JP2018178016A - Mechanical physical property measuring method - Google Patents

Mechanical physical property measuring method Download PDF

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JP2018178016A
JP2018178016A JP2017082036A JP2017082036A JP2018178016A JP 2018178016 A JP2018178016 A JP 2018178016A JP 2017082036 A JP2017082036 A JP 2017082036A JP 2017082036 A JP2017082036 A JP 2017082036A JP 2018178016 A JP2018178016 A JP 2018178016A
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JP6852538B2 (en
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房恵 金子
Fusae Kaneko
房恵 金子
剛志 古川
Tsuyoshi Furukawa
剛志 古川
岸本 浩通
Hiromichi Kishimoto
浩通 岸本
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Sumitomo Rubber Industries Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a mechanical physical property measuring method which can accurately measure mechanical physical properties such as hardness of structures such as filler and cross-linking materials included in a polymer composite material.SOLUTION: A mechanical physical property measuring method of a polymer composite material containing structures uses a sample having a thickness decided on the basis of the size of the structure in the polymer composite material for measurement.SELECTED DRAWING: None

Description

本発明は、充填剤、架橋材料等の構造体を含む高分子複合材料の力学物性測定方法に関する。 The present invention relates to a method of measuring mechanical properties of a polymer composite material including a structure such as a filler and a crosslinked material.

近年の高分子複合材料に対する市場要求や安全性等を満たすためには、高度に力学物性を制御する必要がある。そのためには、特にナノ〜ミクロスケールにおける力学物性を測定することが非常に重要である。 In order to meet the market requirements and safety of polymer composite materials in recent years, it is necessary to control mechanical properties to a high degree. For that purpose, it is very important to measure mechanical properties particularly at the nano to micro scale.

ナノ〜ミクロスケールにおける力学物性の評価手法として原子間力顕微鏡等が提案されている。しかしながら、高分子複合材料中に存在するシリカ、カーボンブラック等のフィラー、硫黄、加硫促進剤、酸化亜鉛等の架橋材料(架橋剤)等の構造体の硬さ等、各種力学物性を精度よく測定することは困難なのが実情である。 An atomic force microscope or the like has been proposed as an evaluation method of mechanical properties on a nano to micro scale. However, various mechanical properties such as the hardness of the structure such as filler such as silica, carbon black etc., sulfur, vulcanization accelerator, zinc oxide etc. (crosslinking agent) present in the polymer composite material are precisely measured. The fact is that it is difficult to measure.

本発明は、前記課題を解決し、充填剤、架橋材料等の構造体を含む高分子複合材料に関し、該構造体の硬さ等の力学物性を精度良く測定できる力学物性測定方法を提供することを目的とする。 The present invention solves the above-mentioned problems and relates to a polymer composite material including a structure such as a filler and a crosslinked material, and provides a mechanical property measuring method capable of accurately measuring mechanical properties such as hardness of the structure. With the goal.

本発明は、構造体を含む高分子複合材料の力学物性測定方法であって、高分子複合材料中の構造体のサイズを基に決定した厚みを持つ試料を用いて測定することを特徴とする力学物性測定方法に関する。 The present invention is a method for measuring mechanical properties of a polymer composite material containing a structure, which is characterized by using a sample having a thickness determined based on the size of the structure in the polymer composite material. It relates to a method of measuring mechanical properties.

構造体は、充填剤及び架橋材料の少なくとも1種以上であることが好ましい。
構造体のサイズは、透過型電子顕微鏡、走査型電子顕微鏡又は走査型透過X線顕微鏡を用いて測定されたものであることが好ましい。
The structure is preferably at least one or more of a filler and a crosslinking material.
The size of the structure is preferably measured using a transmission electron microscope, a scanning electron microscope or a scanning transmission X-ray microscope.

試料は、高分子複合材料中の構造体の大きさと同程度の厚みに調整したものであることが好ましい。
試料表面と接触させてナノ〜ミクロスケールの高分子複合材料の力学物性を測定することが好ましい。
The sample is preferably adjusted to the same thickness as the size of the structure in the polymer composite material.
It is preferable to measure the mechanical properties of the nano to micro scale polymer composite material by contacting the sample surface.

本発明によれば、構造体を含む高分子複合材料の力学物性測定方法であって、高分子複合材料中の構造体のサイズを基に決定した厚みを持つ試料を用いて測定することを特徴とする力学物性測定方法であるので、充填剤、架橋材料等の構造体を含む高分子複合材料において、該構造体の硬さ等の力学物性を精度良く測定することが可能となる。 According to the present invention, there is provided a method of measuring mechanical properties of a polymer composite material containing a structure, which is characterized by using a sample having a thickness determined based on the size of the structure in the polymer composite material. Since it is a measuring method of mechanical physical properties, it is possible to measure mechanical physical properties such as hardness of the structural body with high accuracy in a polymer composite material containing a structural body such as a filler and a crosslinked material.

