Non-destructive diagnosis method for graft polymerization and pinhole microwave cavity resonator used for the same

Abstract

To provide a non-destructive diagnosis method using graft polymerization reaction by electron beam irradiation of polymeric materials, and high quality functional graft base material.SOLUTION: The non-destructive diagnosis method for graft polymerization diagnoses graft polymerization degree of functional monomer having electrical polarity for a graft base material obtained by graft polymerizing the functional monomer to a crystalline polymer base material. Graft ratio ΔG and amount of change rate ΔB in resonance frequency by microwave dielectric absorption method are detected for N graft base material samples, ΔG / ΔB regression line obtained from N sets of detected (ΔB, ΔG) is used to non-destructively diagnose the functional graft polymerization degree. The detected graft ratio ΔG is compared to reference graft ratio (kt×ΔB) calculated from the detected ΔB and functional graft coefficient kt.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a non-destructive diagnostic method for graft polymerization, a method for inspecting the degree of functional graft polymerization, and a pinhole-type microwave cavity resonator used therefor. [Background technology]

[0002] Graft polymerization is a polymerization method that can impart new functions to existing polymeric materials by polymerizing a monomer with a special function onto the base polymer material. It is extremely useful and has been utilized in a wide range of fields because it can improve the properties and applicability of polymeric materials. For example, by irradiating a polymer such as polyethylene with radiation and combining multiple polymers and monomers, polymers of other monomers are polymerized like branches from the main chain of the base polymer (graft polymerization), improving the functionality of the base polymer.

[0003] When preparing a substrate with desired functionality by graft polymerizing a monomer onto a base polymer, it is necessary to know whether the graft polymerization of the substrate was successful. However, conventionally, the only way to determine this was to estimate the graft ratio, which is calculated by the ratio of the mass of the substrate to the mass increase before and after polymerization. However, measuring the graft ratio requires measuring the mass of the substrate in advance, and it is not possible to determine the graft ratio for a sample after graft polymerization when the mass of the substrate is unknown.

[0004] Meanwhile, the present inventors have previously developed a device capable of observing molecular behavior by a "microwave dielectric absorption method" that uses a microwave cavity resonator fabricated in a cross-pipe shape to measure changes in dielectric constant due to changes in molecular dipole moment as changes in Q value or resonant frequency (Patent Document 1). Furthermore, the inventors have applied this method to establish a "method for evaluating changes in samples containing biological molecules and other hydrous organic polymers" using a microwave cavity resonator (Patent Document 2).

[0005] However, the microwave cavity resonator according to Patent Document 2 requires a container support made of polystyrene or the like to be filled inside the cavity, as shown in Fig. 14. Furthermore, the microwave cavity resonators according to Patent Documents 1 and 2 can obtain a high Q value by making the cavity spherical or cylindrical, but are insertion-type microwave cavity resonators that require a sample to be inserted into a position in the cylindrical cross pipe where the microwave electric field is strong.

[0006]

[0003] Subsequently, the inventor attempted to examine the deterioration state of the conductor insulation coating of distribution cables connected to various equipment in the facility using a microwave dielectric absorption method, but was unable to use the above-mentioned insertion-type cavity resonator as it was. That is, as described above, the insertion-type microwave cavity resonator requires the entire sample to be inserted into its cross pipe due to its structure. Therefore, for distribution cables that cannot be removed or cut from the equipment, the deterioration state of the cable cannot be examined as it is. Furthermore, since a conductor is located at the center of the cable, this conductor has the property of absorbing microwaves. With the above-mentioned insertion-type measuring device, the entire cable is placed inside the cavity resonator, and the conductor absorbs microwaves, which makes it difficult to obtain accurate reflected microwaves.

[0007] Therefore, the present inventors developed a pinhole-type microwave cavity resonator according to Patent Document 3, which enables the measurement of deterioration of the insulating coating of a conductive cable. Figures 15(a) to 15(d) respectively show a perspective view of the pinhole-type microwave cavity resonator according to Patent Document 3, a side view thereof, a side view of the pinhole provided on the side surface thereof being covered with a distribution cable, and a schematic diagram of a measurement device including the pinhole-type microwave cavity resonator.

[0008] The deterioration measuring device for the insulation coating of a conductive cable according to Patent Document 3 includes a microwave cavity resonator (1) having a waveguide (11) and a pinhole (12) in the wall, and as shown in Figure 15(d), at least a holding member (2) capable of holding a cable (C), a Gunn oscillator (3), a circulator (4), an amplifier (5) for amplifying the reflected microwave, and a microwave observation device (6) capable of detecting the amplified reflected microwave are arranged. The cable (C) held by the holding member (2) can tightly cover the outer opening of the pinhole (12) of the microwave cavity resonator (1), while microwaves generated from the Gunn oscillator (3) are introduced into the microwave cavity resonator (1) via the waveguide (11) by the circulator (4), and a portion of the microwaves can leak out from the outer opening of the pinhole (12). The leaked microwaves are irradiated onto the insulator (A) of the cable (C) held by the holding member (2), and the introduced microwaves are reflected within the microwave cavity resonator (1). The reflected microwaves are amplified by the amplifier (5) and can be detected and observed by the microwave observation device (6).

[0009] The pinhole-type microwave cavity resonator (1) according to Patent Document 3 has a cubic outer shape, a cylindrical hollowed-out interior, and a pinhole (12) formed on the side of a flat plate. The microwave band oscillated from the Gunn oscillator (3) shown in Fig. 15(d) is characterized by being in the Q-band (33 to 50 GHz).

[0010] As described above, the microwave dielectric absorption method, such as the cross-pipe (insertion) microwave cavity resonator disclosed in Patent Document 1, measures the change in dielectric constant due to a change in molecular dipole moment as a change in Q value or resonant frequency. Meanwhile, in the degradation measurement of the insulating coating disclosed in Patent Document 3, the dielectric constant of the sample irradiated with microwaves remains unchanged before and after degradation, so the change in resonant frequency is approximately constant. Therefore, like conventional microwave cavity resonators, the pinhole-type microwave cavity resonator disclosed in Patent Document 3 is preferably spherical or cylindrical in shape to achieve a higher Q value. Here, the Q value is defined as Q=f / Δf, where f is the maximum resonant frequency of the sample irradiated with microwaves, and Δf is the half-width of the resonant frequency curve.

[0011] However, as mentioned above, when creating a functional substrate by graft polymerizing a monomer onto a base polymer, the dielectric constant of the microwave-irradiated sample changes significantly before and after graft polymerization, so the change in resonant frequency (f-f') is more important than the Q value (see Figures 11(a) and 11(b)). Therefore, to evaluate the degree of graft polymerization of such functional substrates using the microwave dielectric absorption method, it is not possible to obtain meaningful information using conventional analytical methods that emphasize a high Q value, such as the microwave cavity resonator structure, microwave dielectric absorption method, and graft ratio.

[0012] For example, even if the mass difference (graft ratio) before and after the graft polymerization reaction of a polymer substrate is measured as shown in Figures 12(a) and 12(b), it is impossible to determine whether the difference is due to the graft polymerization of a functional monomer, the graft polymerization of other monomers, or other attachments.Furthermore, even if Fourier transform infrared spectroscopy is performed on multiple graft-polymerized graft substrates, the details of the graft polymerization of functional monomers, etc. cannot be discerned from the shape of the spectral diagrams as shown in Figures 13(a) to 13(h). [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Patent No. 4401700 [Patent Document 2] Patent No. 5737743 [Patent Document 3] Patent No. 5495062 Summary of the Invention [Problem to be solved by the invention]

[0014] Therefore, in this invention, we provide a new method for non-destructively diagnosing the graft polymerization of polymer materials, which replaces conventional methods such as grafting rate, based on the results of measuring the changes in dielectric constant and dielectric loss due to changes in molecular dipole moment using a microwave dielectric absorption method using a pinhole-type X-band microwave cavity resonator developed in this invention, and the calculated value of dipole moment using semi-empirical molecular orbital method. Furthermore, we develop new functional materials that are highly functional and applicable to a wide range of uses using a graft polymerization reaction caused by electron beam irradiation of polymer materials, and provide high-quality functional graft substrates by testing them using this new non-destructive diagnostic method. [Means for solving the problem]

[0015] (1) Non-destructive diagnostic method for the degree of functional graft polymerization The non-destructive diagnostic method for graft polymerization according to the present invention is a method for diagnosing the degree of graft polymerization of a functional monomer having electrical polarity in a graft substrate (weight W(g)) obtained by graft-polymerizing the functional monomer onto a crystalline polymer substrate (weight W0(g), hereinafter also simply referred to as "substrate") (the "degree of graft polymerization of the functional monomer" will hereinafter also be simply referred to as "functional graft polymerization degree"), A method for non-destructively diagnosing the degree of functional graft polymerization in a graft substrate to be diagnosed of the same type as the graft substrate, comprising: detecting the graft rate ΔG=(W-W0) / W0 and the rate of change in resonance frequency ΔB=(f-f') / f (f and f' are the resonance frequencies of the substrate and the graft substrate, respectively) measured by microwave dielectric absorption; and utilizing a regression line of ΔG / ΔB obtained from the N sets of detected data (rate of change in resonance frequency ΔB, graft rate ΔG) (hereinafter also simply referred to as "(ΔB, ΔG)"), comprising: For N graft substrate samples, a pinhole-type microwave cavity resonator with a pinhole on the sidewall was used to generate N sets of data (ΔB, ΔG) detected by a microwave dielectric absorption method in the X-band (9 to 12 GHz). From the N sets of data, the functional graft coefficient k, which is the slope of the regression line, was calculated. t Meanwhile, for the graft substrate to be diagnosed, (ΔB, ΔG) was detected by the microwave dielectric absorption method, and the detected graft rate ΔG, the detected ΔB and the functional graft coefficient k t The standard grafting rate (k t ×ΔB) and comparing these values, the degree of graft polymerization of the functional monomer in the graft substrate to be diagnosed is diagnosed.

