JP2023053773A - Polymer material substrate surface treatment method and polymer material production method - Google Patents

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 The present invention relates to a method for surface treatment of a polymeric material substrate and a method for producing a polymeric material.

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

However, the method using these fluorine-containing compounds is required to be converted to a fluorine-free modification treatment using non-fluorine-based processing agents in consideration of the environment due to international regulations on fluorine-containing processing agents. .

In addition, as fluorine-free water repellent treatment methods using non-fluorine-based processing agents that have already been developed, organic chemical methods using nucleophilic reactions of alkoxide ions (Non-Patent Document 1) and alkylborane are used. A surface modification method (Patent Document 2), a method using photosurface modification (Patent Documents 3 and 4), a method using a silane coupling reaction (Patent Document 5), and the like are known.

Japanese Patent No. 6011852 Japanese translation of PCT publication No. 2019-518119 Japanese Patent Application Publication No. 2019-532008 JP 2019-099786 A Japanese Patent Application Laid-Open No. 2020-029468

J. H. Lee, S. H. Park, S. H. Kim, Polymers, 12, 178 (2020)

However, in these fluorine-free water repellent treatment methods, there is a high possibility that side reactions will occur due to the chemical treatment necessary for generating alkoxide ions (Non-Patent Document 1), and generally the reactivity is high and controllable. The use of difficult alkylboranes (Patent Document 2), the substrate surface chemical structure being limited to hydroxyl groups and the like due to reaction with treatment chemicals (Patent Documents 3 and 5), the chemistry of both the substrate and the treatment chemicals Water repellent treatment without introducing a chemical structure corresponding to a binder, such as the need to precisely control the structure (Patent Document 4), and water repellent without limiting the surface chemical structure of the polymer material substrate. It was difficult to process.

The present invention has been made in view of the above circumstances, and it is possible to express high water repellency to polymer material substrates having various surface chemical structures without introducing a chemical structure corresponding to a binder. Provided are a method for surface treatment of a polymeric material substrate and a method for producing a polymeric material, which can be used.

The present inventors discovered that by irradiating a hydrocarbon-based agent having a vinyl group on the surface of a polymer material substrate having various surface chemical structures with ultraviolet rays, the alkyl group can be chemically bonded, resulting in high repellency. The inventors have found that water can be expressed, and completed the present invention.
That is, the present invention provides the following techniques.

[1] A vinyl compound represented by the following general formula (1) is brought into contact with the surface of a polymer material substrate (excluding a fabric substrate) and irradiated with ultraviolet rays to remove the polymer material substrate. A method for surface treatment of a polymer material substrate for imparting water repellency to the surface.
R-CH=CH ₂ (1)
(In the formula, R represents an alkyl group having 6 or more carbon atoms.)
[2] The method for surface treatment of a polymer material substrate according to [1], wherein R is an alkyl group having 6 to 20 carbon atoms.
[3] The method for surface treatment of a polymer material substrate according to [1] or [2], wherein the ultraviolet rays have a wavelength of 150 to 400 nm.
[4] The polymer material substrate according to any one of [1] to [3], wherein ultraviolet rays are irradiated so that the illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW/cm ² . surface treatment method.
[5] A method for producing a polymer material, comprising the step of bringing a vinyl compound represented by the following general formula (1) into contact with the surface of a polymer material substrate (excluding a fabric substrate) and irradiating with ultraviolet rays. .
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 [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 rays have a wavelength of 150 to 400 nm.
[8] Manufacture of the polymer material according to any one of [5] to [7], wherein ultraviolet rays are irradiated so that the illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW/cm ² . Method.

According to the present invention, there is provided a method for surface treatment of a polymer material substrate that can develop high water repellency to polymer material substrates having various surface chemical structures without introducing a chemical structure corresponding to a binder. and methods of making polymeric materials are provided.