従来及び本発明における測定試料の模式図の一例。An example of the schematic diagram of the measurement sample in the past and this invention. 実施例の試料で得られた窒素K殼吸収端のマッピング画像の一例。An example of the mapping image of the nitrogen K soot absorption edge acquired with the sample of the Example. 実施例、比較例1〜2で得られたAFM像の一例。An example of an AFM image obtained by an example and comparative examples 1-2.

本発明は、構造体を含む高分子複合材料の力学物性測定方法であって、高分子複合材料中の構造体のサイズを基に決定した厚みを持つ試料を用いて測定することを特徴とする力学物性測定方法である。 The present invention is a method for measuring mechanical properties of a polymer composite material containing a structure, which is characterized by using a sample having a thickness determined based on the size of the structure in the polymer composite material. It is a mechanical property measurement method.

例えば、原子間力顕微鏡を用いて、フィラー、架橋材料等の構造体を含む高分子複合材料を測定する際、ミクロトーム等で切削した平滑面を観察するが、測定時にカンチレバーで高分子複合材料(試料)を押し込むことになる。そのため、図1(a)に示されているように、高分子複合材料中の構造体が試料厚みより小さい場合、変形しない構造体を押し込んでも、その奥側に存在する構造体よりも柔らかい高分子材料が変形するために、構造体の硬さなどの力学物性を正確に測定できない。 For example, when measuring a polymer composite material including a structure such as a filler or a crosslinked material using an atomic force microscope, a smooth surface cut with a microtome or the like is observed. The sample will be pushed in. Therefore, as shown in FIG. 1 (a), when the structure in the polymer composite material is smaller than the sample thickness, even if a structure that is not deformed is pressed, the softness is higher than that of the structure present in the back side. Because the molecular material is deformed, mechanical properties such as hardness of the structure can not be accurately measured.

一方、本発明では、例えば、構造体のサイズと同程度の試料厚みにする方法等、高分子複合材料中の構造体のサイズを基に決定した厚みを持つ試料を力学物性の測定に供することで、図1(b)に示されているように、カンチレバーで押し込んだ構造体の奥側に構造体よりも柔らかい高分子材料が無いような状態で測定することが可能になる。よって、高分子複合材料中に存在する構造体について、硬さ等の各種力学物性を精度良く、正確に測定できる。 On the other hand, in the present invention, a sample having a thickness determined based on the size of the structure in the polymer composite material, such as a method of making the sample thickness approximately the same as the size of the structure, is provided for measurement of mechanical properties. Thus, as shown in FIG. 1 (b), measurement can be performed in a state where there is no polymer material softer than the structure on the back side of the structure that is pushed in by the cantilever. Therefore, various mechanical physical properties such as hardness can be accurately measured accurately for the structure present in the polymer composite material.

本発明の方法に供される高分子複合材料は、構造体を含む複合材料である。
構造体とは、高分子複合材料中に含まれる充填剤、加硫材料等が凝集して形成された1nm〜100μm程度のクラスターである。構造体は、透過電子顕微鏡(TEM)、走査型電子顕微鏡(SEM)、走査型透過X線顕微鏡(STXM)の各種手法でサイズを決定できるものであれば問題なく、フィラー等の高分子中で溶けない材料だけでなく、酸化亜鉛、加硫促進剤、硫黄等の高分子中に溶ける材料でもよい。
The polymer composite provided for the method of the present invention is a composite containing a structure.
The structure is a cluster of about 1 nm to 100 μm formed by aggregation of a filler, a vulcanized material and the like contained in the polymer composite material. There is no problem in the structure as long as the structure can be determined by various methods such as a transmission electron microscope (TEM), a scanning electron microscope (SEM), and a scanning transmission X-ray microscope (STXM). Not only materials that do not dissolve, but also materials that can dissolve in polymers such as zinc oxide, vulcanization accelerators, sulfur and the like may be used.

構造体として、具体的には、充填剤、架橋材料等を挙げられる。
充填剤としては、カーボンブラック、シリカ;mM・xSiO・zHO(式中、Mはアルミニウム、カルシウム、マグネシウム、チタン及びジルコニウムよりなる群より選択された少なくとも1種の金属、又は該金属の酸化物、水酸化物、水和物若しくは炭酸塩を示し、mは1〜5、xは0〜10、yは2〜5、zは0〜10の範囲の数値を示す。)、などが挙げられる。
Specifically as a structure, a filler, a crosslinking material, etc. are mentioned.
As the filler, carbon black, silica; mM 2 · xSiO y · zH 2 O (wherein, M 2 is at least one metal selected from the group consisting of aluminum, calcium, magnesium, titanium and zirconium, or the metal M represents an oxide, hydroxide, hydrate or carbonate of metal, m represents 1 to 5, x represents 0 to 10, y represents 2 to 5 and z represents a numerical value in the range of 0 to 10), Etc.