[0016] The non-destructive diagnostic method for graft polymerization according to the present invention comprises: A method for non-destructively diagnosing the degree of graft polymerization (degree of functional graft polymerization) of a functional monomer in a graft substrate obtained by graft polymerizing an electrically polar functional monomer onto a crystalline polymer substrate, comprising: (S1) preparing N samples of graft substrates (hereinafter also referred to as "N samples"); (S2) detecting the grafting rate ΔG of each of the N samples; (S3) detecting a rate of change ΔB in the resonant frequency of each of the N samples by an X-band microwave dielectric absorption method using the pinhole-type microwave cavity resonator; (S4) A regression line of (ΔB, ΔG) detected for the N samples is calculated, and the slope of the line is the functional graft coefficient k t and (S5) The graft rate ΔG and the rate of change in resonance frequency ΔB (ΔB, ΔG) are detected for a graft substrate to be diagnosed, and the detected graft rate ΔG and the detected ΔB are combined to calculate the functional graft coefficient k t The standard grafting rate (k t × ΔB) to diagnose the degree of functional graft polymerization in the graft substrate to be diagnosed; Includes:

[0017] In the non-destructive diagnostic method for graft polymerization according to the present invention, the step (S1) of preparing N samples of graft substrates includes: Preparing a sample of crystalline polymer substrate (S1·1)W0(g); (S1·2) irradiating the sample of the crystalline polymer substrate with an electron beam; (S1·3) preparing an aqueous monomer solution by mixing the functional monomer in water; (S1·4) immersing the sample of the crystalline polymer substrate irradiated with the electron beam in the aqueous monomer solution; (S1·5) immersing the sample of the crystalline polymer substrate immersed in the aqueous monomer solution in a thermostatic chamber and performing graft polymerization to obtain a sample of the graft substrate of W(g); (S1·6) performing the steps (S1·1) to (S1·5) on N samples of the crystalline polymer substrate to prepare N samples of the graft substrate (N samples); Includes:

[0018] In the non-destructive diagnosis method for graft polymerization according to the present invention, the step (S1·3) of preparing a monomer aqueous solution by mixing the functional monomer in water may include, when the functional monomer is hydrophobic, (S1·3·1) preparing a hydrophilic nonpolar monomer; (S1·3·2) preparing an aqueous monomer solution by mixing the hydrophilic nonpolar monomer together with the hydrophobic functional monomer in water; Includes:

[0019] In the non-destructive diagnostic method for graft polymerization according to the present invention, the step (S3) of detecting a rate of change in resonant frequency ΔB of each of the N samples by an X-band microwave dielectric absorption method using the pinhole-type microwave cavity resonator comprises: (S3·1) preparing a microwave source that generates X-band microwaves; (S3·2) preparing a pinhole-type X-band microwave cavity resonator having a pinhole on a sidewall thereof; (S3·3) A step of placing a sample of the graft base material in the vicinity of a pinhole of the microwave cavity resonator through which the oscillating microwave generated from the microwave generating source is guided.

[0020] In the non-destructive diagnostic method for graft polymerization according to the present invention, the step (S4) of determining a regression line of (ΔB, ΔG) detected for the N samples and determining the functional graft coefficient kt, which is the slope of the regression line, comprises: (S4·1) For each graft base material sample i, the graft ratio ΔG i and the rate of change of the resonant frequency ΔB i Ratio of ΔG i / ΔB i and (S4·2) Said ΔG i / ΔB i Using (ΔG i / ΔB i -k) 2 Calculate the k that minimizes the sum of the functional graft coefficient k t and Includes:

[0021] In the non-destructive diagnostic method for graft polymerization according to the present invention, the step (S5) of diagnosing the degree of functional graft polymerization of the graft substrate to be diagnosed includes: (S5·1) detecting (ΔB, ΔG) of the graft substrate to be diagnosed; (S5·2) The detected ΔB and the functional graft coefficient k t Using the standard grafting rate (k t ×ΔB); (S5·3) The detected grafting rate ΔG and the calculated standard grafting rate (k t × ΔB), the grafting difference ratio δg = 100 × |ΔG-k t ×ΔB| / (k t ×ΔB).

[0022] In the non-destructive diagnosis method for graft polymerization according to the present invention, it is preferable to calculate the dipole moment of each molecule of the electrically polar functional monomer, the substrate, and the graft substrate by a semi-empirical molecular orbital method. When the functional monomer is hydrophobic, the dipole moment of each molecule of the hydrophobic functional monomer, the hydrophilic non-polar monomer, the substrate, and the graft substrate formed by graft polymerization of the functional monomer onto the substrate may be calculated by a semi-empirical molecular orbital method. (2) Method for testing the degree of functional graft polymerization and functional graft substrate

[0023] The method for testing the degree of functional graft polymerization according to the present invention is to measure the functional graft coefficient k by graft-polymerizing a functional monomer onto a crystalline polymer substrate having a known resonance frequency f. t In a known graft substrate, A test method for estimating the functional graft ratio ΔG of a test graft substrate (weight W(g)) of the same type as the above by an X-band microwave dielectric absorption method using a pinhole-type microwave cavity resonator having a pinhole on the side wall surface, comprising: (S7) a step of bringing an arbitrary point of the graft substrate to be inspected close to the pinhole of the microwave cavity resonator within an effective distance d and detecting a microwave resonance frequency f' of the arbitrary point; (S8) Calculate the rate of change in the resonant frequency ΔB = (f-f') / f and use the known graft coefficient k t Using k t ×ΔB; The calculated standard grafting rate k t ×ΔB can be estimated as the functional graft rate of the graft substrate to be inspected.

[0024] The method for testing the degree of functional graft polymerization according to the present invention is to measure the functional graft coefficient k by graft-polymerizing a functional monomer onto a crystalline polymer substrate having a known resonance frequency f. t In a known graft substrate, A method for inspecting the homogeneity of the degree of graft polymerization (functional graft polymerization degree) of a functional monomer of a graft substrate (weight W (g)) of the same type as the above by an X-band microwave dielectric absorption method using a pinhole-type microwave cavity resonator having a pinhole on the side wall surface, comprising: (S9) A step of bringing any M points on the graft substrate to be inspected close to the pinhole of the microwave cavity resonator within an effective distance d, and detecting the microwave resonance frequency f' at each point; (S10) calculating the rate of change of the resonant frequency at each M point ΔB=(f-f') / f; The homogeneity of the graft substrate to be inspected can be confirmed from the degree of variation in the obtained rate of change ΔB.

[0025] The method for inspecting the degree of functional graft polymerization according to the present invention is a method for inspecting the degree of functional graft polymerization for confirming the homogeneity of the graft substrate to be inspected, comprising: (S11) The rate of change of the resonant frequency at each point M obtained in step (S10) ΔB i Average value of

number

number

[0026] The functional graft substrate according to the present invention is prepared by the above step (S12). Resonant frequency difference rate

number

[0027] The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention is a device for measuring the microwave resonance characteristics (resonance frequency) of a crystalline polymer substrate by a microwave dielectric absorption method, The microwave cavity resonator includes a pinhole-type microwave cavity resonator having a pinhole opened in a side wall surface of a rectangular parallelepiped whose upper and lower bottom surfaces are connected by four side wall surfaces, a microwave generating source capable of oscillating an X-band (9 to 12 GHz) oscillating microwave, a circulator capable of introducing the oscillating microwave into the microwave cavity resonator, and a microwave observer capable of detecting the power and frequency of the microwave reflected in the microwave cavity resonator, The oscillating microwave generated from the microwave generating source is introduced into the microwave cavity resonator via a waveguide by a circulator, a part of the introduced oscillating microwave leaks out from the pinhole, the leaked microwave leaking out from the pinhole is irradiated onto the coated polymer substrate located close to the pinhole within an effective distance d, and is reflected into the microwave cavity resonator, and together with the introduced oscillating microwave, is reflected in the microwave cavity resonator to form a reflected microwave, and the power and frequency of the reflected microwave can be detected by the microwave observation device.

[0028] In the pinhole-type X-band microwave resonance characteristic measuring device according to the present invention, the pinhole-type microwave cavity resonator has a rectangular parallelepiped shape with its upper and lower bottom surfaces connected by four side wall surfaces, and its interior is hollowed out in a rectangular parallelepiped shape, with a pinhole corresponding to mode TE102 being opened in one of the side wall surfaces.

[0029] In the pinhole-type X-band microwave resonance characteristic measuring device of the present invention, the pinhole formed on the side wall surface is a rectangle with long and short sides of 4 mm ± 1 mm and 8 mm ± 1 mm, respectively.

[0030] The pinhole-type X-band microwave resonance characteristic measuring device of the present invention is characterized in that the microwave cavity resonator is formed from metal with a thickness of 2 mm ± 0.5 mm, and the inner diameter of the hollowed-out rectangular parallelepiped is 10 mm × 23 mm × 45 mm.

[0031] In the pinhole-type X-band microwave resonance characteristic measuring device according to the present invention, an effective distance d from the pinhole may be d=2 mm. [Effects of the Invention]

[0032] The non-destructive diagnostic method for graft polymerization according to the present invention can diagnose the degree of graft polymerization (degree of functional graft polymerization) of an electrically polar functional monomer for a graft substrate (weight W) obtained by graft polymerizing the functional monomer onto a substrate (crystalline polymer substrate; weight W0).

