JP6951985B2

JP6951985B2 - Resin composition and water blocking material

Info

Publication number: JP6951985B2
Application number: JP2018026252A
Authority: JP
Inventors: 英史小澤; 勉芳谷
Original assignee: Furukawa Electric Co Ltd
Current assignee: Furukawa Electric Co Ltd
Priority date: 2018-02-16
Filing date: 2018-02-16
Publication date: 2021-10-20
Anticipated expiration: 2038-02-16
Also published as: JP2019143003A

Description

本発明は、樹脂組成物及び止水材に関する。 The present invention relates to a resin composition and a water blocking material.

戸建住宅の外壁には、換気口を設けたり、給配水管やエアコン配管を通したり、配線を通したりするための貫通部が設けられる。この貫通部には通常、貫通パイプが設置され、外壁と貫通パイプとの間の空隙にはシーリング材などが配され、空隙を封鎖して雨水等の侵入を防いでいる。
また、特許文献１には、外壁貫通部に設置するパイプに弾性部材を有するフランジ部材（ツバ部）を設け、このフランジ部材をねじで外壁に押し付けて、パイプと壁面との間の止水性を確保する技術が開示されている。 The outer wall of the detached house is provided with a ventilation port, a through portion for passing a water supply / distribution pipe and an air conditioner pipe, and a through portion for passing the wiring. A penetrating pipe is usually installed in this penetrating portion, and a sealing material or the like is arranged in the gap between the outer wall and the penetrating pipe to block the gap and prevent rainwater or the like from entering.
Further, in Patent Document 1, a flange member (flange portion) having an elastic member is provided on the pipe installed in the outer wall penetrating portion, and the flange member is pressed against the outer wall with a screw to prevent water from being stopped between the pipe and the wall surface. The technology to secure is disclosed.

特許第５８３０４５５号公報Japanese Patent No. 5830455

住宅の外壁は通常、サイディングやモルタルでデザイン加工されている。したがって、上記特許文献１記載の技術を適用する場合でも、弾性部材と壁面との密着性を高めて十分な止水性を確保するためには、外壁の凹凸デザインを落として平面を出した上で、貫通パイプを設置する必要があった。また、住宅は一般に、数十年間という長期に亘り居住するものであるため、貫通パイプと外壁との間の止水性は、長期間、持続的に確保する必要がある。
そこで本発明は、住宅外壁等の凹凸面に対して、当該凹凸面を処理せずにそのまま適用した場合でも、圧力下（凹凸面に押し付けた状態で）、当該凹凸にしっかりと追従して密着することができ、かつ、この圧力下の追従密着性を長期に亘り発現し続けることができ、その結果、優れた止水性を長期間、持続的に発現することができる樹脂組成物及び止水材を提供することを課題とする。 The exterior walls of houses are usually designed with siding or mortar. Therefore, even when the technique described in Patent Document 1 is applied, in order to improve the adhesion between the elastic member and the wall surface and secure sufficient water stopping property, the uneven design of the outer wall is dropped to make a flat surface. , It was necessary to install a through pipe. In addition, since a house generally resides for a long period of several decades, it is necessary to continuously secure the water stoppage between the through pipe and the outer wall for a long period of time.
Therefore, the present invention firmly follows and adheres to an uneven surface such as an outer wall of a house under pressure (in a state of being pressed against the uneven surface) even when the uneven surface is applied as it is without being treated. And, as a result, the resin composition and the water-stopping property can continuously develop the follow-up adhesion under the pressure for a long period of time, and as a result, excellent water-stopping property can be continuously developed for a long period of time. The subject is to provide materials.

本発明者らは上記課題に鑑み、弾性を有する種々の組成ないし物性の樹脂組成物を調製し、それらの止水性能を検討した。その結果、圧力下において凹凸面に対して優れた追従性を示し、かつ、この追従密着状態を長期間維持することができる樹脂組成物を調製するに至った。そして、この樹脂組成物の物性と上記の止水性能との関係について検討を進めた結果、２５％圧縮モジュラスが小さく一定の柔らかさを有しながら、圧力変形状態における経時的な応力緩和も抑えられた物性の樹脂組成物により、上記課題を解決できることを見い出すに至った。本発明はこれらの知見に基づきさらに検討を重ね、完成されるに至ったものである。 In view of the above problems, the present inventors have prepared resin compositions having various compositions or physical properties having elasticity, and examined their water-stopping performance. As a result, we have prepared a resin composition that exhibits excellent followability to uneven surfaces under pressure and can maintain this follow-up close contact state for a long period of time. As a result of studying the relationship between the physical properties of this resin composition and the above-mentioned water-stopping performance, the 25% compression modulus is small and has a certain softness, while suppressing stress relaxation over time in a pressure deformation state. It has been found that the above-mentioned problems can be solved by the resin composition having the above-mentioned physical characteristics. The present invention has been further studied based on these findings and has been completed.