上記mM・xSiO・zHOで表される充填剤の具体例としては、水酸化アルミニウム(Al(OH))、アルミナ(Al、Al・3HO(水和物))、クレー(Al・2SiO)、カオリン(Al・2SiO・2HO)、パイロフィライト(Al・4SiO・HO)、ベントナイト(Al・4SiO・2HO)、ケイ酸アルミニウム(AlSiO、Al(SiO・5HOなど)、ケイ酸アルミニウムカルシウム(Al・CaO・2SiO)、水酸化カルシウム(Ca(OH))、酸化カルシウム(CaO)、ケイ酸カルシウム(CaSiO)、ケイ酸マグネシウムカルシウム(CaMgSiO)、水酸化マグネシウム(Mg(OH))、酸化マグネシウム(MgO)、タルク(MgO・4SiO・HO)、アタパルジャイト(5MgO・8SiO・9HO)、酸化アルミニウムマグネシウム(MgO・Al)、チタン白(TiO)、チタン黒(Ti2n−1)などが挙げられる。このような充填剤を含む高分子材料では、充填剤が凝集したクラスターが形成される。なお、上記充填剤の配合量は、高分子材料中のポリマー成分100質量部に対して、10〜200質量部が好ましい。 Specific examples of the filler represented by the above-mentioned mM 2 · x SiO y · z H 2 O include aluminum hydroxide (Al (OH) 3 ), alumina (Al 2 O 3 , Al 2 O 3 · 3 H 2 O (water) ), Clay (Al 2 O 3 · 2 SiO 2 ), kaolin (Al 2 O 3 · 2 SiO 2 · 2 H 2 O), pyrophyllite (Al 2 O 3 · 4 SiO 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.), calcium aluminum 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, clusters in which the filler is aggregated are formed. In addition, as for the compounding quantity of the said filler, 10-200 mass parts is preferable with respect to 100 mass parts of polymer components in polymeric material.

架橋材料は、ゴム組成物の架橋に関与する材料であり、各種加硫剤(架橋剤)、加硫促進剤、酸化亜鉛、等が挙げられる。 The crosslinking material is a material involved in the crosslinking of the rubber composition, and includes various vulcanizing agents (crosslinking agents), vulcanization accelerators, zinc oxide, and the like.

加硫剤としては、タイヤ工業で一般的なものを使用でき、硫黄加硫剤(粉末硫黄等の硫黄からなる加硫剤);1,6−ヘキサメチレン−ジチオ硫酸ナトリウム・二水和物、1,6−ビス(N,N’−ジベンジルチオカルバモイルジチオ)ヘキサンなどの硫黄を含む加硫剤:等が挙げられる。 As a vulcanizing agent, those generally used in the tire industry can be used, and a sulfur vulcanizing agent (a vulcanizing agent comprising sulfur such as powdered sulfur); 1,6-hexamethylene-sodium dithiosulfate dihydrate, Sulfur-containing vulcanizing agents such as 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) hexane: and the like.

加硫促進剤としては、グアニジン類、スルフェンアミド類、チアゾール類、チウラム類、ジチオカルバミン酸塩類、チオウレア類、キサントゲン酸塩類等、タイヤ工業で公知の各種加硫促進剤が挙げられる。なお、それぞれの架橋材料の配合量は、高分子材料中のポリマー成分100質量部に対して、0.1〜15質量部が好ましい。 The vulcanization accelerator includes various vulcanization accelerators known in the tire industry, such as guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, xanthogenates and the like. In addition, as for the compounding quantity of each crosslinking material, 0.1-15 mass parts is preferable with respect to 100 mass parts of polymer components in polymeric material.

高分子複合材料を構成する高分子材料としては特に限定されず、従来公知のものが挙げられる。例えば、1種類以上の共役ジエン系化合物を用いて得られるゴム材料、該ゴム材料と1種類以上の樹脂とが複合された複合材料を適用できる。共役ジエン系化合物としては特に限定されず、イソプレン、ブタジエンなどの公知の化合物が挙げられる。 It does not specifically limit as a polymeric material which comprises polymeric composite material, A conventionally well-known thing is mentioned. For example, a rubber material obtained by using one or more conjugated diene compounds, and a composite material in which the rubber material and one or more resins are complexed can be applied. The conjugated diene compound is not particularly limited, and examples thereof include known compounds such as isoprene and butadiene.

ゴム材料としては、天然ゴム(NR)、イソプレンゴム(IR)、ブタジエンゴム(BR)、スチレンブタジエンゴム(SBR)、アクリロニトリルブタジエンゴム(NBR)、クロロプレンゴム(CR)、ブチルゴム(IIR)、ハロゲン化ブチルゴム(X−IIR)、スチレンイソプレンブタジエンゴム(SIBR)などの二重結合を有するポリマーが挙げられる。また、前記ゴム材料、複合材料などの高分子材料は、水酸基、アミノ基などの変性基を1つ以上含むものでもよい。 As rubber materials, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), halogenated Polymers having double bonds such as butyl rubber (X-IIR) and styrene isoprene butadiene rubber (SIBR) can be mentioned. The polymer material such as the rubber material and the composite material may contain one or more modifying groups such as a hydroxyl group and an amino group.

