JP2017003387A - Method for evaluating response characteristics of internal structure of polymeric material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for evaluating response characteristics of the internal structure of a polymeric material precisely.SOLUTION: A method is provided in which response characteristics obtained by performing curve fitting is evaluated for a scattering strength curve obtained by performing X-ray scattering measurement or neutron scattering measurement by radiating an X-ray or a neutron ray onto a polymeric material while performing dynamic viscoelasticity measurement and response characteristics of the internal structure of a polymeric material is evaluated.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for evaluating response characteristics of an internal structure of a polymer material.

In a polymer material such as a rubber material, the response characteristic of the internal structure is an important physical quantity that affects various physical properties of the product such as energy loss. For example, in a tire that is a rubber product, the response characteristic of the internal structure is It is closely related to energy loss, and energy loss is closely related to fuel efficiency and grip performance.

Until now, the internal structure of the polymer material itself could be observed using an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). However, the response characteristics of the internal structure could not be evaluated by observation with an electron microscope.

As a method for measuring the energy loss of a polymer material, a method for evaluating the value of loss tangent (tan δ) obtained from dynamic viscoelasticity measurement is widely used (see Patent Document 1). However, this method has a large error, and even if the value of tan δ is approximately the same, the tire rolling performance may differ, and the measurement accuracy is not sufficiently satisfactory.

In recent years, methods for evaluating energy loss of polymer materials from X-ray scattering measurement and neutron scattering measurement have also been proposed (see Patent Documents 2 and 3). However, this method evaluates the response characteristic in a static state, and does not evaluate the response characteristic in a dynamic state.

JP 2009-46088 A International Publication No. 2013/064405 JP 2014-102210 A

An object of the present invention is to solve the above-mentioned problems and to provide a method for evaluating the response characteristics of the internal structure of a polymer material with high accuracy.

The present invention provides an internal structure of a polymer material by performing X-ray scattering measurement or neutron scattering measurement by irradiating the polymer material with X-rays or neutron rays while performing dynamic viscoelasticity measurement. The present invention relates to a method for evaluating the response characteristics of a computer.

In the present invention, by synchronizing the exposure of the X-ray detector or the neutron detector with the pulse signal transmitted from the viscoelasticity tester, the dynamic viscosity is determined based on the time when the pulse signal is first transmitted. It is preferable to divide one period of the elasticity measurement into an arbitrary number of times and perform the X-ray scattering measurement or the neutron scattering measurement.

The X-ray scattering measurement is preferably a small angle X-ray scattering measurement, and the neutron scattering measurement is preferably a small angle neutron scattering measurement.

The polymer material is preferably a composite material including one or more conjugated diene compounds and one or more fillers.

In this invention, it is preferable to measure in the area | region whose q represented by the following (Formula 1) is 10 nm <^-1> or less using the said X-ray or the said neutron beam.

In the present invention, inertia of 1 nm to 100 μm obtained by curve fitting with the following (Expression 2) and (Expression 3) to the scattering intensity curve I (q) obtained by the X-ray scattering measurement or the neutron scattering measurement. it is preferred to evaluate the response characteristic with a radius R _g.

In the present invention, using the above (Equation 2) and (Equation 3), from the scattering intensity curve I _(horizontal) (q) in the direction horizontal to the stretching direction of the dynamic viscoelasticity measurement, the dynamic A radius of inertia R _{g (horizontal)} in a direction horizontal to the stretching direction of the viscoelasticity measurement is calculated, and a scattering intensity curve I _(vertical) (q _{) in} a direction perpendicular to the stretching direction of the dynamic viscoelasticity measurement is calculated. ) To calculate the inertial radius R _{g (vertical)} in the direction perpendicular to the stretching direction of the dynamic viscoelasticity measurement, and the variation in the aspect ratio obtained from the following (formula 4) and (formula 5) It is preferable to evaluate the response characteristics using the phase difference φ with respect to the input frequency of the dynamic viscoelasticity measurement.

According to the present invention, while performing dynamic viscoelasticity measurement, X-ray scattering or neutron scattering measurement is performed by irradiating X-rays or neutrons, so that the response characteristics of the internal structure can be obtained in a dynamic state. Since it can measure, energy loss etc. can be evaluated with high measurement accuracy.