[0033] The graft rate ΔG = (W-W0) / W0 detected for each of the N graft base material samples and the change rate of the resonant frequency ΔB = (f-f') / f measured by the microwave dielectric absorption method were used to calculate the regression line of ΔG / ΔB. The functional graft coefficient k, which is the slope of the line, was calculated from N sets of data (ΔB, ΔG). t The degree of functional graft polymerization in the same type of graft substrate to be diagnosed is nondestructively diagnosed using the above method. That is, the (ΔB, ΔG) of the graft substrate to be diagnosed is detected by microwave dielectric absorption method, and the detected graft rate ΔG, the detected ΔB, and the functional graft coefficient k are calculated. t The standard grafting rate (k t ×ΔB) and comparing these, the degree of graft polymerization of the functional monomer in the graft substrate to be diagnosed can be diagnosed.

[0034] This standard grafting rate (k t × ΔB) is considered to be the contribution of the grafting rate ΔG due to the graft polymerization of functional monomers with electrical polarity. The detected grafting rate ΔG detected by the microwave dielectric absorption method for the graft substrate to be diagnosed and the standard grafting rate (k t If a difference occurs in the graft matrix (ΔB), it suggests that other non-polar monomers or other deposits have adhered to the graft substrate under diagnosis.

[0035] As described above, the non-destructive diagnostic method for the degree of functional graft polymerization according to the present invention combines microwave dielectric absorption spectroscopy with the conventional evaluation of the degree of graft polymerization based on the graft ratio ΔG, thereby establishing a quantitative and non-destructive method for evaluating graft substrates in which electrically polar monomers are graft-polymerized onto a substrate. The combination of microwave dielectric absorption spectroscopy and semi-empirical molecular orbital analysis further clarifies the details of graft polymerization.

[0036] That is, in the case of the present invention, when the molecular structure is changed by graft polymerizing an electrically polar functional monomer onto a base material, the change in resonant wavelength ΔB=(f-f') / f is determined using a microwave dielectric absorption method, and the dipole moment of the desired functional monomer to be polymerized is predicted in advance using a semi-empirical molecular orbital method, whereby the contribution of the functional monomer to the increase in the graft ratio can be evaluated.

[0037] The method for testing the degree of functional graft polymerization according to the present invention includes grafting a functional monomer onto a crystalline polymer substrate having a known resonance frequency f, and measuring the functional graft coefficient k t By using a graft substrate with a known value, the functional graft rate of the graft substrate to be inspected and the uniformity of the functional graft polymerization can be inspected. For example, the uniformity of the functional graft polymerization can be confirmed from the variation in the rate of change in the resonant frequency ΔB at different points M of the graft substrate to be inspected.

[0038] Alternatively, the rate of change in the resonant frequency at each of the points M of the graft substrate to be inspected ΔB i Average value of

number

number

[0039] (Pinhole-type X-band microwave resonance characteristic measurement device) The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention includes a microwave generating source that generates an oscillating microwave, a pinhole-type microwave cavity resonator into which the oscillating microwave is introduced, and a microwave observation device that can detect the power and frequency of the reflected microwave formed by reflection within the microwave cavity resonator.The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention uses wavelengths in the X-band (9 to 12 GHz) that are longer than the wavelengths of microwaves used in conventional microwave resonance characteristic measuring devices, and therefore can obtain a response that is averaged in the thickness direction, taking into account the effects of not only the surface of the polymer material to which the microwave is irradiated, but also the unevenness formed on the back surface.

[0040] (pinhole) This pinhole-type microwave cavity resonator is preferably a rectangular parallelepiped with its upper and lower bottom surfaces connected by four sidewalls, and the interior of the microwave cavity resonator is hollowed out in a rectangular parallelepiped shape. In the present invention, since the change in resonance wavelength (ΔB) is measured using X-band microwaves, there is no need to increase the sensitivity (Q value) of the microwave cavity resonator more than necessary. Therefore, there is no need to hollow out the interior of the microwave cavity resonator of the present invention in a spherical or cylindrical shape to achieve high sensitivity, and it can be easily molded and manufactured at low cost.

[0041] The pinhole formed in the sidewall of the pinhole-type X-band microwave resonance characteristic measurement device of the present invention is characterized by a rectangular shape with long and short sides of 4 mm ± 1 mm and 8 mm ± 1 mm, respectively. The shape and size of this pinhole were determined through trial and error to accommodate microwaves in mode TE102 in the pinhole-type microwave cavity resonator of the present invention, and measurements can be performed using microwaves leaking from the pinhole. In other words, there is no need to insert an irradiated object such as a polymer substrate into the microwave cavity resonator. Instead, the irradiated object can be placed close to or covered by the pinhole from the outside, within an effective distance d = 2 mm from the pinhole, allowing for effective measurement of ΔB and other parameters using the microwave dielectric absorption method. [Brief explanation of the drawings]

[0042] [Figure 1] FIG. 1 is a flow chart of a non-destructive diagnostic method for the degree of functional graft polymerization according to an embodiment. [Figure 2(a)] 1 shows the preparation of a substrate for a non-destructive diagnostic method for the degree of functional graft polymerization according to an embodiment. [Figure 2(b)] Non-destructive diagnostic method for functional graft polymerization degree according to the embodiment, irradiation with electron beams or the like. [Figure 2(c)] 1 shows the preparation of an aqueous monomer solution for a non-destructive diagnostic method for the degree of functional graft polymerization according to an embodiment. [Figure 2(d)] 1 shows a non-destructive diagnostic method for the degree of functional graft polymerization according to an embodiment, in which the substrate is immersed in an aqueous monomer solution. [Figure 2(e)] FIG. 2 is a flow chart showing each stage of graft polymerization in the non-destructive diagnostic method for the degree of functional graft polymerization according to the embodiment. [Figure 3] FIG. 1 is a graph showing a regression line between the rate of change ΔB in resonance frequency between the base material and the graft base material and the graft ratio. [Figure 4] Photographs of the apparatus according to the present invention include (a) a perspective plan view of a microwave dielectric absorption measuring apparatus, (b) a perspective plan view of a pinhole-type X-band microwave cavity resonator in which a sample is placed, and (c) an enlarged photograph of a side wall surface of the microwave cavity resonator in which a pinhole is opened. [Figure 5] 1 is a conceptual diagram of a pinhole-type X-band microwave resonance characteristic measuring device according to the present invention. [Figure 6] Photographs of sample samples placed on a cardboard sheet laid on a stainless steel tray, including (a) an oblique photograph of sample samples No. 1 to No. 11, (b) a plan photograph of sample No. 11, and (c) a photograph showing the surface temperature measurement of the sample samples. [Figure 7] (a) Graph of radical concentration and exposure time in air, (b) Photograph of irradiated sample placed in a zippered freezer bag, (c) Photograph of dry ice box (using 8 kg of dry ice). [Figure 8] (a) Molecular model of the substrate (polyethylene compound), (b) Molecular model of the A and B monomers, (c) Molecular model of the B polymer (polyacrylic acid), and (d) Molecular model of the graft substrate, showing the non-destructive diagnostic method for graft polymerization according to the present invention. [Figure 9] (a) Photograph of the process in which a polyethylene substrate was immersed in an aqueous monomer solution transferred to an Erlenmeyer flask and the atmosphere was replaced with argon for 10 minutes to reduce the dissolved oxygen in the solution, (b) a photograph of a thermostatic chamber, and (c) a photograph of the Erlenmeyer flask in the thermostatic chamber. [Figure 10] FIG. 10 is a measurement table showing the masses W0 (g) of samples obtained by cutting each of the samples of substrates No. 1 to No. 11 according to the examples into quarters. [Figure 11] Graphs showing microwave resonance curves (reflected microwave power versus microwave frequency), where (a) only the intensity of the reflected microwave power is varied, and (b) only the microwave frequency is varied. [Figure 12] (a) Graph of W-W0 (mass of graft substrate - mass of polyethylene substrate) and absorbed dose, (b) Graph of graft ratio and absorbed dose. [Figure 13(a)] This is a spectrum diagram of the microwave resonance frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement for the base material (polyethylene compound). [Figure 13(b)]FIG. 11B is a spectrum diagram of the microwave resonance frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement on sample 11b. [Figure 13(c)] FIG. 10 is a spectrum diagram of the microwave resonant frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement for sample 3a. [Figure 13(d)] A spectrum diagram of the microwave resonance frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement for sample 6b (bottom). [Figure 13(e)] FIG. 1B is a spectrum diagram of the microwave resonant frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement for sample 1b. [Figure 13(f)] A spectrum diagram of the microwave resonant frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement on sample 5c. [Figure 13(g)] 10 is a spectrum diagram of the microwave resonant frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement for sample 7c. [Figure 13(h)] A spectrum diagram of the microwave resonant frequency of each sample, which is a spectrum diagram of Fourier transform infrared spectroscopy measurement for sample 6c. [Figure 14] A photograph of an insertion-type microwave cavity resonator and a schematic diagram showing the electric field distribution inside it. [Figure 15] (a) A perspective view of a pinhole-type microwave dielectric absorption measuring device described in Patent Document 3, (b) a side view of the same, (c) a cross-sectional view of the same side in a state where a pinhole provided on the side is covered with a wiring cable, and (d) a schematic diagram of the measuring device. DETAILED DESCRIPTION OF THE INVENTION

[0043] Hereinafter, with reference to the drawings, embodiments and examples of (1) a non-destructive diagnostic method for graft polymerization according to the present invention, (2) a method for inspecting the degree of functional graft polymerization and a functional graft substrate, and (3) a pinhole-type X-band microwave resonance characteristic measuring device will be described. Note that the same reference numerals will be used for the same components throughout the drawings. (1) Non-destructive diagnostic method for the degree of functional graft polymerization

[0044] The non-destructive diagnostic method for functional graft polymerization degree according to the present invention is a method for diagnosing the graft polymerization degree (functional graft polymerization degree) of a functional monomer having electrical polarity, for a graft substrate obtained by graft polymerizing the functional monomer onto a crystalline polymer substrate.

[0045] The weight of this polymeric substrate is W0 (g), and the weight of the graft-polymerized substrate is W (g). For simplicity, hereinafter, the "polymeric substrate" will be simply referred to as the "substrate," and the "graft-polymerized substrate" (or "graft-polymerized graft substrate") will be simply referred to as the "graft substrate."