上記樹脂としては特に限定されず、例えば、ゴム工業分野で汎用されているものが挙げられ、例えば、C5系脂肪族石油樹脂、シクロペンタジエン系石油樹脂などの石油樹脂が挙げられる。 The resin is not particularly limited, and examples thereof include those widely used in the rubber industry, such as petroleum resins such as C5 aliphatic petroleum resins and cyclopentadiene petroleum resins.

上記高分子複合材料は、タイヤ用材料等、ゴム工業分野で汎用されている他の配合剤(シランカップリング剤、ステアリン酸、各種老化防止剤、オイル、ワックスなど)を含むものでもよい。高分子複合材料は、公知の混練方法などを用いて製造できる。 The above-mentioned polymer composite material may contain other compounding agents (silane coupling agent, stearic acid, various anti-aging agents, oil, wax, etc.) widely used in the rubber industry, such as tire materials. The polymer composite material can be manufactured using a known kneading method or the like.

以下、本発明の力学物性測定方法の一例を具体的に説明する。
例えば、先ず、X線吸収量の測定により、高分子複合材料中の構造体のサイズを測定し、次いで、得られたサイズに基いて試料の厚みを決定し、作製した試料(高分子複合材料)について各種装置を用いて、各種力学物性を測定する方法、等が挙げられる。
Hereinafter, an example of the physical-physical-property measuring method of this invention is demonstrated concretely.
For example, first, the size of the structure in the polymer composite material is measured by measuring the amount of X-ray absorption, and then the thickness of the sample is determined based on the obtained size, and the prepared sample (polymer composite material And the like, methods of measuring various mechanical properties using various devices, and the like.

X線吸収量を測定する方法としては、高輝度X線を用いて試料の微小領域におけるX線吸収スペクトルを測定する手法であるマイクロXAFS(X−ray Absorption Fine Structure)等が挙げられる。通常のXAFSは、空間分解能を有しないため、試料全体の吸収量を検出するのに対し、マイクロXAFSは、試料の微小領域におけるX線吸収スペクトルを測定する測定方法であり、通常、100nm以下程度の空間分解能を有している。そのため、マイクロXAFSを採用することにより、試料中に含まれているそれぞれの架橋材料、充填剤等の吸収を検知し、硫黄加硫剤、加硫促進剤、充填剤等、各材料の吸収量の違いを検出できる。 Examples of a method of measuring the amount of X-ray absorption include micro XAFS (X-ray Absorption Fine Structure), which is a method of measuring an X-ray absorption spectrum in a minute area of a sample using high-intensity X-rays. While ordinary XAFS does not have spatial resolution, it detects the amount of absorption of the entire sample, whereas micro XAFS is a measurement method that measures the X-ray absorption spectrum in a minute area of the sample, and is usually about 100 nm or less Has a spatial resolution of Therefore, by using micro XAFS, the absorption of each cross-linking material, filler, etc. contained in the sample is detected, and the absorption amount of each material, such as sulfur vulcanizing agent, vulcanization accelerator, filler, etc. Can detect differences in

空間分解能に優れるという点から、マイクロXAFSは軟X線領域で測定する方法(マイクロNEXAFS)が好ましく、走査型透過X線顕微鏡(STXM:Scanning Transmission X−ray Microscopy)法やX線光電子顕微鏡(XPEEM:X−ray Photo emission electron microscopy)法、等が挙げられる。 From the viewpoint of excellent spatial resolution, the method of measuring in the soft X-ray region (micro NEXAFS) is preferable for micro XAFS, and a scanning transmission X-ray microscope (STXM) method or an X-ray photoelectron microscope (XPEEM) : X-ray Photo emission electron microscopy) method etc. are mentioned.

ポリマー中の硫黄加硫剤、加硫促進剤がX線損傷しやすいため、X線損傷が起きにくい方法での測定が望ましく、この点から、X線損傷が生じにくいSTXM法の方が好適である。また、測定の際、試料を冷却することでX線損傷を防ぐことが更に好ましい。 Since sulfur vulcanizing agents and vulcanization accelerators in polymers are susceptible to X-ray damage, it is desirable to use a method that is less susceptible to X-ray damage, and from this point of view the STXM method, which is less likely to cause X-ray damage, is preferred. is there. Further, it is more preferable to prevent X-ray damage by cooling the sample at the time of measurement.

STXM法は、フレネルゾーンプレートで集光した高輝度X線を試料の微小領域に照射し、試料を抜けた光(透過光)と入射光を測定することで微小領域のX線吸収量を測定できる。なお、フレネルゾーンプレートの代わりに、X線反射ミラーを用いたKirkpatrick−Baez(K−B)集光系で高輝度X線を集光してもよい。 The STXM method irradiates high-intensity X-rays collected by a Fresnel zone plate to a small area of a sample, and measures the amount of X-ray absorption in the small area by measuring the light (transmitted light) and incident light passing through the sample. it can. In addition, instead of the Fresnel zone plate, high brightness X-rays may be collected by a Kirkpatrick-Baez (K-B) focusing system using an X-ray reflecting mirror.