すなわち上記課題は以下の発明により解決された。
〔１〕
熱可塑性エラストマーと、酸変性樹脂と、該熱可塑性エラストマー及び該酸変性樹脂の合計１００質量部に対して８０〜３１０質量部の金属水酸化物と、１６０〜４６０質量部の軟化剤とを含有する樹脂組成物。
〔２〕
前記熱可塑性エラストマーが、スチレン系熱可塑性エラストマーを含む、〔１〕記載の樹脂組成物。
〔３〕
前記熱可塑性エラストマー及び前記酸変性樹脂の合計に占める前記酸変性樹脂の割合が１０〜４０質量％である、〔１〕又は〔２〕記載の樹脂組成物。
〔４〕
ＪＩＳＫ６２５４のＣ法に準拠して測定される２５％圧縮応力が３００ｋＰａ以下である、〔１〕〜〔３〕のいずれか記載の樹脂組成物。
〔５〕
ドーナツ状に成形されてなる、〔１〕〜〔４〕のいずれか記載の樹脂組成物。
〔６〕
前記樹脂組成物を、孔径４０ｍｍ、外径６０ｍｍ、厚さ６．７ｍｍの平板ドーナツ状に成形し、該ドーナツ状成形品を、孔径３７．１ｍｍの円筒型パイプが円筒軸方向端部に有する外径１０５ｍｍのステンレス製フランジ表面に、該ドーナツ状試験片の孔の中央部に前記円筒型パイプの孔が位置するように配し、該ドーナツ状成形品の前記フランジ側とは反対の側にはサイディング板（ニチハ社製、商品名：モエンエクセラード１６ニューグランドールシリーズＩＥＰＢ３１１Ｎ）を、該サイディング板の凹凸面が該ドーナツ状成形品側となるように配し、前記サイディング板の凹凸面と前記フランジ表面との最短距離が２．０ｍｍとなるまで該フランジと該サイディング板とをねじ締めした状態とし、前記パイプ内に高さ１０ｃｍまで２５℃の水を入れた場合に、３０℃で、３０分間以上水漏れを生じない、〔１〕〜〔４〕のいずれか記載の樹脂組成物。
〔７〕
前記樹脂組成物を、孔径４０ｍｍ、外径６０ｍｍ、厚さ６．７ｍｍの平板ドーナツ状に成形し、該ドーナツ状成形品を、孔径３７．１ｍｍの円筒型パイプが円筒軸方向端部に有する外径１０５ｍｍのステンレス製フランジ表面に、該ドーナツ状試験片の孔の中央部に前記円筒型パイプの孔が位置するように配し、該ドーナツ状成形品の前記フランジ側とは反対の側にはサイディング板（ニチハ社製、商品名：モエンエクセラード１６ニューグランドールシリーズＩＥＰＢ３１１Ｎ）を、該サイディング板の凹凸面が該ドーナツ状成形品側となるように配し、前記サイディング板凹凸面と前記フランジ表面との最短距離が２．０ｍｍとなるまで該フランジと該サイディング板とをねじ締めした状態とし、３０℃で１２５時間静置し、その後、前記パイプ内に高さ１０ｃｍまで２５℃の水を入れた場合に、３０℃で、３０分間以上水漏れを生じない、〔１〕〜〔４〕のいずれか記載の樹脂組成物。
〔８〕
止水材として用いる、〔１〕〜〔７〕のいずれか記載の樹脂組成物。
〔９〕
熱可塑性エラストマーと、酸変性樹脂と、該熱可塑性エラストマー及び該酸変性樹脂の合計１００質量部に対して８０〜３１０質量部の金属水酸化物と、１６０〜４６０質量部の軟化剤とを含有する樹脂組成物からなる止水材。
〔１０〕
前記熱可塑性エラストマーがスチレン系熱可塑性エラストマーを含む、〔９〕記載の止水材。
〔１１〕
前記樹脂組成物中、前記熱可塑性エラストマー及び前記酸変性樹脂の合計に占める前記酸変性樹脂の割合が１０〜４０質量％である、〔９〕又は〔１０〕記載の止水材。
〔１２〕
前記樹脂組成物の、ＪＩＳＫ６２５４のＣ法に準拠して測定される２５％圧縮応力が３００ｋＰａ以下である、〔９〕〜〔１１〕のいずれか記載の止水材。
〔１３〕
ドーナツ状に成形されてなる、〔９〕〜〔１２〕のいずれか記載の止水材。
〔１４〕
前記止水材を、孔径４０ｍｍ、外径６０ｍｍ、厚さ６．７ｍｍの平板ドーナツ状に成形し、該ドーナツ状成形品を、孔径３７．１ｍｍの円筒型パイプが円筒軸方向端部に有する外径１０５ｍｍのステンレス製フランジ表面に、該ドーナツ状試験片の孔の中央部に前記円筒型パイプの孔が位置するように配し、該ドーナツ状成形品の前記フランジ側とは反対の側にはサイディング板（ニチハ社製、商品名：モエンエクセラード１６ニューグランドールシリーズＩＥＰＢ３１１Ｎ）を、該サイディング板の凹凸面が該ドーナツ状成形品側となるように配し、前記サイディング板の凹凸面と前記フランジ表面との最短距離が２．０ｍｍとなるまで該フランジと該サイディング板とをねじ締めした状態とし、前記パイプ内に高さ１０ｃｍまで２５℃の水を入れた場合に、３０℃で、３０分間以上水漏れを生じない、〔１１〕〜〔１３〕のいずれか記載の止水材。
〔１５〕
前記止水材を、孔径４０ｍｍ、外径６０ｍｍ、厚さ６．７ｍｍの平板ドーナツ状に成形し、該ドーナツ状成形品を、孔径３７．１ｍｍの円筒型パイプが円筒軸方向端部に有する外径１０５ｍｍのステンレス製フランジ表面に、該ドーナツ状試験片の孔の中央部に前記円筒型パイプの孔が位置するように配し、該ドーナツ状成形品の前記フランジ側とは反対の側にはサイディング板（ニチハ社製、商品名：モエンエクセラード１６ニューグランドールシリーズＩＥＰＢ３１１Ｎ）を、該サイディング板の凹凸面が該ドーナツ状成形品側となるように配し、前記サイディング板の凹凸面と前記フランジ表面との最短距離が２．０ｍｍとなるまで該フランジと該サイディング板とをねじ締めした状態とし、３０℃で１２５時間静置し、その後、前記パイプ内に高さ１０ｃｍまで２５℃の水を入れた場合に、３０℃で、３０分間以上水漏れを生じない、〔１１〕〜〔１４〕のいずれか記載の止水材。
That is, the above problem was solved by the following invention.
[1]
Contains 80 to 310 parts by mass of metal hydroxide and 160 to 460 parts by mass of softening agent with respect to 100 parts by mass of the total of the thermoplastic elastomer, the acid-modified resin, and the thermoplastic elastomer and the acid-modified resin. to the resin composition.
[2 ]
The resin composition according to [1 ], wherein the thermoplastic elastomer contains a styrene-based thermoplastic elastomer .
[3 ]
Wherein the thermal ratio of the thermoplastic elastomer and the acid-modified resin to the total of the acid-modified resin is 10 to 40 wt%, [1] or [2] resin composition.
[4]