[0046] In the present invention, a graft substrate to which the functionality of the functional monomer is imparted is obtained by graft polymerizing an electrically polar functional monomer onto a substrate (crystalline polymer substrate). However, as described below, other monomers may be graft polymerized onto the substrate along with the desired functional monomer, or other deposits may adhere to the substrate, and the desired functionality may not necessarily be imparted. Therefore, hereinafter, a graft substrate to which the desired functionality has been imparted through graft polymerization of the desired functional monomer will be referred to as a "functional graft substrate," to distinguish it from a "graft substrate" simply obtained as a result of graft polymerization. Therefore, the above-mentioned "functional graft polymerization degree," defined in the present invention as the graft polymerization degree of the functional monomer, is substantially synonymous with the graft polymerization degree of the "functional graft substrate."

[0047] The non-destructive diagnostic method for the degree of functional graft polymerization of the present invention first detects the graft rate ΔG = (W - W0) / W0 for each of N graft-polymerized graft base materials, and the rate of change in resonant frequency ΔB = (f - f') / f as determined by microwave dielectric absorption, where f and f' are the resonant frequencies of the base material and the graft base material, respectively.

[0048] Then, the regression line of (ΔG / ΔB) obtained from the detected N sets of (resonance frequency change rate ΔB, graft rate ΔG) is used to non-destructively diagnose the degree of functional graft polymerization in a graft substrate of the same type as the graft substrate.

[0049] That is, for N graft-based samples, a pinhole-type microwave cavity resonator with a pinhole on the sidewall is used to generate N sets of data (ΔB, ΔG) detected by microwave dielectric absorption spectroscopy in the X-band (9-12 GHz). The functional graft coefficient k, which is the slope of the regression line, is then calculated from these N sets of data. t Ask for.

[0050] On the other hand, the (ΔB, ΔG) of the graft substrate to be diagnosed is detected by the microwave dielectric absorption method. The detected ΔB and the functional graft coefficient k t From this, the standard grafting rate (k t × ΔB).

[0051] The non-destructive diagnostic method for the degree of functional graft polymerization according to the present invention is based on the detected ΔG of the graft substrate to be diagnosed and the calculated standard graft rate (k t ×ΔB), the degree of graft polymerization of the functional monomer in the graft substrate to be diagnosed (functional graft polymerization degree) can be diagnosed.

[0052] As described above, in the non-destructive diagnostic method of the present invention for the degree of functional graft polymerization, an electrically polar functional monomer is graft-polymerized onto a crystalline polymer substrate. However, even if the graft ratio ΔG=(W-W0) / W0 is calculated as in the conventional method, it is not possible to determine whether the weight W (g) of the graft substrate is due to the graft polymerization of the functional monomer or to other monomers or other deposits graft-polymerized with the functional monomer.

[0053] Therefore, in the present invention, it is preferable to calculate in advance the dipole moments of the electrically polar functional monomer and crystalline polymer substrate, and the graft substrate (functional graft substrate) having the desired functionality to be obtained by graft polymerization of these, by semi-empirical molecular orbital methods. If the dipole moments of the substrate, functional monomer, other monomers, etc. are calculated in advance, the type of graft-polymerized monomer can be estimated by determining the change in resonant frequency (ΔB=(f-f') / f) of the substrate and graft substrate before and after graft polymerization by microwave dielectric absorption spectroscopy. The reason for this is as follows.

[0054] (Principles of microwave cavity resonator measurement) It is known that the change in the dielectric constant of a test object can be measured with high sensitivity by the microwave dielectric absorption method using a microwave cavity resonator. In general, if ε is the dielectric constant of the test object, then: ε=ε1-iε2 ε1: real part of the dielectric constant ε2: Imaginary part of dielectric constant (S dielectric loss) holds true.

[0055] Furthermore, the microwave dielectric absorption method using a microwave cavity resonator can measure the Q value (Q=f / Δf) of the resonant frequency curve of a test object and the change in resonant frequency (f-f') as shown in Figures 11(a) and 11(b). In the relational expressions for these quantities shown below, f is the resonant frequency of the test object, Δf is the half-width of the resonant frequency curve, f' is the resonant frequency of the test object after a change in molecular structure due to, for example, a chemical change, and Δf' is the half-width of the resonant frequency curve of the test object after the change.

[0056] (Q value) Regarding the Q value, the following relationship holds: Q=f / Δf ΔQ -1 =(Δf-Δf') / f∝ε2 Therefore, the change in the Q value is proportional to the imaginary part of the dielectric constant (dielectric loss).

[0057] (Change in resonant frequency ΔB) The following relationship holds for the change in resonant frequency (f-f'): ΔB=(f-f') / f∝ε1 Therefore, the rate of change of the resonant frequency ΔB is proportional to the real part of the dielectric constant.

[0058] For example, when the molecular structure of the test specimen is substantially constant, as in the case of measuring the deterioration of the insulation coating of a conductive cable in Patent Document 3, the magnitude of the reflected microwave power may change, but the resonant frequency of the microwave does not change significantly, as shown in Figure 11(a). On the other hand, when the molecular structure of the test specimen changes from a polymer base material to a graft base material in which an electrically polar functional monomer is polymerized before and after graft polymerization, as in the present invention, the resonant frequency of the microwave may change significantly from f to f', as shown in Figure 11(b).

[0059] Therefore, when graft-polymerizing an electrically polar functional monomer onto a substrate as in the present invention, the dipole moments of the substrate, functional monomer, other monomers to be graft-polymerized together, and the graft substrate with the desired functionality (functional graft substrate) can be calculated in advance using semiempirical molecular orbital methods. The type of graft-polymerized monomer can then be estimated by measuring the change in resonant frequency (ΔB = (f-f') / f) of the substrate and graft substrate before and after graft polymerization using microwave dielectric absorption. For example, if the weight of the graft substrate increases but the resonant frequency remains unchanged, it can be assumed that a nonpolar monomer, rather than the desired functional monomer, has adhered to the substrate. However, since crystalline polymer substrates and other monomers to be graft-polymerized together with the functional monomer are often electrically nonpolar and their dipole moments can be ignored, predictions using semiempirical molecular orbital methods are not necessarily required in such cases.

[0060] (Application of microwave dielectric absorption method to graft polymerization) Thus, in the past, graft polymerization was evaluated primarily using the graft ratio ΔG = (W - W0) / W0, focusing on the increase in the mass of the substrate due to graft polymerization. However, the non-destructive diagnostic method for the degree of functional graft polymerization according to the present invention focuses on the change in dielectric constant accompanying graft polymerization and diagnoses the graft ratio of graft polymerization using microwave dielectric absorption spectroscopy. That is, when the molecular structure changes due to the graft polymerization of an electrically polar functional monomer onto a polymer substrate, the change in resonant frequency (ΔB = (f - f') / f) is determined using microwave dielectric absorption spectroscopy, and the dipole moment of the desired functional monomer to be polymerized can be predicted in advance using semi-empirical molecular orbital analysis, allowing the contribution of the desired functional monomer to the increase in the graft ratio to be evaluated.

[0061] As described above, the non-destructive diagnostic method for the degree of functional graft polymerization according to the present invention combines microwave dielectric absorption spectroscopy and semi-empirical molecular orbital analysis to establish a quantitative and non-destructive method for evaluating graft substrates formed by graft polymerization of electrically polar monomers.

[0062] [Embodiment] The non-destructive diagnostic method for the degree of functional graft polymerization according to the present invention will be described below with reference to embodiments and examples.

[0063] The non-destructive diagnostic method for functional graft polymerization degree of the present embodiment is a method for non-destructively diagnosing the graft polymerization degree (functional graft polymerization degree) of a functional monomer having electrical polarity in a graft substrate obtained by graft polymerizing the functional monomer onto a crystalline polymer substrate, the method comprising: (S1) Step of preparing N samples of graft base materials (hereinafter also referred to as "N samples"). (S2) A step of detecting the grafting rate ΔG of each of the N samples. (S3) A step of detecting the rate of change ΔB of the resonant frequency of each of the N samples by an X-band microwave dielectric absorption method using the pinhole-type microwave cavity resonator. (S4) A regression line of (ΔB, ΔG) detected for the N samples is calculated, and the slope of the line is the functional graft coefficient k t Steps to find (S5) The graft rate ΔG and the rate of change in resonance frequency ΔB (ΔB, ΔG) are detected for a certain graft substrate to be diagnosed, and the detected graft rate ΔG and the detected ΔB are combined to calculate the functional graft coefficient k t The standard grafting rate (k t × ΔB) to diagnose the degree of functional graft polymerization in the graft substrate to be diagnosed.

[0064] In this embodiment, as an example, as shown in the flow diagram of Figure 1, a polyethylene sheet (graft substrate) with deodorizing function was produced by graft polymerizing sodium styrene sulfonate (hydrophobic functional monomer A) and acrylic acid (hydrophilic non-polar monomer B) onto a high-density polyethylene sheet (substrate). This was then used as a graft substrate sample to assess the degree of graft polymerization of the hydrophobic functional monomer (sodium styrene sulfonate). Below, the above steps (S1) to (S5) will be described in detail using examples. (1-1) Preparation of graft substrate

[0065] The above step (S1) of preparing N samples of graft base materials includes the following steps (S1·1) to (S1·5). (S1·1) Step of preparing a sample of substrate (crystalline polymer substrate) W0(g) (S1·2) A step of irradiating the substrate sample with an electron beam. (S1·3) A step of preparing an aqueous monomer solution by mixing the functional monomer with water. (S1·4) A step of immersing the substrate sample irradiated with the electron beam in the aqueous monomer solution. (S1·5) immersing the substrate sample immersed in the monomer aqueous solution in a thermostatic chamber and performing graft polymerization to obtain a graft substrate sample of W(g); (S1·6) A step of performing the above steps (S1·1) to (S1·5) on N base material samples to prepare N graft base material samples (N samples).