An example of the scattering intensity curve obtained by the SAXS measurement in Example 1. The time change of R _{g (horizontal)} and R _{g (vertical)} in Example 1. The input frequency of the dynamic viscoelasticity measurement in Example 1 and the time change of an aspect ratio.

The present invention performs X-ray scattering measurement or neutron scattering measurement by irradiating the polymer material with X-rays or neutron rays while performing dynamic viscoelasticity measurement. This is a method for evaluating response characteristics.

In the present invention, the X-ray scattering measurement or the neutron scattering measurement is performed simultaneously with the dynamic viscoelasticity measurement, thereby adding a periodic strain to the response characteristics of the internal structure of the polymer material by the dynamic viscoelasticity measurement. Since it can be measured in a state, that is, in a dynamic state, the energy compared with the technique for evaluating the value of loss tangent (tan δ) obtained from dynamic viscoelasticity measurement shown in Patent Document 1 Loss can be evaluated with high measurement accuracy.

Further, the radius of inertia R _g of the cluster formed by agglomeration of the filler in the polymer material is calculated by X-ray scattering measurement or neutron scattering measurement proposed in Patent Document 2, and this R _g is used. Therefore, the method of evaluating the energy loss of a polymer material estimates the energy loss from the dispersion state of the filler. Therefore, in the case of a polymer material having the same dispersion state of the filler, the difference in energy loss is calculated. It was difficult to evaluate with high accuracy. In contrast, in the present invention, by measuring the response characteristics of the internal structure in a dynamic state, the difference in energy loss can be evaluated with high accuracy even for polymers having the same dispersion state of the filler. be able to.

Further, the X-ray scattering measurement or neutron scattering measurement proposed in Patent Document 3 is used to calculate a correlation length ξ of 0.1 nm to 100 μm, which is presumed to correspond to the distance between the crosslinking points of the polymer, and this ξ is used. Therefore, the method for evaluating the energy loss of a polymer material can accurately evaluate the energy loss of any polymer material regardless of the presence or absence of a filler. However, since the energy loss is measured in a static state, the hardness (strength) of the bonded state between the polymer material and the filler cannot be determined. On the other hand, since the present invention measures response characteristics in a dynamic state, the hardness of the combined state of the polymer material and the filler can also be evaluated. This makes it possible to evaluate response characteristics that take into account the hardness of the bonded state of the polymer material and the filler, so that the difference in energy loss can be evaluated with higher accuracy compared to measurement in a static state. can do.

As a method for simultaneously performing dynamic viscoelasticity measurement and X-ray scattering measurement or neutron scattering measurement, for example, exposure of an X-ray detection device or a neutron detection device to a pulse signal transmitted from a viscoelasticity tester By synchronizing the two, the period of dynamic viscoelasticity measurement is divided into an arbitrary number of times based on the time when the pulse signal was first transmitted (t = 0), and X-ray scattering measurement or neutron scattering measurement is performed. This technique is suitable.

The timing at which the pulse signal is first transmitted is not particularly limited. For example, the point where the displacement in the dynamic viscoelasticity measurement is 0 (when the starting strain is added) is used for analysis. Convenient.

The number of times of dividing one cycle of dynamic viscoelasticity measurement is not particularly limited, but can follow the inclination of clusters formed by aggregation of metal atoms and clusters formed by aggregation of fillers. The number of times is convenient for analysis.

Dynamic viscoelasticity measurement measures the response when a sample is periodically distorted (deformed). Deformation (strain) modes include tension (stretching), compression, shear, and bending. However, tension and compression are suitable for measuring energy loss. Other conditions such as initial strain, frequency, and dynamic strain amplitude can be appropriately set according to the polymer material to be measured.

An apparatus that can be used for dynamic viscoelasticity measurement is not particularly limited, and for example, a general apparatus such as a spectrometer manufactured by Ueshima Seisakusho Co., Ltd. can be used.

In the present invention, in order to more accurately evaluate the response characteristics (particularly energy loss) of the internal structure of the polymer material, as X-ray scattering measurement, SAXS (Small) measures the scattering intensity by irradiating the polymer material with X-rays. Angle X-ray Scattering Small angle X-ray scattering (scattering angle: usually 10 degrees or less) measurement can be suitably employed. In small-angle X-ray scattering, structural information of a substance can be obtained by measuring X-rays that are scattered by irradiating the substance with X-rays, and having a small scattering angle. , Can analyze the regular structure at several nanometer level.