The resin composition according to any one of [1] to [3], wherein the 25% compressive stress measured according to the C method of JIS K 6254 is 300 kPa or less.
[ 5 ]
The resin composition according to any one of [1] to [4 ], which is formed into a donut shape.
[ 6 ]
The resin composition is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. When the flange and the siding plate are screwed together until the shortest distance to the flange surface is 2.0 mm, and water at 25 ° C. up to a height of 10 cm is poured into the pipe, the temperature is 30 ° C. The resin composition according to any one of [1] to [4 ], which does not cause water leakage for 30 minutes or more.
[ 7 ]
The resin composition is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. The flange and the siding plate are screwed together until the shortest distance to the flange surface is 2.0 mm, and the pipe is allowed to stand at 30 ° C. for 125 hours, and then water at 25 ° C. up to a height of 10 cm is placed in the pipe. The resin composition according to any one of [1] to [4 ], which does not cause water leakage for 30 minutes or more at 30 ° C.
[ 8 ]
The resin composition according to any one of [1] to [7 ], which is used as a water blocking material.
[ 9 ]
Contains 80 to 310 parts by mass of metal hydroxide and 160 to 460 parts by mass of softening agent with respect to 100 parts by mass of the total of the thermoplastic elastomer, the acid-modified resin, and the thermoplastic elastomer and the acid-modified resin. A water blocking material made of a resin composition.
[ 10 ]
The water blocking material according to [9 ], wherein the thermoplastic elastomer contains a styrene-based thermoplastic elastomer.
[11]
The water blocking material according to [9] or [10], wherein the ratio of the acid-modified resin to the total of the thermoplastic elastomer and the acid-modified resin in the resin composition is 10 to 40% by mass.
[ 12 ]
The water blocking material according to any one of [9 ] to [ 11 ], wherein the 25% compressive stress of the resin composition measured in accordance with the C method of JIS K 6254 is 300 kPa or less.
[13]
The water blocking material according to any one of [9] to [12], which is formed into a donut shape.
[14]
The water blocking material is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. When the flange and the siding plate are screwed together until the shortest distance to the flange surface is 2.0 mm, and water at 25 ° C. is poured into the pipe to a height of 10 cm, the temperature is 30 ° C. The water blocking material according to any one of [11] to [13], which does not cause water leakage for 30 minutes or more.
[15]
The water blocking material is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. The flange and the siding plate were screwed together until the shortest distance to the flange surface was 2.0 mm, allowed to stand at 30 ° C. for 125 hours, and then placed in the pipe at 25 ° C. up to a height of 10 cm. The water blocking material according to any one of [11] to [14], which does not cause water leakage at 30 ° C. for 30 minutes or more when water is added.