[0066] (Polyethylene sheet with deodorizing properties) As described below, N graft substrate samples were prepared using a high-density polyethylene sheet as the substrate (crystalline polymer substrate), sodium p-styrenesulfonate hydrate as the hydrophobic functional monomer A, and acrylic acid as the hydrophilic nonpolar monomer B (step (S1)). In the examples below, the desired monomer to be graft polymerized onto the substrate (polyethylene sheet) is hydrophobic functional monomer A (sodium p-styrenesulfonate hydrate), and the objective is to obtain a polyethylene sheet with added deodorizing function as a functional graft substrate by graft polymerization. [Example]

[0067] Step (S1·1) of preparing a substrate Step (S1·1) is a step of preparing a substrate (crystalline polymer substrate) of W0(g) (see FIG. 2(a)).

[0068] (Base material, chemicals, equipment) ·Base material used The substrate samples used were high-density polyethylene sheets (DuPont Tyvek (registered trademark) hard type 1070D) with a thickness of 0.15 mm. The mass of each substrate sample before electron beam irradiation was defined as W0 (g). Three of these substrate samples were then stacked and placed in a gas-barrier bag, which was then evacuated and sealed (see Figures 6(a) to (c)). This was done so that even if the high-density polyethylene sheet inside the gas-barrier bag reacts with air or the like after electron beam irradiation, the middle sheet would remain intact and usable. Chemicals used Sodium p-styrenesulfonate hydrate (Tokyo Chemical Industry Co., Ltd.), sodium p-styrenesulfonate (Fujifilm Wako Pure Chemical Industries, Ltd.), acrylic acid (Nacalai Tesque, Inc.) ·Equipment used Gas barrier bag (Fukusuke Kogyo Co., Ltd.), vacuum sealer, dry ice, dry ice box, silicone double cap, screw vial (110 mL), beaker, glass manifold, silicone tubing, long syringe needle, syringe needle

[0069] A total of 11 substrate samples were prepared using the above three-ply high-density polyethylene sheets (0.15 mm thick, W0(g)) (see Figure 6(a)). [Example]

[0070] A step of irradiating the substrate with an electron beam (S1·2) Step (S1·2) is the step of irradiating the substrate with an electron beam (see Figure 2(b)). Electron beam irradiation was performed at Kansai Electron Beam Co., Ltd. (Mihama-cho, Fukui Prefecture) using the equipment listed in Table 1. [Table 1]

[0071] (Preparation of electron beam irradiated substrate) Prior to electron beam irradiation, the substrate sample (high-density polyethylene sheet) was cooled to approximately -20°C in a freezer. The cooled substrate sample was placed on a tray and irradiated with 30 kGy of electron beam radiation in one go. The samples were then irradiated with cumulative doses of 60 kGy, 120 kGy, and 210 kGy. The surface temperature of the substrate sample (high-density polyethylene sheet) rose by 1°C after 2 kGy of electron beam irradiation. Hereinafter, the substrate sample (high-density polyethylene sheet) irradiated with electron beam radiation will also be referred to as the "irradiated sample."

[0072] (electron beam irradiation) As shown in Figures 6(a) to 6(c), the substrate sample was fixed with tape and placed on a cardboard sheet laid on a stainless steel tray. The dose was measured using a dosimeter (CTA dosimeter) every 60 kGy of irradiation. The surface temperature of the sample was also measured every 30 Gy of irradiation (see Figure 6(c)).

[0073] [Table 2]

[0074] In Table 2, "sealed" refers to a sealed gas-barrier bag containing a three-ply sample, while "open" refers to an unsealed gas-barrier bag. The "sealed" bag prevents air from entering the gas-barrier bag, avoiding reaction with the radicals generated in the irradiated sample (substrate sample after electron beam irradiation). Figure 7(a) is a graph showing the alkyl radical concentration at various temperatures versus exposure time in air (Saito and Sugo, "Cats and Graft Polymerization," Maruzen Co., Ltd.). This shows that radicals do not disappear if stored at a low temperature, the dry ice temperature of -78°C.

[0075] (Storage of electron beam irradiated substrate) Therefore, to prevent the loss of radicals due to contact between the irradiated sample and air, the irradiated sample was immediately placed in a freezer bag and cooled with dry ice (see Figures 7(b) and (c)). That is, the irradiated sample was placed in a zippered freezer bag (Figure 7(b)) and cooled with dry ice. 8 kg of dry ice was used in the dry ice box in Figure 7(c). [Example]

[0076] Step S1·3: Preparing an aqueous monomer solution Step (S1·3) is a step of preparing an aqueous monomer solution by mixing a functional monomer with water (see Figure 2(c)).

[0077] If the functional monomer is hydrophilic, the functional monomer is mixed with water to prepare an aqueous monomer solution. However, if the functional monomer is hydrophobic, step (S1·3) includes the following steps (S1·3·1) and (S1·3·2). (S1·3·1) Preparation of hydrophilic nonpolar monomer B (S1·3·2) A step of preparing a monomer aqueous solution by mixing the hydrophobic functional monomer A and the hydrophilic nonpolar monomer B in water.

[0078] (Preparation of aqueous monomer solution) In this example, sodium p-styrenesulfonate was used as the hydrophobic functional monomer A, and acrylic acid was used as the nonpolar monomer B. The molecular models of each are shown in Figure 8(b). A and B were then mixed with water in a mass ratio of 1:1:2 to prepare an aqueous monomer solution. [Example]

[0079] (Calculation of dipole moment by semi-empirical molecular orbital method) FIG. 8 shows the non-destructive diagnostic method for graft polymerization according to the present invention, including (a) a molecular model diagram of the substrate (polyethylene compound), (b) a molecular model diagram of monomers A and B (sodium p-styrenesulfonate, acrylic acid), (c) a molecular model diagram of polymer B (polyacrylic acid), and (d) a molecular model diagram of the graft substrate.

[0080] The dipole moments of the molecular models of the above materials used in the graft polymerization in this embodiment were calculated by the semi-empirical molecular orbital method using Winmosta. The calculated dipole moments (Debye) are displayed above the molecular model diagrams shown in Figures 8(a) to 8(d).

[0081] According to this, the dipole moment of the polyethylene model compound (n-octane) is 0.000 (Debye). The dipole moments of sodium p-styrenesulfonate (functional monomer A) and acrylic acid (monomer B) are 14.389 (Debye) and 1.912 (Debye), respectively. Furthermore, in the molecular model of the graft substrate in Figure 8(d) to which these functional monomers A and B have been added, the dipole moment is 13.014 (Debye), which is confirmed to be increased compared to the polyethylene model compound of the substrate (Figure 8(a)).

[0082] Therefore, when the weight of the substrate increases due to graft polymerization, if the dipole moment of the graft substrate increases significantly, it can be assumed that the desired functional monomer A has been grafted. Conversely, if the dipole moment of the graft substrate does not increase and remains approximately 0 despite an increase in the weight of the substrate, it can be assumed that monomer B, not the desired functional monomer A, has adhered to the substrate. [Example]

[0083] A step (S1·4) of immersing the substrate irradiated with the electron beam in an aqueous monomer solution. In step (S1·4), the substrate (irradiated sample) irradiated with the electron beam in step (S1·2) is immersed in the monomer aqueous solution prepared in step (S1·3) (see Figure 2(d)). In step (S1·2), the 11 polyethylene substrates (irradiated samples) stored in dry ice after electron beam irradiation were each cut into quarters.

[0084] (Preparation of aqueous monomer solution) Argon substitution and graft polymerization As shown in Figure 9(a), the monomer aqueous solution prepared in step (S1·3) was transferred to an Erlenmeyer flask. Next, a polyethylene substrate (irradiated sample) cut into quarters was immersed in the monomer aqueous solution and argon was substituted for 10 minutes to reduce the dissolved oxygen in the solution. [Example]

[0085] A step (S1·5) of graft polymerization in a thermostatic bath In step (S1·5), the irradiated sample immersed in the monomer aqueous solution in step (S1·4) is placed in a thermostatic bath to allow graft polymerization (see Fig. 2(e)). Fig. 9(b) is a photograph of the thermostatic bath, and Fig. 9(c) is a photograph of the Erlenmeyer flask in the thermostatic bath.

[0086] After degassing the irradiated sample immersed in the monomer aqueous solution in step (S1·4), it was immersed in water in a thermostatic chamber set at 50°C (Figure 9(b) and (c)), and the graft polymerization reaction was initiated. The sample was immersed for 2, 5, 10, and 20 hours, after which it was removed, washed, and dried. [Example]

[0087] Step (S1·6) of preparing N samples of graft substrate Step (S1·6) is a step in which the above steps (S1·1) to (S1·5) are performed on N substrates (crystalline polymer substrates) to prepare N graft substrate samples (see FIGS. 2(a) to 2(e)). As described above, in the example of this embodiment, N=11 (see FIG. 6(a)). However, since each substrate was cut into quarters in Example 5, N=11×4=44 graft substrate samples (hereinafter simply referred to as "samples" or "graft substrate samples") were obtained, as shown in FIG. 10. (1-2) Step (S2) of determining the graft ratio ΔG

[0088] Step (S2) is a step of determining the graft ratio ΔG of each of the N samples (graft base material samples).

[0089] (Calculation of graft ratio) The mass W (g) of the graft substrate sample dried in step (S1·6) was measured, and the graft ratio ΔG was calculated. As mentioned above, the mass of the high-density polyethylene sheet substrate before graft polymerization was W0 (g) (see Figure 10), and the graft ratio ΔG was calculated using the following equation 1.