In order to obtain detailed molecular structure information from the SAXS measurement, it is desirable that an X-ray scattering profile with a high S / N ratio can be measured. Therefore, the X-rays emitted from the synchrotron preferably have a luminance of at least 10 ¹⁰ (photons / sec / mrad ² / mm ² /0.1% bw) or more. Note that bw represents the band width of X-rays emitted from the synchrotron. Examples of such synchrotrons include beam lines BL03XU, BL08B2, and BL20XU of a large synchrotron radiation facility SPring-8 owned by the High Brightness Photoscience Research Center.

The X-ray luminance (photons / sec / mrad ² / mm ² /0.1% bw) is preferably 10 ¹⁰ or more, more preferably 10 ¹² or more. Although an upper limit is not specifically limited, It is preferable to use the X-ray intensity below the extent that there is no radiation damage.

The number of photons (photons / sec) of the X-ray is preferably 10 ⁷ or more, more preferably 10 ⁹ or more. Although an upper limit is not specifically limited, It is preferable to use the X-ray intensity below the extent that there is no radiation damage.

Similarly, in the present invention, in order to more accurately evaluate the response characteristics (particularly energy loss) of the internal structure of the polymer material, as a neutron scattering measurement, SANS that measures the scattering intensity by irradiating the polymer material with a neutron beam (Small Angle Neutron Scattering Small Angle Neutron Scattering (scattering angle: usually 10 degrees or less)) measurement can be suitably employed. In small-angle neutron scattering measurement, the structure information of a substance can be obtained by measuring the neutron beam that is scattered by irradiating the substance with a neutron beam, which has a small scattering angle. , Can analyze the regular structure at several nanometer level.

Similar to the SAXS measurement, the neutron flux intensity (neutrons / cm ² / s) of the neutron beam is preferably 10 ³ or more, more preferably 10 ⁴ in that a neutron scattering profile having a high S / N ratio can be obtained. That's it. Although an upper limit is not specifically limited, It is preferable to use the neutron flux intensity below the grade which does not have radiation damage.

The neutron beam used for neutron scattering measurement such as SANS in terms of obtaining such neutron flux intensity is the beam line SANS-J of the JRR-3 research reactor owned by the Japan Atomic Energy Agency. High intensity proton accelerator facility J-PARC attached SANS equipment (BL15 TAIKAN, BL20 iMATERIA, etc.), South Korea KAERI (Korea Atomic Energy Research Institute) owned reactor HANARO (High-fluxSadAvS AdvancedAdSantSadS AdvancedAdvSantAdvS) ) Etc. can be used.

In the X-ray scattering measurement or the neutron scattering measurement, it is necessary to measure a finer molecular structure of the polymer material. Is preferably measured in a region of 10 nm ⁻¹ or less. The q (nm ⁻¹ ) region is desirable from the viewpoint that smaller information can be obtained as the numerical value increases. Therefore, the q region is more preferably 20 nm ⁻¹ or less.

X-rays scattered in the SAXS measurement are detected by an X-ray detection device, and an image is generated by an image processing device or the like using X-ray detection data from the X-ray detection device.

Examples of the X-ray detector include a two-dimensional detector (X-ray film, nuclear dry plate, X-ray imaging tube, X-ray fluorescence intensifier tube, X-ray image intensifier, X-ray imaging plate, X-ray CCD. , Amorphous body for X-rays, etc.), a line sensor one-dimensional detector can be used. An X-ray detection device may be selected as appropriate depending on the type and state of the polymer material to be analyzed.

As the image processing apparatus, an apparatus capable of generating a normal X-ray scattering image based on X-ray detection data obtained by the X-ray detection apparatus can be appropriately used.

The SANS measurement can be measured by the same principle as the SAXS measurement. The scattered neutron beam is detected by the neutron beam detection device, and the image is generated by the image processing device using the neutron beam detection data from the neutron beam detection device. Is done. Here, as described above, as the neutron beam detection device, a known two-dimensional detector, a one-dimensional detector, and an image processing device that can generate a known neutron scattering image can be used. Good.