本発明の樹脂組成物及び止水材は、住宅外壁等の凹凸面に対して適用した場合でも、圧力下、当該凹凸にしっかりと追従して密着することができ、かつ、この圧力下の追従密着性を長期に亘り発現し続けることができ、それゆえ優れた止水性を長期間、持続的に発現することができる。 Even when the resin composition and the water blocking material of the present invention are applied to an uneven surface such as an outer wall of a house, the resin composition and the water blocking material can firmly follow and adhere to the uneven surface under pressure, and follow the unevenness under the pressure. Adhesion can be continuously developed for a long period of time, and therefore excellent water stopping property can be continuously developed for a long period of time.

実施例に記載の止水性試験に用いた試験具が組み立てられた状態を模式的に示す正面図である。It is a front view which shows typically the state in which the test tool used for the water-stopping test described in an Example is assembled.

［樹脂組成物］
本発明の樹脂組成物は、２５％圧縮応力が３００ｋＰａ以下であり、かつ、３０℃で１２５日経過後の緩和弾性率が９．０ｋＰａ以上という特有の物性を有している。２５％圧縮応力が３００ｋＰａ以下であることにより、樹脂組成物に一定の高い凹凸追従性が付与される。つまり、圧力下における凹凸面への追従密着性を十分に高めることができる。
また、３０℃で１２５日後の緩和弾性率が９．０ｋＰａ以上であることにより、圧力変形状態における経時的な応力緩和が抑えられて長期に亘り一定の高い応力も発現することができる。そのため、圧力をかけて凹凸面に追従、密着させた樹脂組成物は、その追従密着状態を長期に亘り安定に維持することができる。
すなわち、本発明の樹脂組成物は、凹凸追従性（変形性）と弾性という、互いに相反する特性の両立をこれまでにない高いレベルで実現したものであり、例えば、住宅用貫通部材等の止水材として好適な、特異な物性を有している。
本発明の樹脂組成物の形態は、溶媒を含有せずに固形分で構成されていてもよいし。また、溶媒中に樹脂成分等が溶解した状態にあり、成形時等に溶媒を揮発させて用いる形態でもよい。なお、本発明の樹脂組成物が溶媒を含有する形態であっても、本発明で規定する圧縮応力や緩和弾性率の値は、溶媒を除いた状態における樹脂組成物の物性である。
[Resin composition]
The resin composition of the present invention has peculiar physical properties such that a 25% compressive stress is 300 kPa or less and a relaxation elastic modulus after 125 days at 30 ° C. is 9.0 kPa or more. When the 25% compressive stress is 300 kPa or less, a certain high unevenness followability is imparted to the resin composition. That is, it is possible to sufficiently improve the follow-up adhesion to the uneven surface under pressure.
Further, since the relaxation elastic modulus at 30 ° C. after 125 days is 9.0 kPa or more, the stress relaxation over time in the pressure deformation state can be suppressed, and a constant high stress can be exhibited for a long period of time. Therefore, the resin composition that follows and adheres to the uneven surface by applying pressure can stably maintain the follow-up adhesion state for a long period of time.
That is, the resin composition of the present invention realizes both unevenness-following property (deformability) and elasticity, which are mutually contradictory characteristics, at an unprecedented high level. It has peculiar physical properties suitable as a water material.
The form of the resin composition of the present invention may be composed of a solid content without containing a solvent. Further, the resin component or the like may be dissolved in the solvent, and the solvent may be volatilized and used at the time of molding or the like. Even if the resin composition of the present invention contains a solvent, the values of the compressive stress and the relaxation elastic modulus specified in the present invention are the physical properties of the resin composition in a state where the solvent is removed.