[0090] [Formula 1] Graft ratio ΔG (%) = 100 (W-W0) / W0 W0: Mass of the substrate W: Mass of graft base material

[0091] Figures 12(a) and (b) show graphs of the grafting rate calculated using Equation 1 for each absorbed dose. Figure 12(a) is a graph of W-W0 (mass of graft substrate - mass of polyethylene substrate) versus absorbed dose, and Figure 12(b) is a graph of the grafting rate ΔG versus absorbed dose. As can be seen from these figures, it is difficult to understand the details of graft polymerization from the grafting rate, etc. In other words, it is not possible to determine whether it was monomer A or monomer B that underwent graft polymerization. (1-3) Step (S3) of detecting the rate of change ΔB of the resonant frequency

[0092] Step (S3) is a step of detecting the rate of change ΔB of the resonant frequency of each of the N samples by the X-band microwave dielectric absorption method using the pinhole-type microwave cavity resonator. The rate of change ΔB of the resonant frequency is calculated by the following equation 2:

[0093] [Formula 2] Rate of change ΔB(%)=100×(f-f') / f f: Resonance frequency of the substrate f': Resonance frequency of the graft substrate

[0094] In this section (1-3), the following steps (S3·1) to (S3·3) constituting (S3) of the non-destructive diagnostic method for the degree of functional graft polymerization according to the present invention will be described. (S3·1) A step of preparing a microwave generating source that generates X-band microwaves. (S3·2) A step of preparing a pinhole-type X-band microwave cavity resonator having a pinhole on the side wall. (S3·3) A step of placing a sample of the graft base material in the vicinity of a pinhole of the microwave cavity resonator through which the microwave generated from the microwave generation source is guided.

[0095] (Microwave dielectric absorption measurement device) Step (S3·1) is a step of preparing a microwave generation source (see FIG. 4(a)). In this embodiment, the frequency band of the X-band (8 GHz to 12 GHz) is used, and therefore the frequency of the microwave generated by this microwave generation source includes the frequency band of the X-band.

[0096] (microwave cavity resonator) Step (S3·2) is a step of preparing a pinhole-type X-band microwave cavity resonator with a pinhole on the sidewall. The details will be described later. Figures 4(c) and 4(b) show the resonant frequency of 9.458 GHz and the mode TE 102 This is an enlarged photograph of a pinhole-type X-band microwave cavity resonator with Q=3000. The pinhole size on the side wall of this cavity resonator is 8mm x 4mm, and the mode TE 102 A pinhole is opened at this position (measurement hole in Figure 4(c)).

[0097] (Microwave dielectric absorption measurement device) Fig. 4(a) shows a photograph of the microwave dielectric absorption measuring device used in this embodiment. As described above, the microwave dielectric absorption measuring device is composed of a microwave generation source, a pinhole-type X-band microwave cavity resonator, a power sensor, a microwave observation device such as an oscilloscope, a circulator, and the like, all connected by a waveguide. Fig. 4(b) is an enlarged photograph of the microwave cavity resonator after a sample has been placed on the pinhole (measurement hole). Similar to the pinhole-type X-band microwave cavity resonator, the microwave dielectric absorption measuring device will also be described in detail later.

[0098] Using the microwave dielectric absorption measurement device, the rate of change in resonant frequency, ΔB, of each of the 11 × 4 graft substrate samples was measured by the microwave dielectric absorption method. From these graft substrate samples, seven suitable model numbers of graft substrate samples (and substrate samples) were selected, varying as much as possible the electron beam absorbed dose, the irradiation atmosphere (open / sealed), and the graft polymerization time. These conditions and the graft ratio, ΔG, are summarized in Table 3.

[0099] [Table 3]

[0100] For the samples of the seven model numbers listed in Table 3, the rate of change in resonance frequency ΔB obtained for each sample by the microwave dielectric absorption method is shown in Table 4.

[0101] [Table 4] (1-4) The regression line of (ΔB, ΔG) is calculated, and the functional graft coefficient k t Step (S4) to find

[0102] In step (S4), a regression line of (ΔB, ΔG) detected for the N samples is obtained, and the functional graft coefficient k t This step (S4) consists of steps (S4·1) and (S4·2). That is, (S4·1) For each graft base material sample i, the graft ratio ΔG i and the rate of change of the resonant frequency ΔB i Ratio of ΔG i / ΔB i Steps to find (S4·2) Above ΔG i / ΔB i Using (ΔG i / ΔB i -k) 2 Calculate the k that minimizes the sum of the functional graft coefficient k tSteps to find

[0103] Using the microwave cavity measurement results shown in Table 4, (ΔB, ΔG) were plotted, and the regression line obtained by steps (S4·1) and (S4·2) is shown in Figure 3. The regression line was obtained as in Example 8 below. [Example]

[0104] Functional graft coefficient k t In Figure 3, the sample with model number "7c" is significantly different from the positions of the other samples, so a regression line was calculated for the six samples excluding this one. The correlation coefficient was 0.99.

[0105] (Measurement results using microwave dielectric absorption method) The relationship between the significant graft rate (%) ΔG and ΔB determined from the results of microwave dielectric absorption measurement, i.e., the regression line, is calculated as shown in Equation 3 below, and the slope of the line is the functional graft coefficient k t is k t =1611307.

[0106] [Formula 3] (Grafting rate) ΔG (%) = 1611307 × ΔB (change rate of resonance frequency) [Example]

[0107] Fourier transform infrared spectroscopy (Fourier transform infrared spectroscopy measurement results) To compare with the measurement results obtained by the microwave dielectric absorption method in Example 8, a conventional Fourier transform infrared spectroscopy measurement was performed. The resonance frequency of each of the seven samples was detected using the following Fourier transform infrared spectrophotometer, and the results shown in Figure 13 were obtained. Measuring equipment Agilent Technologies, Inc. Fourier transform infrared spectrophotometer (FTIR) Cary 630 FTIR Spectrophotometer Measurement sample (Shown in the leftmost column of Table 3)

[0108] Figure 13 shows the Fourier transform infrared spectroscopic spectra of each sample: (a) substrate (polyethylene compound), (b) on sample 11b, (c) in sample 3a, (d) under sample 6b, (e) in sample 1b, (f) on sample 5c, (g) in sample 7c, and (h) in sample 6c.

[0109] As described above, even if Fourier transform infrared spectroscopy is performed, it is not possible to determine from the shape of the spectrum diagrams such as those shown in Figures 13(a) to 13(h) whether the change in shape is due to the graft polymerization of a functional monomer or to other monomers or other deposits graft polymerized together with the functional monomer.

[0110] For example, in Figure 3, the sample with the closest ΔB to the above-mentioned "7c" model number is "1b" model number. However, their ΔG values ​​are approximately 660 and 220, respectively. The plot for "1b" is close to the regression line, while the plot for "7c" deviates significantly from the regression line. This is likely due to the weight increase of the graft substrate, not due to efficient graft polymerization of electrically polar functional monomers, but due to the graft polymerization of nonpolar monomers and other deposits, even though the grafting rate ΔG of "7c" model number is high. However, comparing the absorption curves at the resonant frequencies of "7c" model number and "1b" model number in Figure 13(g) and (e) does not reveal any discernible difference between them, and thus does not allow us to understand the details of the graft polymerization, as was the case with the microwave dielectric absorption method.

[0111] As described above, the measurement results obtained by the microwave dielectric absorption method of the present invention are expected to provide more useful information about graft polymerization than the measurement results obtained by conventional Fourier transform infrared spectroscopy. (1-5) Standard grafting rate (k t Step S5: Non-destructive diagnosis of graft polymerization by (ΔB × ΔB)

[0112] Step (S5) detects the graft rate ΔG and the rate of change in resonance frequency ΔB (ΔB, ΔG) for a graft substrate to be diagnosed, and calculates the functional graft coefficient k t The standard grafting rate (k t ×ΔB) to diagnose the degree of functional graft polymerization in the graft substrate to be diagnosed.

[0113] In the following explanation, the sample with the model number "7c" in Table 4 and Figure 3 is considered to be the graft substrate to be diagnosed for convenience. As mentioned above, the relational expression (Equation 3) between the rate of change in resonance frequency ΔB and the graft rate ΔG is obtained, and the functional graft coefficient k t =1611307. (Formula 3):ΔG(%)=1611307×ΔB

[0114] As mentioned above, in Figure 3, the graft ratio ΔG of "7c in" measured by the microwave dielectric absorption method was 658.3%. That is, the graft ratio ΔG of the graft substrate "7c in" to be diagnosed is 658.3%, but by substituting the measurement result ΔB = 0.000169 by the microwave dielectric absorption method into (Equation 3), the graft ratio ΔG is considered to be equivalent to 272.3%. The graft ratio (k t × ΔB) is referred to as the "standard graft ratio" as described above.

[0115] Therefore, the grafting rate ΔG of the diagnosed graft substrate "7c" was measured to be 658.3%, but the standard grafting rate, which is the contribution of the grafting rate ΔG due to the graft polymerization of electrically polar functional monomers estimated from the results of measurements using microwave dielectric absorption method, is thought to be approximately 272.3%. The contribution of this difference is suggested to be due to other non-polar monomers and other attachments.

[0116] As mentioned above, an increase in the dipole moment increases the dielectric constant, and the dipole moment and the dielectric constant ΔB are proportional. Therefore, an increase in the reaction products due to the graft polymerization of electrically polar functional monomers means an increase in the dipole moment. Therefore, the excessive increase in the graft rate ΔG of the diagnosed graft substrate "7c" is thought to be due to an increase in the reaction by-products of the nonpolar monomer, suggesting an increase in mass, i.e., graft rate, without an increase in dipole moment. (2) Method for testing the degree of functional graft polymerization and functional graft substrate

[0117] In this embodiment, a method for testing the degree of functional graft polymerization of a test graft substrate is described, which involves estimating the functional graft rate, confirming its homogeneity, and selecting the test graft substrate by the test. The test graft substrate selected by the test is defined as a "functional graft substrate" as a substrate in which the functional monomer has been successfully graft-polymerized.