In the present invention, either X-ray scattering measurement or neutron scattering measurement may be adopted. However, since a sufficient S / N ratio can be obtained even if the exposure time is short, X using high intensity X-rays is used. Line scattering measurements are preferred.

Although it does not specifically limit as a polymeric material in this invention, A conventionally well-known thing is mentioned, For example, the composite material containing 1 or more types of conjugated diene type compounds and 1 or more types of filler is applicable. It does not specifically limit as a conjugated diene compound, Well-known compounds, such as isoprene and a butadiene, are mentioned.

Such conjugated diene compounds include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber ( IIR), halogenated butyl rubber (X-IIR), styrene isoprene butadiene rubber (SIBR), and other polymers having a double bond. The polymer material such as the composite material may include one or more modifying groups such as a hydroxyl group and an amino group.

As the polymer material, for example, a composite material including a functional group having at least one metal coordination ability in the molecular structure can be suitably applied. Here, the functional group having metal coordinating ability is not particularly limited as long as it has metal coordinating ability, and examples thereof include functional groups containing metal coordinating atoms such as oxygen, nitrogen, and sulfur. It is done. Specific examples include a dithiocarbamic acid group, a phosphoric acid group, a carboxylic acid group, a carbamic acid group, a dithioic acid group, an aminophosphoric acid group, and a thiol group. Only one type of the functional group may be included, or two or more types may be included.

As the coordination metal for the functional group, for example, Fe, Cu, Ag, Co, Mn, Ni, Ti, V, Zn, Mo, W, Os, Mg, Ca, Sr, Ba, Al, Si, etc. Is mentioned. For example, in a polymer material containing a compound having such a metal atom (M ¹ ) and containing a functional group having a metal coordination ability (such as —COO), each —COOM is coordinated to form a large number of — When COOM ¹ overlaps, a cluster in which metal atoms are aggregated is formed.
As the amount of the metal atom ^{(M 1),} with respect to 100 parts by mass of the polymer components in the polymer material, preferably 0.01 to 200 parts by weight.

Examples of the filler include carbon black, silica; mM ² · xSiOy · zH ₂ O (wherein M ² is at least one metal selected from the group consisting of aluminum, calcium, magnesium, titanium, and zirconium, or A metal oxide, hydroxide, hydrate or carbonate; m is 1 to 5, x is 0 to 10, y is 2 to 5, and z is a numerical value in the range of 0 to 10). Etc.

Specific examples of the filler represented by the above mM ² · xSiO _y · zH ₂ O include aluminum hydroxide (Al (OH) ₃ ), alumina (Al ₂ O ₃ , Al ₂ O ₃ .3H ₂ O (water Japanese)), clay (Al ₂ O ₃ .2SiO ₂ ), kaolin (Al ₂ O ₃ .2SiO ₂ .2H ₂ O), pyrophyllite (Al ₂ O ₃ .4SiO ₂ .H ₂ O), bentonite ( Al ₂ O ₃ · 4SiO ₂ · 2H ₂ O), aluminum silicate (Al ₂ SiO ₅ , Al ₄ (SiO ₂ ) ₃ · 5H ₂ O, etc.), aluminum calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂₎ ), calcium hydroxide (Ca _(OH) 2), calcium oxide (CaO), calcium silicate _(Ca 2 _SiO 4), magnesium calcium silicate (CaMgSiO ₄ , Magnesium hydroxide (Mg _(OH) 2), magnesium oxide (MgO), talc _{(MgO · 4SiO 2 · H 2} O), attapulgite _{(5MgO · 8SiO 2 · 9H 2} O), magnesium aluminum oxide (MgO · Al ₂ O ₃ ), titanium white (TiO ₂ ), titanium black (Ti _n O _2n-1 ) and the like. In a polymer material containing such a filler, a cluster in which the filler is aggregated is formed. In addition, as a compounding quantity of the said filler, 10-200 mass parts is preferable with respect to 100 mass parts of polymer components in a polymeric material.

