced pressure. XPS measurements were performed on the polymer material substrates before and after surface treatment using PMMA, polyvinyl chloride, ABS resin, polycarbonate, and nylon 6. The contact angle of each surface with water was also measured. The results of the XPS measurement are shown in Figure 1. The C1s spectrum is shown in Figure 2. The measurement results of the carbon content are shown in Table 1. The results of the water contact angle measurements are shown in Table 2.

[0036] [Table 1]

[0037] [Table 2]

[0038] By reacting 1-octadecene on the surface of a polymer material substrate, an increase in carbon components was observed (Figure 1, Table 1), and an increase in carbon-carbon bond components derived from the introduced alkyl groups was confirmed (Figure 2). Furthermore, the contact angle with water was 100° or more, imparting water repellency (Table 2).

[0039] (Experimental Example 2) A 1.6 g / L hexane solution of 1-octadecene was applied to the surface of various polymer substrates (polyethylene terephthalate (Lumirror® T60 manufactured by Toray Industries, Inc.) and polyimide (Kapton® 200H manufactured by Toray DuPont Co., Ltd.)) in the form of a 50 μm thick film, and the surface was irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of the ultraviolet irradiation was 172 nm.

[0040] The surface-treated polymer material was then washed with hexane and dried under reduced pressure. XPS measurements were performed on the polymer material substrate before and after the surface treatment. The transmittance of each was also measured. The results of the XPS measurement are shown in Figure 3. The C1s spectrum is shown in Figure 4. When polyethylene terephthalate was used as the polymer material substrate, the results of measuring the permeability of the polymer material substrate before surface treatment and the polymer material after surface alkylation treatment are shown in FIG. The measurement results of the carbon content are shown in Table 3. The results of the water contact angle measurements are shown in Table 4.

[0041] [Table 3]

[0042] [Table 4]

[0043] By reacting 1-octadecene on the surface of the polymer material substrate, an increase in the carbon component was observed (Figure 3, Table 3), and an increase in the carbon-carbon bond component derived from the introduced alkyl group was confirmed (Figure 4). Furthermore, the contact angle with water was 100° or more, imparting water repellency (Table 4).

[0044] Furthermore, for a transparent polymer material (polyethylene terephthalate), the transmittance of the polymer material after alkylation surface treatment remained almost unchanged compared to before surface treatment, confirming that the transparency of the polymer material substrate could be maintained even after reaction with 1-octadecene, and that the introduction of alkyl groups had little effect on the substrate (Figure 5).

[0045] (Experimental Example 3) A 60 g / L hexane solution of 1-tetradecene was applied to the surface of a 50 μm thick film-like polymer material substrate (polyethylene terephthalate (Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc.)) and irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of the ultraviolet irradiation was 172 nm.

[0046] The surface-treated polymer material was then washed with hexane and dried under reduced pressure. The contact angle with water was 100°, imparting water repellency. The results of measuring the permeability of the polymer material substrate before surface treatment and the polymer material after surface alkylation treatment are shown in FIG. The transmittance of the polymer material after alkylation surface treatment remained almost unchanged compared to before surface treatment, confirming that the transparency of the polymer material substrate could be maintained even after reaction with 1-tetradecene, and that the introduction of alkyl groups had little effect on the substrate (Figure 6).

[0047] Figure 7 shows the FT-IR difference spectra measured by the ATR method before and after the surface treatment of various polymer materials, obtained by applying a 1-octadecene solution to the polymer materials and then irradiating them with a xenon excimer lamp. It was confirmed that alkyl groups were introduced onto the surface of the polymer materials in all cases by the surface treatment.

[0048] It has been revealed that by contacting the surface of a polymer material substrate with a vinyl compound and irradiating it with ultraviolet light, it is possible to achieve high water repellency for polymer material substrates with various surface chemical structures without introducing a chemical structure equivalent to a binder and without causing deterioration of the substrate. [Industrial Applicability]

[0049] The surface treatment method of the present invention for polymeric substrates allows for chemical bonding of alkyl groups to the surface of the polymeric substrate simply by irradiating a vinyl compound having a terminal carbon-carbon double bond with ultraviolet light. In other words, the surface treatment method of the present invention for polymeric substrates is a safe and simple method that utilizes a photoreaction. Without using conventional fluorine-containing compounds or introducing a chemical structure equivalent to a binder, the method can exhibit high water repellency comparable to that of fluorine-based surface treatment materials for polymeric substrates with various surface chemical structures. Even if the polymer material substrate has poor heat resistance, chemical resistance, and light resistance, the reaction can be carried out at room temperature, so the method can be applied to polymer material substrates with various surface chemical structures, and alkyl groups can be introduced onto the surface of the polymer material without causing deterioration of the substrate due to light irradiation. Therefore, the surface treatment method of the present invention for polymer material substrates can be used as a method for producing water-repellent members, circuit boards, environmentally friendly products, general industrial product members, and the like.

Claims

1. A surface treatment method for a polymer material substrate (excluding fabric substrates), comprising contacting the surface of the polymer material substrate with a vinyl compound represented by the following general formula (1), and then irradiating the surface with ultraviolet light, thereby imparting water repellency to the surface of the polymer material substrate, the water contact angle of which is 100° or more: R-CH=CH ２ (1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

2. 2. The surface treatment method for a polymer material substrate according to claim 1, wherein R is an alkyl group having 6 to 20 carbon atoms.

3. 3. The surface treatment method for a polymer material substrate according to claim 1, wherein the ultraviolet light has a wavelength of 150 to 400 nm.

4. The illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW / cm ２ The method for treating the surface of a polymer material substrate according to any one of claims 1 to 3, wherein ultraviolet light is irradiated so as to achieve the above-mentioned.

5. A method for producing a polymer material, comprising the steps of contacting a surface of a polymer material substrate (excluding fabric substrates) with a vinyl compound represented by the following general formula (1), and then irradiating the surface with ultraviolet light, The method for producing a polymer material, wherein the surface of the polymer material has a contact angle with water of 100° or more. R-CH=CH ２ (1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

6. The method for producing a polymer material according to claim 5, wherein R is an alkyl group having 6 to 20 carbon atoms.

7. The method for producing a polymer material according to claim 5 or 6, wherein the ultraviolet light has a wavelength of 150 to 400 nm.

8. The illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW / cm ２ The method for producing a polymer material according to any one of claims 5 to 7, wherein ultraviolet light is irradiated so as to form a polymer material.

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