X線エネルギーで走査するため光源には連続X線発生装置が必要であり、詳細な化学状態を解析するには高いS/N比及びS/B比のX線吸収スペクトルを測定する必要がある。そのため、シンクロトロンから放射されるX線は、少なくとも1010(photons/s/mrad/mm/0.1%bw)以上の輝度を有し、且つ連続X線源であるため、測定には最適である。尚、bwはシンクロトロンから放射されるX線のband widthを示す。 A light source requires a continuous X-ray generator for scanning with X-ray energy, and it is necessary to measure X-ray absorption spectra of high S / N ratio and S / B ratio to analyze detailed chemical state . Therefore, the X-ray emitted from the synchrotron has a brightness of at least 10 10 (photons / s / mrad 2 / mm 2 /0.1% bw) and is a continuous X-ray source. Is the best. Here, bw indicates the band width of the X-ray emitted from the synchrotron.

高輝度X線の輝度(photons/s/mrad/mm/0.1%bw)は、好ましくは1010以上、より好ましくは1011以上、更に好ましくは1012以上である。上限は特に限定されないが、放射線ダメージがない程度以下のX線強度を用いることが好ましい。 The luminance (photons / s / mrad 2 / mm 2 /0.1% bw) of high luminance X-rays is preferably 10 10 or more, more preferably 10 11 or more, and still more preferably 10 12 or more. The upper limit is not particularly limited, but it is preferable to use an X-ray intensity not more than a level that causes no radiation damage.

また、高輝度X線の光子数(photons/s)は、好ましくは10以上、より好ましくは10以上である。上限は特に限定されないが、放射線ダメージがない程度以下のX線強度を用いることが好ましい。 Further, the photon number (photons / s) of high brightness X-ray is preferably 10 7 or more, more preferably 10 9 or more. The upper limit is not particularly limited, but it is preferable to use an X-ray intensity not more than a level that causes no radiation damage.

高輝度X線を用いて走査するエネルギー範囲は、好ましくは4000eV以下、より好ましくは1500eV以下、更に好ましくは1000eV以下である。4000eVを超えると、目的とする高分子複合材料を分析できないおそれがある。下限は特に限定されない。 The energy range scanned with high-intensity X-rays is preferably 4000 eV or less, more preferably 1500 eV or less, and further preferably 1000 eV or less. If it exceeds 4000 eV, the target polymer composite material may not be analyzed. The lower limit is not particularly limited.

上記のマイクロXAFS法を用いて、充填剤、架橋材料等の構造体を含む高分子複合材料のX線吸収スペクトル測定を行い、次いでマッピング画像(得られたX線吸収スペクトルの2次元マッピングによる画像)、各材料の標準スペクトル、等を解析することで、試料中に含まれる各構造体の化学状態の特定及びそのサイズ、分散状態を観察できる。 Using the above-mentioned micro XAFS method, X-ray absorption spectrum measurement of a polymer composite material including a structure such as a filler and a crosslinked material is performed, and then a mapping image (an image by two-dimensional mapping of the obtained X-ray absorption spectrum By analyzing the standard spectrum of each material, etc., it is possible to observe the specification of the chemical state of each structure contained in the sample and the size and dispersion state thereof.

なお、本発明における構造体のサイズは、STXM等で観察した構造体のサイズの平均値である。つまり、STXM等に供した試料(高分子複合材料)中に存在する各構造体のサイズの平均値である。構造体の形状が球形の場合には球の直径をその構造体のサイズとし、針状又は棒状の場合には短径をその構造体のサイズとし、不定型の場合には中心部からの平均粒径を構造体のサイズとする。 The size of the structure in the present invention is an average value of the sizes of the structures observed by STXM or the like. That is, it is an average value of the sizes of the respective structures present in the sample (polymer composite material) subjected to STXM or the like. When the shape of the structure is spherical, the diameter of the sphere is the size of the structure, and in the case of needle or rod, the minor diameter is the size of the structure. The particle size is the size of the structure.

次いで、測定された試料中の構造体(充填剤、架橋材料等)のサイズに基いて、図1(b)に示されているような構造体のサイズと同程度の試料厚みにする方法、等により、構造体のサイズを基に試料の厚みを決定する。 Then, based on the size of the structure (filler, crosslinked material, etc.) in the measured sample, a method of making the sample thickness similar to the size of the structure as shown in FIG. 1 (b), Determine the thickness of the sample based on the size of the structure, etc.

試料の厚みは、構造体の力学物性を精度良く測定できる範囲で適宜設定すればよいが、(構造体のサイズ)×0.5≦試料の厚み≦(構造体のサイズ)×2.0の範囲に調整することが好ましく、(構造体のサイズ)×0.7≦試料の厚み≦(構造体のサイズ)×1.7の範囲に調整することがより好ましい。 The thickness of the sample may be appropriately set within the range where the mechanical properties of the structure can be measured with high accuracy, but (size of structure) × 0.5 ≦ sample thickness ≦ (size of structure) × 2.0 It is preferable to adjust in the range, and it is more preferable to adjust in the range of (size of structure) × 0.7 ≦ sample thickness ≦ (size of structure) × 1.7.