The above composite materials include other compounding agents (silane coupling agents, zinc oxide, stearic acid, various anti-aging agents, oils, waxes, vulcanizing agents, vulcanization accelerators, crosslinking agents, etc. that are widely used in the rubber industry. ) May be included. Such a composite material can be manufactured using a known kneading method or the like. Examples of such composite materials include those used as tire rubber materials.

Next, a method for analyzing a scattering intensity curve obtained by X-ray scattering measurement or neutron scattering measurement of a polymer material will be specifically described. When a SAXS measurement or a SANS measurement is performed on a polymer material containing a functional group containing a metal atom and having a metal coordination ability or a composite material containing a filler such as silica, for example, the obtained scattering intensity curve is as follows: By analyzing by this method, the inertia radius (Rg) of the cluster (scatterer) of 1 nm to 100 μm can be obtained.

Curve fitting is performed using the following (Expression 2) to (Expression 3) on the scattering intensity curve I (q) obtained by SAXS measurement and SANS measurement in FIG. 1 and the like, and the fitting parameter is obtained by the least square method. .

Among the obtained fitting parameters, it is presumed that the inertia radius Rg of the molecular structure having a size of 1 nm to 100 μm corresponds to a cluster formed by aggregation of metal atoms and a cluster formed by aggregation of filler.

A dynamic viscoelasticity measuring and implementing an X-ray scattering measurement or neutron scattering measurements simultaneously, radius of gyration R _g will vary in accordance with the cycle of variations in the dynamic viscoelasticity measurement. Here, the dynamic viscoelasticity measurement is performed from the scattering intensity curve I _(horizontal) (q) in the direction horizontal to the stretching direction of the dynamic viscoelasticity measurement using the above (formula 2) and (formula 3). _Is calculated from the scattering intensity curve I _(vertical) (q) in the direction perpendicular to the stretching direction of the dynamic viscoelasticity measurement. Of inertia ratio R _{g (vertical)} in a direction perpendicular to the stretching direction of dynamic viscoelasticity measurement, and by using the following (formula 4) and (formula 5), variation in aspect ratio and dynamic viscoelasticity measurement The phase difference φ from the input frequency can be calculated.

The scattering intensity curve I _(horizontal) (q) can be calculated by partially averaging the azimuthal angle in a direction horizontal to the stretching direction of the dynamic viscoelasticity measurement. Similarly, the scattering intensity curve I _(vertical) (q) can be calculated by partially averaging the azimuthal angle in a direction perpendicular to the stretching direction of the dynamic viscoelasticity measurement.
Specifically, Azimuthal Angle when calculating the scattering intensity curve I _(horizontal) (q) includes 0 ° when the completely horizontal direction is 0 ° in the stretching direction of the dynamic viscoelasticity measurement − What is necessary is just to set it as the arbitrary angle range of 135 degrees-225 degrees including the arbitrary angle range of 45 degrees-45 degrees, and / or 180 degrees. In addition, Azimuthal Angle when calculating the scattering intensity curve I _(vertical) (q) includes 90 °, an arbitrary angle range of 45 ° to 135 °, and / or 270 ° and 225 ° to 315 °. Any angle range may be used.

The phase difference φ and its tangent tan φ are highly correlated with the energy loss of the polymer material, and the smaller the φ and tan φ, the smaller the energy loss. Therefore, the dynamic viscoelasticity measurement and the X-ray scattering measurement or the neutron scattering measurement are performed at the same time, and φ and tan φ are obtained using (Expression 2) to (Expression 5), thereby evaluating the energy loss of the polymer material. Is possible.

The reason why there is a correlation between φ and tan φ and energy loss is not necessarily clear, but is estimated as follows.
The composite material containing silica will be described as an example. Silica clusters have a rugby ball-type aggregate structure, and the inclination (shape) of the aggregate structure changes when strain is applied by dynamic viscoelasticity measurement. Therefore, the aspect ratio varies. φ is the difference between the fluctuation wave of the aspect ratio and the input frequency of dynamic viscoelasticity measurement. If φ and tanφ are small, the contribution of viscosity in the viscoelasticity of the composite material is small and the energy loss is small. Is presumed to mean.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
Isoprene rubber (IR): Nippon IR2200 made by Nippon Zeon Co., Ltd.
Butadiene rubber (BR): BR730 manufactured by JSR Corporation
Silica: Nipol VN3 manufactured by Tosoh Silica Corporation
Silane coupling agents A to C: prototype
Stearic acid: Stearic acid “椿” manufactured by NOF Corporation
Sulfur: Powder sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd. 1: Noxeller CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator 2: Noxeller D (1,3-diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

(Manufacturing method of the molded product used in Example 1 and Comparative Examples 1 and 2)
According to the formulation shown in Table 1, the mixture was kneaded with a Banbury kneader and a roll kneader, and the kneaded material was press-molded at 170 ° C. for 20 minutes to obtain a molded product. The obtained molded product (sample) was evaluated by the following test method. The results are shown in Table 2.