[0118] (Method for testing the degree of functional graft polymerization) The method for testing the degree of functional graft polymerization according to the present invention is to measure the functional graft coefficient k by graft-polymerizing a functional monomer onto a crystalline polymer substrate having a known resonance frequency f. t Then, the homogeneity of the degree of graft polymerization (functional graft polymerization degree) of the functional monomer can be inspected for a graft substrate (weight W (g)) of the same type as this known graft substrate (same crystalline polymer substrate and functional monomer). (2-1) Method for estimating the functional graft ratio ΔG of the graft substrate to be tested

[0119] (Method for estimating functional graft ratio ΔG) The inspection method according to this embodiment uses a pinhole-type microwave cavity resonator with a pinhole in the sidewall (see FIG. 4) to estimate the functional graft ratio ΔG of the inspected graft substrate by an X-band microwave dielectric absorption method, and includes the following steps (S7) and (S8). (S7) A step of bringing an arbitrary point of the graft substrate to be inspected close to the pinhole of the microwave cavity resonator within an effective distance d and detecting the microwave resonance frequency f' of the arbitrary point. (S8) Calculate the rate of change in the resonant frequency ΔB = (f-f') / f and use the known graft coefficient k t Using the standard grafting rate k t Steps to calculate ×ΔB

[0120] According to this method, the standard grafting rate k calculated in step (S8) t ×ΔB is estimated as the functional graft ratio of the graft substrate to be inspected, and the functional graft ratio ΔG, which indicates the effective functionality, can be obtained. (2-2) Method for confirming the homogeneity of the graft substrate to be inspected

[0121] (How to check homogeneity) The inspection method according to this embodiment is a method for inspecting the uniformity of the degree of polymerization of functional grafts in an inspected graft substrate, and includes the following steps (S9) and (S10). (S9) A step of bringing any M points on the graft substrate to be inspected close to the pinhole of the microwave cavity resonator within an effective distance d and detecting the microwave resonance frequency f' at each point. (S10) Step of calculating the rate of change of the resonant frequency at each M point ΔB=(f-f') / f

[0122] The homogeneity of the graft substrate to be inspected can be qualitatively confirmed from the degree of variation in the rate of change ΔB determined in step (S10). That is, if the variation in the rate of change ΔB is large, there is variation in the graft polymerization of the functional monomer in the graft substrate to be inspected, and if the variation in the rate of change ΔB is small, it is understood that the functional monomer has been graft polymerized uniformly on the graft substrate to be inspected. (2-3) Testing method for graft substrate to be tested

[0123] (Testing method) The testing method according to this embodiment is a method for testing a graft substrate to be tested. In addition to the above-described method for testing the degree of functional graft polymerization for confirming the homogeneity of the graft substrate to be tested, the testing method can be performed by further including the following steps (S11) and (S12). (S11) The rate of change of the resonant frequency at each point M obtained in step (S10) ΔB i Average value of

number

number

[0124] Then, the resonant frequency difference rate δ calculated in step (S12) f By this test, for example, the resonant frequency difference rate δ f If the difference is within 2%, the graft substrate can be deemed to have passed the test. Such a graft substrate can then be certified as a "functional graft substrate" that exhibits the desired function. (3) Pinhole-type X-band microwave resonance characteristic measurement device

[0125] (Pinhole-type X-band microwave resonance characteristic measurement device) The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention is a device for measuring the microwave resonance characteristics (resonance frequency) of a crystalline polymer substrate by a microwave dielectric absorption method. Figure 5 shows a schematic diagram of the device.

[0126] The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention includes a pinhole-type microwave cavity resonator 1 having a pinhole 12 opened in a side wall of a rectangular parallelepiped whose upper and lower bottom surfaces are connected by four side walls, a microwave generation source 3 capable of emitting an oscillating microwave, a circulator 4 capable of introducing the oscillating microwave into the microwave cavity resonator 1, and a microwave observation device 6 capable of detecting the power and frequency of the microwave reflected within the microwave cavity resonator 1 (see FIGS. 4(a) to (c)). The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention is characterized in that the radio wave band of the oscillating microwave oscillated from the microwave generation source 3 is the X-band (9 to 12 GHz).

[0127] (Microwave observation instrument) These devices are connected by a waveguide 11 as shown in Fig. 5. In Fig. 5, the microwave observation device 6 is composed of an oscilloscope 61 and a power sensor 62, which are connected to the circulator 4 by the waveguide 11, respectively.

[0128] (reflected microwaves) In the pinhole-type X-band microwave resonance characteristic measuring device of the present invention, an oscillating microwave generated from a microwave generating source 3 is introduced into a microwave cavity resonator 1 via a waveguide 11 by a circulator 4. A part of the introduced oscillating microwave leaks out from a pinhole 12, and the leaked microwave leaking out from the pinhole 12 is irradiated onto a coated polymer substrate located within an effective distance d from the pinhole 12, and is reflected into the microwave cavity resonator 1. Then, the leaked microwave, together with the introduced oscillating microwave that does not leak out from the pinhole 12, is reflected in the microwave cavity resonator 1 to form a reflected microwave.

[0129] The pinhole-type X-band microwave resonance characteristic measuring device according to the present invention can detect the power and frequency of this reflected microwave using a power sensor 62 and an oscilloscope 61 of a microwave observation device 6. In Fig. 5, the reflected microwave emitted from microwave cavity resonator 1 is observed by microwave observation device 6 (oscilloscope 61 and power sensor 62) via circulator 4.

[0130] (pinhole) As described above, the pinhole-type microwave cavity resonator 1 according to the present invention is preferably formed of a metal with a thickness of 2 mm±0.5 mm (see FIGS. 5(a) to 5(c)). Its shape is preferably a rectangular parallelepiped with its upper and lower bottom surfaces connected by four sidewalls. The interior of the microwave cavity resonator 1 is hollowed out in a rectangular parallelepiped shape, and the inner diameter of the rectangular parallelepiped is preferably 10 mm × 23 mm × 45 mm to accommodate the X-band (9 to 12 GHz). A pinhole 12 corresponding to mode TE102 is formed in one of the sidewalls.

[0131] The pinhole 12 formed in the sidewall surface of the pinhole-type microwave cavity resonator 1 of the present invention is characterized by a rectangular shape with long and short sides of 4 mm±1 mm and 8 mm±1 mm, respectively. The shape and size of this pinhole 12 were determined through trial and error so as to accommodate microwaves of mode TE102 in the pinhole-type microwave cavity resonator 1 of the present invention, and the leaky microwaves can be effectively irradiated onto a sample, such as a coated polymer substrate, placed within an effective distance d of 2 mm from the pinhole 12. Therefore, a microwave-transmitting silica glass or similar material with a thickness of 2 mm or less may be placed on the pinhole 12, and the sample, such as a polymer substrate, may be placed directly on top of the quartz glass to irradiate the leaky microwave.

[0132] The non-destructive diagnostic method for functional graft polymerization degree, functional graft substrate, and pinhole-type X-band microwave resonance characteristic measuring device according to the present invention have been described above, but the present invention is not limited to the above-described embodiments and examples. The polymer substrate, monomer, device, etc. used in the non-destructive diagnostic method for functional graft polymerization degree according to the present invention, as well as the materials, types, and other factors constituting the irradiation device and system, are not particularly limited, and their dimensions and other factors can also be changed as appropriate.

[0133] In addition, the present invention can be implemented in various forms with various improvements, modifications, and changes made based on the knowledge of those skilled in the art without departing from the spirit of the present invention. [Industrial Applicability]

[0134] The present invention makes it possible to obtain a material (functional graft substrate) with added functionality by graft polymerizing an electrically polar functional monomer onto a crystalline polymer substrate, and the non-destructive diagnostic method and inspection method for graft polymerization according to the present invention can be used to inspect and test the functionality of the functional graft substrate. [Explanation of symbols]

[0135] 1: Pinhole-type microwave cavity resonator 11: Waveguide 12: Pinhole 13: Gas inlet pipe 2: Holding member 3: Microwave source (or Gunn oscillator) 31: Gunn oscillator power supply 4: Circulator 5: Amplifier 51: Amplifier power supply 6: Microwave observation equipment 61: Oscilloscope 62: Power sensor 7: Frequency counter 8: Isolator 9: Variable resistance attenuator C: Cable P: conductor A: Insulator

Claims

1. A functional monomer with electrical polarity is mixed with a crystalline polymer substrate (weight W ０ In a method for diagnosing the degree of graft polymerization of a functional monomer for a graft substrate (weight W (g)) graft-polymerized onto a polymerizable monomer (weight W (g) (hereinafter, also referred to simply as "substrate")), the "degree of graft polymerization of the functional monomer" is also referred to simply as "functional graft polymerization degree" below. For each of the N graft-polymerized graft substrate samples, the graft ratio ΔG = (W − W ０ ) / W ０ and detecting the rate of change in the resonant frequency ΔB=(ff-ff') / f (f and f' are the resonant frequencies of the base material and the graft base material, respectively) by microwave dielectric absorption method; A method for non-destructively diagnosing the degree of functional graft polymerization in a graft substrate to be diagnosed of the same type as the graft substrate, using a regression line of ΔG / ΔB obtained from N sets of detected data (resonance frequency change rate ΔB, graft rate ΔG) (hereinafter also simply referred to as "(ΔB, ΔG)"), comprising: For N graft-based material samples, N sets of data (ΔB, ΔG) were generated by detecting them using a pinhole-type microwave cavity resonator with a pinhole on the sidewall surface by a microwave dielectric absorption method in the X-band (9 to 12 GHz), From the N sets of data, the functional graft coefficient k, which is the slope of the regression line, ｔ Seeking On the other hand, for the graft substrate to be diagnosed, Detecting (ΔB, ΔG) by the microwave dielectric absorption method, The detected graft rate ΔG, the detected ΔB, and the functional graft coefficient k ｔ The standard grafting rate (k ｔ × ΔB), By comparing these, the degree of graft polymerization of the functional monomer in the graft substrate to be diagnosed is diagnosed, thereby forming a non-destructive diagnostic method for the degree of functional graft polymerization.