試料の作製は、上記サイズの試料の作製が可能な方法を適宜選択すればよい。例えば、ナイフ、はさみ、カミソリ等で小片を切り出し、切り出した小片をクライオミクロトーム等を用いて切削して平滑面を形成することで作製できる。 For preparation of the sample, a method capable of preparing a sample of the above size may be appropriately selected. For example, a small piece can be cut out with a knife, scissors, a razor, or the like, and the cut small piece can be cut using a cryomicrotome or the like to form a smooth surface.

続いて、所定厚みに調整し、かつ平滑面が形成された試料について、力学物性を測定する。力学物性を測定する方法は特に限定されないが、試料表面と接触することで力学物性を測定する方法が望ましく、例えば、原子間力顕微鏡だけでなく、走査型フォース顕微鏡、ナノインデンター等も挙げられる。このように試料表面を接触させて測定することで、ナノ〜ミクロスケールで測定が可能となる。 Then, mechanical physical properties are measured about the sample which adjusted to predetermined thickness and in which the smooth surface was formed. The method of measuring the mechanical properties is not particularly limited, but a method of measuring the mechanical properties by contacting with the sample surface is desirable. For example, not only atomic force microscopes, but also scanning force microscopes, nano indenters, etc. may be mentioned. . By contacting the sample surface and measuring in this manner, measurement can be made on a nano to micro scale.

原子間力顕微鏡(AFM)は、先端に探針が装着されたカンチレバーを備えたもので、試料がAFMによって観察される場合、探針が試料の表面を走査する。探針は、試料の表面に沿って動く。探針の動きは、カンチレバーにより検出される。カンチレバーによって検出された探針の動きが画像化されることにより、AFM像が得られる。AFMでは、試料の表面の立体的な形状が検出される。AFMでは、更に試料の表面の硬さ、摩擦力等の力学的特性が測定できる。 An atomic force microscope (AFM) comprises a cantilever with a probe attached to its tip, and when the sample is observed by AFM, the probe scans the surface of the sample. The probe moves along the surface of the sample. The movement of the probe is detected by the cantilever. By imaging the movement of the probe detected by the cantilever, an AFM image is obtained. AFM detects the three-dimensional shape of the surface of a sample. AFM can also measure mechanical properties such as surface hardness and friction of the sample.

使用可能なAFMとして、Bruker AXS社製MultiMode8、日立ハイテクサイエンス社製E−sweep等が例示されるが、これらの機種に限定されるものではない。AFMの測定条件は、試料の種類や表面状態に応じて適宜選択される。例えば、タングステン、イリジウム、窒化珪素等を材質とする探針が使用できる。図3(a)、(b)。(c)は、AFM像の一例である(後述の実施例、比較例1〜2)。 Examples of usable AFMs include MultiMode 8 manufactured by Bruker AXS, E-sweep manufactured by Hitachi High-Tech Science Co., etc., but the present invention is not limited to these models. The measurement conditions of AFM are appropriately selected according to the type of sample and the surface state. For example, a probe made of tungsten, iridium, silicon nitride or the like can be used. Fig.3 (a), (b). (C) is an example of an AFM image (Example mentioned later, Comparative examples 1-2).

本発明では、AFMの任意のモードで力学物性を測定でき、適切な測定モードを適宜選択し、観察すればよい。適切な測定モードは、ポリマーの種類や、AFM観察に供される試料の表面状態に応じて選択される。例えば、試料の表面の(微少領域)の硬さが測定されるフォースモジュレーションモード、試料の表面における弾性率やヤング率の分布が測定可能なフォースボリュームモード、更にはフォースカーブ測定が挙げられる。また、コンタクトモード、タッピングモード、ノンコンタクトモードも挙げられる。 In the present invention, mechanical physical properties can be measured in an arbitrary mode of AFM, and an appropriate measurement mode may be appropriately selected and observed. An appropriate measurement mode is selected according to the type of polymer and the surface condition of the sample to be subjected to AFM observation. For example, a force modulation mode in which the hardness of a (small area) of the surface of the sample is measured, a force volume mode in which distribution of elastic modulus and Young's modulus on the surface of the sample can be measured, and force curve measurement can be mentioned. Moreover, a contact mode, a tapping mode, and a noncontact mode are also mentioned.

本発明の方法において、例えば、高分子複合材料中の構造体の硬さ等は、AFMで測定可能な力学的特性である。フォーボリューム測定で得られるフォースカーブを、HertzやDMT、JKRなどの力学モデルでフィッティングすることで、ヤング率を算出できる。 In the method of the present invention, for example, the hardness or the like of the structure in the polymer composite material is a mechanical property that can be measured by AFM. The Young's modulus can be calculated by fitting the force curve obtained by the four-volume measurement with a mechanical model such as Hertz, DMT, or JKR.