[Example 1: Simultaneous implementation of dynamic viscoelasticity measurement and SAXS measurement]
<Dynamic viscoelasticity measurement>
In a viscoelasticity testing machine (spectrometer manufactured by Ueshima Seisakusho Co., Ltd.) set at 60 ° C., a 10 mm × 10 mm sample was held and fixed with a chuck. Then, after applying an initial strain of 10% to this sample in a tensile mode, a dynamic viscoelasticity measurement was performed by repeatedly applying a strain of a frequency of 10 Hz and a dynamic strain amplitude of 5%.

<SAXS measurement>
By irradiating X-rays every 10 msec with respect to a sample during viscoelasticity measurement, where the displacement of dynamic viscoelasticity measurement is 0, and performing small angle X-ray scattering (SAXS) measurement under the following conditions The structural change of the internal structure of the molded product was observed. One period of viscoelasticity was divided into 10 parts. An example of the obtained scattering intensity curve is shown in FIG.
(Conditions for SAXS measurement)
X-ray luminance: 5 × 10 ¹² photons / sec / mrad ² / mm ² /0.1% bw
X-ray photon count: 2 × 10 ⁹ photons / sec
X-ray energy: 8 keV (BL08B2), 23 keV (BL20XU)
Distance from sample to detector: 3m (BL08B2), 160m (BL20XU)
(SAXS detector)
Two-dimensional detector: Imaging intensifier and CCD camera

<SAXS data processing>
The scattering intensity curve I _(horizontal) (q) in the direction horizontal to the stretching direction of the dynamic viscoelasticity measurement obtained from the measurement with BL08B2, and the scattering intensity curve in the same direction obtained from the measurement with BL20XU I _(horizontal) (q) was combined by the method of least squares. The same was applied to the scattering intensity curve I _(vertical) (q) in the direction perpendicular to the stretching direction of the dynamic viscoelasticity measurement. The two curves were combined by fixing the scattering intensity curve obtained from BL08B2 on the wide angle side and shifting the scattering intensity curve obtained from BL20XU on the small angle side.

Curve fitting is performed on the combined scattering intensity curve I (q) using (Equation 2) and (Equation 3), and the fitting parameter Rg (inertial radius of 1 nm to 100 μm) is measured by dynamic viscoelasticity. The minimum square method was used for each of a horizontal direction and a vertical direction in the stretching direction. FIG. 2 shows changes over time in R _{g (horizontal)} and R _{g (vertical)} .

By analyzing the obtained R _{g (horizontal)} and R _{g (vertical)} using (Equation 4) and (Equation 5), the degree of variation in the aspect ratio of Rg with respect to the input frequency of dynamic viscoelasticity measurement The phase difference φ and its tangent tan φ were calculated. FIG. 3 shows the input frequency of the dynamic viscoelasticity measurement and the time change of the aspect ratio. The calculated phase difference φ was 0.34551 [rad], and tan φ was 0.35995.

[Comparative Example 1: Scanning Electron Microscope (SEM) Measurement]
At room temperature, the sample was observed with a scanning electron microscope (XL30 manufactured by Nippon FEI Co., Ltd.).

[Comparative Example 2: Transmission electron microscope (TEM) measurement]
The sample was cut to a thickness of 50 nm with a microtome (LEICA ultramicrotome EM VC6) and observed with a transmission electron microscope (JEM2100F, manufactured by JEOL Ltd.).

From Table 2, in Example 1 in which dynamic viscoelasticity measurement and SAXS measurement were simultaneously performed, it was not possible in Comparative Example 1 in which not only internal structure measurement but also SEM measurement was performed, and in Comparative Example 2 in which TEM measurement was performed. It became clear that even energy loss, which is a response characteristic of the internal structure, can be measured.