＜２５％圧縮応力＞
本発明の樹脂組成物は、上記の通り、２５％圧縮応力が３００ｋＰａ以下である。つまり、一定の柔らかな物性を有し、圧力下における凹凸面への追従性に優れている。
本発明の樹脂組成物は、２５％圧縮応力が２７０ｋＰａ以下が好ましく、２５０ｋＰａ以下がより好ましく、２３０ｋＰａ以下がさらに好ましい。また、上記２５％圧縮応力は通常は３０ｋＰａ以上であり、４０ｋＰａ以上が実際的である。
樹脂組成物の２５％圧縮応力は、ＪＩＳＫ６２５４のＣ法に準拠して測定される。より具体的には、後述する実施例に記載の方法により決定することができる。
<25% compressive stress >
As described above, the resin composition of the present invention has a 25% compressive stress of 300 kPa or less. That is, it has a certain soft physical property and is excellent in following the uneven surface under pressure.
The resin composition of the present invention preferably has a 25% compressive stress of 270 kPa or less, more preferably 250 kPa or less, and even more preferably 230 kPa or less. The 25% compressive stress is usually 30 kPa or more, and 40 kPa or more is practical.
The 25% compressive stress of the resin composition is measured according to the C method of JIS K 6254. More specifically, it can be determined by the method described in Examples described later.

＜３０℃で１２５日後の緩和弾性率＞
本発明の樹脂組成物は、上記の通り、３０℃で１２５日経過後の緩和弾性率が９．０ｋＰａ以上である。つまり、圧力変形状態において、経時的な応力緩和が抑えられて一定の弾性を維持することができる。その結果、圧力をかけて凹凸面へ追従、密着させた樹脂組成物は、当該追従密着状態を長期に亘り維持することができる。
本発明の樹脂組成物は、３０℃で１２５日経過後の緩和弾性率が９．２ｋＰａ以上が好ましい。また、上記緩和弾性率は通常は１００ｋＰａ以下であり、９０ｋＰａ以下が実際的であり、８０ｋＰａ以下とすることも好ましい。
３０℃で１２５日経過後の緩和弾性率は、特開２０１３−１３４４７７号公報の段落［００２３］〜［００２５］に記載された方法に準じて測定することができる。より具体的には、後述する実施例に記載の方法により決定することができる。 <Relaxation modulus after 125 days at 30 ° C>
As described above, the resin composition of the present invention has a relaxed elastic modulus of 9.0 kPa or more after 125 days at 30 ° C. That is, in the pressure deformation state, stress relaxation over time can be suppressed and constant elasticity can be maintained. As a result, the resin composition that follows and adheres to the uneven surface by applying pressure can maintain the follow-up adhesion state for a long period of time.
The resin composition of the present invention preferably has a relaxed elastic modulus of 9.2 kPa or more after 125 days at 30 ° C. Further, the relaxed elastic modulus is usually 100 kPa or less, 90 kPa or less is practical, and 80 kPa or less is also preferable.
The relaxed elastic modulus after 125 days at 30 ° C. can be measured according to the method described in paragraphs [0023] to [0025] of JP2013-134477A. More specifically, it can be determined by the method described in Examples described later.