2. A method for non-destructively diagnosing the degree of graft polymerization (degree of functional graft polymerization) of a functional monomer having electrical polarity in a graft substrate obtained by graft polymerizing the functional monomer onto a crystalline polymer substrate, comprising: (S1) N graft base material samples (hereinafter also referred to as "N samples"). ) (S2) detecting the grafting rate ΔG of each of the N samples; (S3) detecting a rate of change ΔB in the resonant frequency of each of the N samples by an X-band microwave dielectric absorption method using the pinhole-type microwave cavity resonator; (S4) A regression line of (ΔB, ΔG) detected for the N samples is calculated, and the slope of the line is used as the functional graft coefficient k ｔ and (S5) Detecting the graft rate ΔG and the rate of change in resonance frequency ΔB (ΔB, ΔG) for a certain graft substrate to be diagnosed, and calculating the functional graft coefficient k ｔ The standard grafting rate (k ｔ × ΔB) to diagnose the degree of functional graft polymerization in the graft substrate to be diagnosed; The non-destructive diagnostic method for the degree of functional graft polymerization according to claim 1, comprising:

3. The step (S1) of preparing N samples of graft substrates includes: (S1.1)W ０ (g) preparing a sample of the crystalline polymer substrate; (S1.2) Irradiating the sample of the crystalline polymer substrate with an electron beam; (S1.3) preparing an aqueous monomer solution by mixing the functional monomer in water; (S1·4) a step of immersing the sample of the crystalline polymer substrate irradiated with the electron beam in the aqueous monomer solution; (S1.5) immersing the sample of the crystalline polymer substrate immersed in the aqueous monomer solution in a thermostatic chamber and performing graft polymerization to obtain a sample of the graft substrate of W (g); (S1·6) performing the steps (S1·1) to (S1·5) on N samples of the crystalline polymer substrate to prepare N samples of the graft substrate (N samples); The non-destructive diagnostic method for the degree of functional graft polymerization according to claim 2, comprising:

4. In the step (S1·3) of preparing a monomer aqueous solution by mixing the functional monomer in water, when the functional monomer is hydrophobic, (S1.3.1) preparing a hydrophilic non-polar monomer; (S1.3.2) preparing a monomer aqueous solution by mixing the hydrophilic non-polar monomer together with the hydrophobic functional monomer in water; The non-destructive diagnostic method for the degree of functional graft polymerization according to claim 3, comprising:

5. The step (S3) of detecting a rate of change ΔB in the resonant frequency of each of the N samples by an X-band microwave dielectric absorption method using the pinhole-type microwave cavity resonator includes: (S3.1) A step of preparing a microwave generating source that oscillates an X-band microwave; (S3.2) preparing a pinhole-type X-band microwave cavity resonator having a pinhole opened on a side wall surface; (S3.3) placing a sample of the graft base material in the vicinity of a pinhole of the microwave cavity resonator through which the microwave generated from the microwave generation source is guided; The non-destructive diagnostic method for the degree of functional graft polymerization according to claim 2, comprising:

6. A regression line of (ΔB, ΔG) detected for the N samples was obtained, and the functional graft coefficient k ｔ The step (S4) of obtaining (S4 1) For each graft base material sample i, the graft ratio ΔG ｉ and the rate of change of the resonant frequency ΔB ｉ The ratio ΔG ｉ / ΔB ｉ and (S4・2) The above ΔG ｉ / ΔB ｉ Using (ΔG ｉ / ΔB ｉ -k) ２ The functional graft coefficient k is calculated by minimizing the sum of ｔ and The non-destructive diagnostic method for the degree of functional graft polymerization according to claim 2, comprising:

7. The step (S5) of diagnosing the functional graft polymerization degree of the graft substrate to be diagnosed includes: (S5.1) detecting (ΔB, ΔG) of the graft substrate to be diagnosed; (S5 2) The detected ΔB and the functional graft coefficient k ｔ Using the standard grafting rate (k ｔ ×ΔB); (S5 3) The detected grafting rate ΔG and the calculated standard grafting rate (k ｔ × ΔB), the graft difference ratio δg = 100 × |ΔG−k ｔ ×ΔB| / (k ｔ ×ΔB); The non-destructive diagnostic method for the degree of functional graft polymerization according to claim 2, comprising:

8. 2. A non-destructive diagnostic method for the degree of functional graft polymerization according to claim 1, wherein the dipole moment of each molecule of the electrically polar functional monomer, the base material, and the graft base material is calculated by a semi-empirical molecular orbital method.

9. When the functional monomer is hydrophobic, 5. A non-destructive diagnostic method for the degree of functional graft polymerization according to claim 4, wherein the dipole moment of each molecule of the hydrophobic functional monomer, the hydrophilic nonpolar monomer, the substrate, and the graft substrate formed by graft polymerization of the functional monomer onto the substrate is calculated by a semi-empirical molecular orbital method.

10. The functional graft coefficient k is calculated by graft-polymerizing a functional monomer onto a crystalline polymer substrate with a known resonant frequency f. ｔ In a known graft substrate, For the same type of graft substrate to be tested (weight W (g)), A testing method for estimating the functional graft ratio ΔG of a test graft substrate by an X-band microwave dielectric absorption method using a pinhole-type microwave cavity resonator having a pinhole on a side wall surface, comprising: (S7) a step of bringing an arbitrary point on the graft substrate to be inspected close to the pinhole of the microwave cavity resonator within an effective distance d and detecting a microwave resonance frequency f′ at the arbitrary point; (S8) The rate of change in the resonant frequency ΔB=(ff-f') / f is calculated, and the known graft coefficient k ｔ Using the standard grafting rate k ｔ ×ΔB; The calculated standard grafting rate k ｔ ×ΔB is estimated as the functional graft rate of the graft substrate to be inspected.

11. The functional graft coefficient k is calculated by graft-polymerizing a functional monomer onto a crystalline polymer substrate with a known resonant frequency f. ｔ In a known graft substrate, For the same type of graft substrate to be tested (weight W (g)), A method for inspecting the uniformity of the degree of graft polymerization (functional graft polymerization degree) of a functional monomer of a graft substrate to be inspected by an X-band microwave dielectric absorption method using a pinhole-type microwave cavity resonator having a pinhole opened in a side wall surface, comprising: (S9) A step of bringing any M points on the graft substrate to be inspected close to the pinhole of the microwave cavity resonator within an effective distance d, and detecting the microwave resonance frequency f′ at each point; (S10) calculating the rate of change of the resonant frequency ΔB=(ff−f′) / f at each of the M points; and confirming the homogeneity of the graft substrate to be inspected from the degree of variation in the obtained rate of change ΔB.

12. The method for inspecting the degree of polymerization of functional grafts to confirm the homogeneity of a graft substrate to be inspected according to claim 11, (S11) The rate of change ΔB of the resonant frequency at each of the M points obtained in step (S10) i Average value of [Equation 1] and calculating (S12) The average value ΔB ave Using this, the rate of change in the resonant frequency at each M point ΔB i and the average rate of change ΔB ave The resonant frequency difference rate is the average value of the difference between [Equation 2] and calculating and the resonant frequency difference rate δ ｆ A method for testing the degree of functional graft polymerization, in which a graft substrate to be tested is tested by the following method.

13. By the step (S12) according to claim 12 Resonant frequency difference rate [Equation 3] A test graft substrate for which the following has been calculated: δ ｆ A functional graft substrate that satisfies the following:

14. An apparatus for measuring the microwave resonance characteristics (resonance frequency) of a crystalline polymer substrate by a microwave dielectric absorption method, a pinhole-type microwave cavity resonator having a pinhole formed in a side wall surface of a rectangular parallelepiped whose upper and lower bottom surfaces are connected by four side wall surfaces; a microwave generating source capable of generating microwaves in the X-band (9 to 12 GHz); a circulator capable of introducing the oscillating microwave into the microwave cavity resonator; a microwave observation device capable of detecting the power and frequency of the microwave reflected within the microwave cavity resonator, an oscillating microwave generated from the microwave generating source is introduced into the microwave cavity resonator via a waveguide by a circulator, and a part of the introduced oscillating microwave leaks out from the pinhole; the leaked microwaves leaking from the pinhole are irradiated onto the coated polymer substrate located close to the pinhole within an effective distance d from the pinhole, and are reflected into the microwave cavity resonator, and are reflected together with the introduced oscillation microwaves in the microwave cavity resonator to form reflected microwaves; A pinhole type X-band microwave resonance characteristic measuring device, characterized in that the power and frequency of the reflected microwave can be detected by the microwave observation device.

15. The pinhole-type microwave cavity resonator of claim 14, wherein the pinhole-type microwave cavity resonator has a rectangular parallelepiped shape with upper and lower bottom surfaces connected by four side wall surfaces, the interior of which is hollowed out in a rectangular parallelepiped shape, and a pinhole corresponding to mode TE102 is opened in one side wall surface.

16. The pinhole-type X-band microwave resonance characteristic measuring device according to claim 14, characterized in that the pinhole formed on the side wall surface is a rectangle with long and short sides of 4 mm ± 1 mm and 8 mm ± 1 mm, respectively.

17. The microwave cavity resonator is formed of a metal having a thickness of 2 mm±0.5 mm, 15. The pinhole type X-band microwave resonance characteristic measuring device according to claim 14, wherein the inner diameter of the hollowed-out rectangular parallelepiped is 10 mm x 23 mm x 45 mm.

18. 15. The pinhole-type X-band microwave resonance characteristic measuring device according to claim 14, wherein an effective distance d from the pinhole is d=2 mm.

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