2 shows XPS spectra of the polymer material substrate before surface treatment and the polymer material after surface treatment with 1-octadecene in Experimental Example 1. FIG. 2 shows C1s spectra of the polymer material substrate before surface treatment in Experimental Example 1 and the polymer material after surface treatment with 1-octadecene. 2 shows XPS spectra of the polymer material substrate before surface treatment and the polymer material after surface treatment with 1-octadecene in Experimental Example 2. FIG. 2 shows C1s spectra of the polymer material substrate before surface treatment in Experimental Example 2 and the polymer material after surface treatment with 1-octadecene. UV-visible light transmission spectra of the polymer material base before surface treatment and the polymer material after surface alkylation treatment by reacting with 1-octadecene when film-like polyethylene terephthalate is used as the polymer material base. be. Ultraviolet and visible light transmission spectra of a polymer material base before surface treatment and a polymer material after surface alkylation treatment by reacting with 1-tetradecene when film-like polyethylene terephthalate is used as the polymer material base. be. 1 shows FT-IR difference spectra by the ATR method before and after treatment of surface-treated polymer materials obtained by applying a 1-octadecene solution to various polymer materials and then irradiating them with a xenon excimer lamp.

<Surface treatment method for polymer material substrate>
A method for surface treatment of a polymer material substrate according to one embodiment of the present invention comprises bringing a vinyl compound represented by the following general formula (1) into contact with the surface of a polymer material substrate (excluding a fabric substrate). and applying ultraviolet rays to impart water repellency to the surface of the polymer material substrate.
R—CH═CH ₂ (1)
(In the formula, R represents an alkyl group having 6 or more carbon atoms.)

In the method for surface treatment of a polymer material substrate according to the present embodiment, substrates 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 such as plate, film, powder, and pellets can be used. However, fabric substrates are excluded. In this specification, the polymer material before the surface treatment is sometimes called the polymer material substrate, and the one after the surface treatment is sometimes called the polymer material.

In the method for surface treatment of a polymer material substrate according to the present embodiment, R is preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 20 carbon atoms. An alkyl group having 10 to 20 carbon atoms is more preferable, and an alkyl group having 12 to 18 carbon atoms is particularly preferable. The alkyl group may be linear, branched or cyclic, preferably linear. More preferably, R is a linear alkyl group having 12 to 18 carbon atoms.

In the method for surface treatment of a polymer material substrate according to the present embodiment, a known ultraviolet light source can be used. Examples include low-pressure mercury lamps, high-pressure mercury lamps, ArF or XeCl excimer lasers, excimer lamps, and the like. Thus, the present invention can utilize light of a wide range of wavelengths.

In the method for surface treatment of a polymeric material substrate according to the present embodiment, the alkyl group is chemically treated with an element derived from the polymeric material substrate on the surface of the polymeric material substrate by electron transfer from the vinyl group of the vinyl compound to the polymeric material substrate. For bonding, they are exposed to UV radiation. The wavelength of the ultraviolet rays is preferably 150 nm to 400 nm, more preferably 170 nm to 300 nm.

In order to improve the efficiency of the reaction, it is preferable to irradiate ultraviolet rays having a wavelength of 200 nm or less.

In the method for surface treatment of a polymer material substrate according to the present embodiment, it is preferable to irradiate the polymer material substrate with ultraviolet rays so that the illuminance reaching the polymer material substrate is 0.1 to 100 mW/cm ² . The irradiation time may be about 1 minute to 6 hours, preferably about 1 minute to 30 minutes. These conditions are preferred ranges and are not necessarily particularly limited thereto.

In the method for surface treatment of a polymer material substrate according to the present embodiment, the surface of the polymer material substrate (excluding the fabric substrate) is contacted with the vinyl compound represented by the general formula (1). , a method of contacting the polymer material substrate with the vinyl compound as a liquid, a method of spraying or applying a solution of the vinyl compound onto the polymer material substrate, and a method of immersing the polymer material substrate in the solution of the vinyl compound and then drying it. , a method of introducing the vinyl compound as a gas into a reaction vessel in the presence of a polymer material substrate, and the like.

In the method for surface treatment of a polymer material substrate according to this embodiment, the alkylation reaction proceeds easily at room temperature. This is also one of the major features of the present invention. However, it does not deny heating. It is also possible to heat if necessary.

As used herein, room temperature refers to a temperature that is neither heated nor cooled by an external system. The room temperature may be 1-30°C, and may be 15-25°C.