(Manufacturing method of the molded product used in Example 2 and Comparative Examples 3 and 4)
According to the formulation shown in Table 3, kneading was carried out with a Banbury kneader and a roll kneader, and then the kneaded material was press-molded at 170 ° C. for 20 minutes to obtain molded products (samples) A to C.

[Example 2: Simultaneous implementation of dynamic viscoelasticity measurement and SAXS measurement]
Φ and tan φ were calculated by the same method as in Example 1, and their reciprocals were displayed as an index with sample A as 100. It shows that energy loss is so small that a numerical value is large.

[Comparative Example 3: Dynamic Viscoelasticity Measurement]
The dynamic viscoelasticity measurement was carried out under the same conditions as in Example 1 to measure tan δ, and the reciprocal number was expressed as an index with Sample A as 100. It shows that energy loss is so small that a numerical value is large.

[Comparative example 4: tire rolling performance measurement]
For a sample tire in which each composition of Samples A to C was applied to a tire member, using a rolling resistance tester, with a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) The rolling resistance at the time of running was measured, and Sample A was set as 100 and displayed as an index. The larger the value, the better the rolling performance of the tire and the smaller the energy loss.

From Table 3, it was proved that energy loss can be evaluated by obtaining φ and tan φ in Example 2 in which dynamic viscoelasticity measurement and SAXS measurement were simultaneously performed. Further, φ and tan φ obtained from Example 2 have a high correlation with the tire rolling performance obtained in Comparative Example 4 as compared with tan δ obtained from Comparative Example 3, and are obtained by conventional measurement. Even if it is difficult to evaluate the performance difference with tan δ, it has become clear that the performance difference can be accurately evaluated.

Claims (7)

While conducting dynamic viscoelasticity measurement for polymer material, X-ray scattering measurement or neutron scattering measurement is performed by irradiating with X-ray or neutron beam, thereby improving the response characteristics of the internal structure of the polymer material. How to evaluate. By synchronizing the exposure of the X-ray detector or neutron detector with the pulse signal transmitted from the viscoelasticity tester, one period of dynamic viscoelasticity measurement is based on the time when the pulse signal was first transmitted. The method of evaluating the response characteristics of the internal structure of the polymer material according to claim 1, wherein X-ray scattering measurement or neutron scattering measurement is carried out by dividing the number of The method for evaluating response characteristics of the internal structure of the polymer material according to claim 1 or 2, wherein the X-ray scattering measurement is small-angle X-ray scattering measurement and the neutron scattering measurement is small-angle neutron scattering measurement. The polymer material is a composite material containing one or more kinds of conjugated diene compounds and one or more kinds of fillers. The response characteristic of the internal structure of the polymer material according to any one of claims 1 to 3 is evaluated. Method. The method according to any one of claims 1 to 4, wherein q represented by the following (Formula 1) is measured in an area of 10 nm ^-1 or less using X-rays or neutron rays.

With respect to the X-ray scattering measurement or scattered obtained by neutron scattering intensity curve I (q), by using the radius of gyration _{R g} of 1nm~100μm obtained by curve fitting by the following (Equation 2) and (Equation 3) The method for evaluating the response characteristics of the internal structure of the polymer material according to claim 1, wherein the response characteristics are evaluated.

Using (Equation 2) and (Equation 3), from the scattering intensity curve I _(horizontal) (q) in the direction horizontal to the stretching direction of dynamic viscoelasticity measurement, with respect to the stretching direction of dynamic viscoelasticity measurement In addition, the inertial radius R _{g (horizontal)} in the _horizontal direction is calculated, and from the scattering intensity curve I _(vertical) (q) in the direction perpendicular to the stretching direction of the dynamic viscoelasticity measurement, Calculate the inertial radius R _{g (vertical)} in the direction perpendicular to the stretching direction,
The inside of the polymer material according to claim 6, wherein the response characteristic is evaluated using a phase difference φ between an aspect ratio variation obtained from the following (formula 4) and (formula 5) and an input frequency of dynamic viscoelasticity measurement. A method for evaluating the response characteristics of structures.

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