以上のとおり、本発明の方法によれば、高分子複合材料(試料)中に含まれるフィラー、架橋材料等の構造体について、硬さ等の力学物性を測定することが可能となる。 As described above, according to the method of the present invention, mechanical properties such as hardness can be measured for a structure such as a filler or a cross-linked material contained in a polymer composite material (sample).

実施例に基づいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 Although the present invention will be specifically described based on examples, the present invention is not limited to these.

(試料作成方法)
以下の配合内容に従い、硫黄及び加硫促進剤以外の材料を充填率が58%になるように(株)神戸製鋼所製の1.7Lバンバリーミキサーに充填し、80rpmで140℃に到達するまで混練した(工程1)。工程1で得られた混練物に、硫黄及び加硫促進剤を以下の配合にて添加し、160℃で20分間加硫することでゴム試料を得た(工程2)。
(Sample preparation method)
According to the contents of the following composition, materials other than sulfur and vulcanization accelerator are filled in 1.7L Banbury mixer made by Kobe Steel, Ltd. so that the filling rate is 58%, and until 140 ° C is reached at 80 rpm. It knead | mixed (process 1). Sulfur and a vulcanization accelerator were added to the kneaded product obtained in Step 1 in the following composition, and a rubber sample was obtained by vulcanizing at 160 ° C. for 20 minutes (Step 2).

(配合)
天然ゴム50質量部、ブタジエンゴム50質量部、酸化亜鉛3質量部、ステアリン酸2質量部、粉末硫黄1.2質量部、加硫促進剤CZ1質量部、加硫促進剤DPG0.5質量部。
(Blended)
50 parts by mass of natural rubber, 50 parts by mass of butadiene rubber, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, 1.2 parts by mass of powdered sulfur, 1 parts by mass of vulcanization accelerator CZ, 0.5 parts by mass of vulcanization accelerator DPG.

なお、使用材料は、以下のとおりである。
天然ゴム:TSR20
ブタジエンゴム:宇部興産(株)製BR150B
酸化亜鉛:東邦亜鉛(株)製の銀嶺R
ステアリン酸:日油(株)製の椿
粉末硫黄(5%オイル含有):鶴見化学工業(株)製の5%オイル処理粉末硫黄(オイル分5質量%含む可溶性硫黄)
加硫促進剤CZ:大内新興化学工業(株)製のノクセラーCZ(N−シクロヘキシル−2−ベンゾチアジルスルフェンアミド)
加硫促進剤DPG:大内新興化学工業(株)製のノクセラーD(1,3−ジフェニルグアニジン)
The materials used are as follows.
Natural rubber: TSR20
Butadiene rubber: BR150B manufactured by Ube Industries, Ltd.
Zinc oxide: Ginkgo R manufactured by Toho Zinc Co., Ltd.
Stearic acid: Koji powder sulfur (containing 5% oil) manufactured by NOF Corporation: 5% oil treated powder sulfur manufactured by Tsurumi Chemical Industry Co., Ltd. (soluble sulfur containing 5% by mass of oil)
Vulcanization accelerator CZ: Noccellar CZ (N-cyclohexyl-2-benzothiazylsulfenamide) manufactured by Ouchi Emerging Chemical Industry Co., Ltd.
Vulcanization accelerator DPG: Noxceler D (1,3-diphenylguanidine) manufactured by Ouchi Shinko Chemical Co., Ltd.

〔比較例1〜2〕
加硫ゴムシートからカミソリなどを用いて小片を切り出した。切り出した小片を更にクライオミクロトームを用いて切削して平滑面を作製し、マイカ板にマウントした。
(比較例1)試料厚み:2mm
(比較例2)試料厚み:500nm
Comparative Examples 1 and 2
Small pieces were cut out of the vulcanized rubber sheet using a razor or the like. The cut pieces were further cut using a cryomicrotome to produce a smooth surface, and mounted on a mica plate.
(Comparative Example 1) Sample thickness: 2 mm
(Comparative Example 2) Sample thickness: 500 nm

〔実施例〕
比較例と同様に、加硫ゴムシートから切り出した小片を更にクライオミクロトームを用いて切削して平滑面を作製し、マイカ板にマウントした。
試料厚み:STXM法を用いて測定した加硫促進剤のサイズから1μmとした(図2:NEXAFSの2次元マッピングを行って得られた窒素K殼吸収端のマッピング画像の一例)。
〔Example〕
As in the comparative example, a small piece cut out of the vulcanized rubber sheet was further cut using a cryomicrotome to prepare a smooth surface, which was then mounted on a mica plate.
Sample thickness: 1 μm from the size of the vulcanization accelerator measured using the STXM method (FIG. 2: an example of a mapping image of the nitrogen K 殼 absorption edge obtained by performing two-dimensional mapping of NEX AFS).