The method for surface treatment of a polymer material substrate according to the present embodiment is a safe and simple reaction operation in which a polymer material substrate in contact with a vinyl compound is irradiated with ultraviolet rays to treat the surface of the polymer material without causing deterioration of the substrate. An alkyl group is introduced thereon, and an excellent effect of being able to express high water repellency is exhibited.

The method for surface treatment of a polymer material substrate according to the present embodiment does not require heat treatment during processing, and thus can contribute to the reduction of energy consumption. In addition, high water repellency is imparted without the use of fluorine- or silicone-containing surface treatment agents, which are conventionally used as surface treatments to impart water repellency to polymer material substrates, and without the use of a chemical structure equivalent to a cross-linking agent. can.

<Method for producing polymer material>
A method for producing a polymer material according to the present embodiment includes a step of contacting a vinyl compound represented by the following general formula (1) and irradiating with ultraviolet rays.
R—CH═CH ₂ (1)
(In the formula, R represents an alkyl group having 6 or more carbon atoms.)

A polymer material having a water-repellent surface can be obtained by the method for producing a polymer material according to the present embodiment. The details of the method for producing the polymer material according to this embodiment are the same as the method for surface treatment of the polymer material substrate described above.

The present invention will be described in more detail below with reference to specific examples. However, the present invention is by no means limited to the examples shown below.

(X-ray photoelectron spectroscopy (XPS) analysis)
Using an X-ray photoelectron spectroscopy (XPS) device (manufactured by ULVAC-PHI, ESCA5800, data analysis software: PHI MultiPak ^™ ), under the following measurement conditions, the polymer material substrate before surface treatment and the polymer material after surface treatment surface was analyzed. This makes it possible to analyze the elemental components and their bonding states up to a depth of approximately 5 nm from the surface.
X-ray source: monochromatic AlKα, beam diameter 800 μmφ, output 100 W, measurement area: 800 μmφ measurement, sample tilt angle: 45°

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 total peak area of all the elemental components in the binding energy range of 0 to 1000 eV was obtained as the carbon content.

Carbon-carbon bond peak area (C-C) near 285.0 eV, carbon-nitrogen bond peak area (C-N, C-O, C-Cl) near 286.0 eV, and carbon near 288 eV The ratio of the carbon-carbon bond peak area (CC) near 285.0 eV to the total area of the oxygen bond peak area (C=O) was obtained as the carbon-carbon bond content.

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

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

(Measurement method of FT-IR by ATR method)
For the polymer material base material before surface treatment and the polymer material after surface treatment, an ATR unit (ATR500M, Ge prism) was attached to a Fourier transform infrared spectrophotometer FT/IR-680 manufactured by JASCO Corporation. measured by The measurement temperature is room temperature, and the measurement room environment is the atmosphere. Using the analysis software attached to the device, a coefficient was set so as to cancel out the common peak (C=O peak, etc.) intensity, and the spectrum before surface treatment was subtracted from the spectrum after surface treatment to obtain an FT-IR difference spectrum.

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

The polymer material after surface treatment was then washed with hexane and dried under reduced pressure. Among these, when PMMA, polyvinyl chloride, ABS resin, polycarbonate and nylon 6 were used as the polymer material base material, XPS measurement was performed on the polymer material base material before surface treatment and the polymer material after surface treatment. Also, the contact angle of each surface to water was measured.
The results of XPS measurements are shown in FIG. Also, the C1s spectrum is shown in FIG.
Table 1 shows the measurement results of the carbon content.
Table 2 shows the measurement results of the contact angle with water.

By reacting 1-octadecene on the surface of the polymer material substrate, an increase in the carbon component was observed (FIG. 1, Table 1), and an increase in the carbon-carbon bond component derived from the introduced alkyl group was confirmed. (Fig. 2).
Moreover, the contact angle with water was 100° or more, and water repellency was imparted (Table 2).

(Experimental example 2)
1- A 1.6 g/L hexane solution of octadecene was applied and irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of ultraviolet irradiation is 172 nm.