<AFM測定>
実施例・比較例で作製した試料の平滑面をフォースボリュームモード測定し、弾性率の分布像(弾性率像)を得た(図3(a):実施例、図3(b):比較例1、図3(c):比較例2)。
装置:Bruker AXS社製 MultiMode8
測定範囲:10μm×10μm
カンチレバー:0.5N/m
周波数:5Hz
<AFM measurement>
The smooth surface of the sample produced in the example and the comparative example was measured in a force volume mode, and a distribution image (elastic modulus image) of elastic modulus was obtained (FIG. 3 (a): example, FIG. 3 (b): comparative example 1, FIG.3 (c): Comparative example 2).
Device: Bruker AXS MultiMode 8
Measurement range: 10 μm × 10 μm
Cantilever: 0.5 N / m
Frequency: 5 Hz

図3の実施例、比較例1、2の弾性率像では、いずれも海島構造が観察されているが、島の数がかなり異なることがわかる。図3(a)の実施例の弾性率像は、島の部分は1〜2μmサイズで、分散状態がSTXM法で観察された加硫促進剤の分散状態と近い。また、島部分は20MPa以上と硬く、海部分は2〜3MPaと柔らかい。このことから島部分は加硫促進剤、海部分は主に高分子だと考えられる。以上の結果から、正確に弾性率マッピング測定が実施されたと考えられる。 Although the sea-island structure is observed in each of the elastic modulus images of the example of FIG. 3 and the comparative examples 1 and 2, it can be seen that the number of islands is considerably different. The elastic modulus image of the example of FIG. 3A has an island part size of 1 to 2 μm, and the dispersed state is close to the dispersed state of the vulcanization accelerator observed by the STXM method. Moreover, the island part is as hard as 20 MPa or more, and the sea part is as soft as 2 to 3 MPa. From this, it is thought that the island part is a vulcanization accelerator and the sea part is mainly a polymer. From the above results, it is considered that elastic modulus mapping measurement was accurately performed.

一方、比較例1は、島部分の数が少ないことがわかる。これは、試料厚みが構造体サイズよりかなり大きいため、構造体が高分子に押し込まれ、硬さが正確に測定できていないと考えられる。また、比較例2も島の数が少ない。これは、試料厚みを薄くしたため、構造体も薄くなり、弾性率が正しく測定できない、又はミクロトームでカットした際、構造体が抜け落ちてしまったためであると考えられる。 On the other hand, Comparative Example 1 shows that the number of island portions is small. This is considered to be because the structure is pressed into the polymer and the hardness can not be accurately measured because the sample thickness is much larger than the structure size. Further, Comparative Example 2 also has a small number of islands. It is considered that this is because the structure is also thinner because the sample thickness is reduced, the elastic modulus can not be measured correctly, or the structure is dropped when cut with a microtome.

更に、加硫促進剤に代えて、硫黄、酸化亜鉛のサイズに合わせて実施した場合や、シリカ、カーボンブラックを添加した試料のフィラーのサイズに合わせて実施した場合についても、実施例と同様、正確に弾性率マッピング測定が実施できた。 Furthermore, in the case where it is carried out in accordance with the size of sulfur and zinc oxide in place of the vulcanization accelerator, and in the case of being carried out according to the size of the filler of the sample to which silica and carbon black are added, Elastic modulus mapping measurement could be performed correctly.

Claims (5)

構造体を含む高分子複合材料の力学物性測定方法であって、
高分子複合材料中の構造体のサイズを基に決定した厚みを持つ試料を用いて測定することを特徴とする力学物性測定方法。
A method of measuring mechanical properties of a polymer composite material including a structure,
A method of measuring mechanical properties characterized by using a sample having a thickness determined based on the size of a structure in a polymer composite material.
構造体は、充填剤及び架橋材料の少なくとも1種以上である請求項1記載の力学物性測定方法。 The method for measuring mechanical properties according to claim 1, wherein the structure is at least one or more of a filler and a crosslinked material. 構造体のサイズは、透過型電子顕微鏡、走査型電子顕微鏡又は走査型透過X線顕微鏡を用いて測定されたものである請求項1又は2記載の力学物性測定方法。 The method for measuring mechanical properties according to claim 1 or 2, wherein the size of the structure is measured using a transmission electron microscope, a scanning electron microscope or a scanning transmission X-ray microscope. 試料は、高分子複合材料中の構造体の大きさと同程度の厚みに調整したものである請求項1〜3のいずれかに記載の力学物性測定方法。 The method for measuring mechanical properties according to any one of claims 1 to 3, wherein the sample is adjusted to a thickness substantially the same as the size of the structure in the polymer composite material. 試料表面と接触させてナノ〜ミクロスケールの高分子複合材料の力学物性を測定する請求項1〜4のいずれかに記載の力学物性測定方法。 The method for measuring mechanical physical properties according to any one of claims 1 to 4, wherein the mechanical physical properties of the nano-to-microscale polymer composite material are measured by contacting the sample surface.
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