The polymer material after surface treatment was then washed with hexane and dried under reduced pressure. XPS measurement was performed on the polymer material base material before surface treatment and the polymer material after surface treatment. In addition, each transmittance was measured.
The results of XPS measurements are shown in FIG. Also, the C1s spectrum is shown in FIG.
FIG. 5 shows the measurement results of the permeability of the polymer material base material before surface treatment and the polymer material after surface alkylation treatment when polyethylene terephthalate was used as the polymer material base material.
Table 3 shows the measurement results of the carbon content.
Table 4 shows the measurement results of the contact angle with water.

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

Furthermore, with regard to the transparent polymer material (polyethylene terephthalate), the transmittance of the polymer material after the alkylation surface treatment is almost unchanged compared to that before the surface treatment, and even if 1-octadecene is reacted, the transparency of the polymer material base material It was confirmed that transparency could be maintained and that the introduction of alkyl groups had little effect on the base material (Fig. 5).

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

The polymer material after surface treatment was then washed with hexane and dried under reduced pressure. The contact angle with water was 100°, and water repellency was imparted.
FIG. 6 shows the measurement results of the transmittance of the polymer material substrate before surface treatment and the polymer material after surface alkylation treatment.
The transmittance of the polymer material after the alkylation surface treatment is almost unchanged compared to that before the surface treatment, and even if 1-tetradecene is reacted, the transparency of the polymer material substrate can be maintained. It was confirmed that there was little effect on the base material (Fig. 6).

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

By bringing the vinyl compound into contact with the surface of the polymer material substrate and irradiating it with ultraviolet rays, the polymer material substrates having various surface chemical structures are exposed to the substrate without introducing a chemical structure corresponding to the binder. It became clear that high water repellency can be expressed without causing deterioration.

In the method for treating the surface of a polymer material substrate of the present invention, an alkyl group can be chemically bonded to the surface of a polymer material substrate simply by irradiating a vinyl compound having a carbon-carbon double bond at its end with an ultraviolet ray. . That is, the method for surface treatment of a polymer material substrate of the present invention is a safe and convenient method utilizing photoreaction. Without using conventionally used fluorine-containing compounds and without introducing a chemical structure corresponding to a binder, it can be applied to polymer material substrates with various surface chemical structures as high as fluorine-based surface treatment materials. Water repellency can be expressed.
Even if the polymer material substrate is inferior in heat resistance, chemical resistance, and light resistance, it is possible to react at room temperature, so it can be applied to polymer material substrates with various surface chemical structures. is possible, and alkyl groups can be introduced onto the polymer material surface without causing deterioration of the substrate due to light irradiation.
Therefore, the method for surface treatment of a polymer material substrate of the present invention can be used as a method for manufacturing members imparted with water repellency, circuit boards, eco-friendly products, and members of industrial products in general.

Claims (8)

A vinyl compound represented by the following general formula (1) is brought into contact with the surface of a polymer material substrate (excluding a fabric substrate) and irradiated with ultraviolet rays to make the surface of the polymer material substrate repellent. A surface treatment method for a polymeric material substrate that imparts water-based properties.
R—CH═CH ₂ (1)
(In the formula, R represents an alkyl group having 6 or more carbon atoms.) 2. The method for surface treatment of a polymer material substrate according to claim 1, wherein said R is an alkyl group having 6 to 20 carbon atoms. 3. The method for surface treatment of a polymer material substrate according to claim 1, wherein said ultraviolet rays have a wavelength of 150 to 400 nm. The method for surface treatment of a polymer material substrate according to any one of claims 1 to 3, wherein the ultraviolet rays are irradiated so that the illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW/cm ² . A method for producing a polymer material, comprising the step of bringing a vinyl compound represented by the following general formula (1) into contact with the surface of a polymer material substrate (excluding a fabric substrate) and irradiating with ultraviolet rays.
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 said R is an alkyl group having 6 to 20 carbon atoms. 7. The method for producing a polymer material according to claim 5, wherein the ultraviolet rays have a wavelength of 150-400 nm. The method for producing a polymer material according to any one of claims 5 to 7, wherein the ultraviolet rays are irradiated so that the illuminance reaching the surface of the polymer material substrate is 0.1 to 100 mW/cm ² .

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