＜樹脂組成物の成分＞
本発明の樹脂組成物は、上記特性を有すれば、その成分組成に特に制限はない。例えば、熱可塑性樹脂をベース樹脂として、必要により軟化剤、フィラー等を配合し、また必要により慣用添加物等を配合し、本発明の樹脂組成物を得ることができる。
なお、樹脂組成物を構成する、下記で説明する樹脂成分の少なくとも一部は、後述するように酸変性された形態であることも好ましい。 <Ingredients of resin composition>
The resin composition of the present invention is not particularly limited in its component composition as long as it has the above characteristics. For example, the resin composition of the present invention can be obtained by using a thermoplastic resin as a base resin, blending a softener, a filler and the like as necessary, and blending a conventional additive and the like as necessary.
It is also preferable that at least a part of the resin components described below constituting the resin composition is in an acid-modified form as described later.

（樹脂成分）
本発明の樹脂組成物は、樹脂成分（ポリマー成分）として、通常は熱可塑性樹脂を含み、樹脂成分のすべてが熱可塑性樹脂であることが好ましい。熱可塑性樹脂の種類は、本発明で規定する物性ないし特性の樹脂組成物を実現できれば特に制限はない。
熱可塑性樹脂の好ましい例としては、ポリスチレン樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂等を挙げることができる。なかでも、本発明に用いる熱可塑性樹脂は熱可塑性エラストマーを含むことが好ましい。本発明の樹脂組成物中の熱可塑性樹脂に占める熱可塑性エラストマーの割合は４０質量％以上が好ましく、より好ましくは５０質量％以上、さらに好ましくは７０質量％以上、さらに好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、本発明の樹脂組成物中の熱可塑性樹脂のすべてが熱可塑性エラストマーであることも好ましい。
熱可塑性エラストマーとしては、スチレン系、ポリウレタン系、ポリアミド系、ポリエステル系の各エラストマーを挙げることができ、これらの１種又は２種以上を用いることができる。以下、本発明に用いる熱可塑性エラストマーの好ましい形態について説明する。 (Resin component)
The resin composition of the present invention usually contains a thermoplastic resin as a resin component (polymer component), and it is preferable that all of the resin components are thermoplastic resins. The type of thermoplastic resin is not particularly limited as long as the resin composition having the physical properties or properties specified in the present invention can be realized.
Preferred examples of the thermoplastic resin include polystyrene resin, polyurethane resin, polyamide resin, polyester resin and the like. Among them, the thermoplastic resin used in the present invention preferably contains a thermoplastic elastomer. The proportion of the thermoplastic elastomer in the thermoplastic resin in the resin composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more. More preferably, it is 90% by mass or more, and it is also preferable that all of the thermoplastic resins in the resin composition of the present invention are thermoplastic elastomers.
Examples of the thermoplastic elastomer include styrene-based, polyurethane-based, polyamide-based, and polyester-based elastomers, and one or more of these elastomers can be used. Hereinafter, preferred forms of the thermoplastic elastomer used in the present invention will be described.

− スチレン系熱可塑性エラストマー −
スチレン系熱可塑性エラストマーとしては、例えば、スチレン−ブタジエンブロック共重合体（ＳＢＲ）、水素添加スチレン−ブタジエンブロック共重合体（ＳＥＢ、スチレン−エチレン／ブチレンブロック共重合体）、スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）、水素添加スチレン−ブタジエン−スチレンブロック共重合体（ＳＥＢＳ、スチレン−エチレン／ブチレン−スチレンブロック共重合体）、スチレン−イソプレンブロック共重合体（ＳＩＲ）、水素添加スチレン−イソプレンブロック共重合体（ＳＥＰ、スチレン−エチレン／プロピレンブロック共重合体）、スチレン−イソプレン−スチレンブロック共重合体（ＳＩＳ）、水素添加スチレン−イソプレン−スチレンブロック共重合体（ＳＥＰＳ、スチレン−エチレン／プロピレン−スチレンブロック共重合体）等が挙げられ、これらの１種又は２種以上を用いることができる。 − Styrene-based thermoplastic elastomer −
Examples of the styrene-based thermoplastic elastomer include a styrene-butadiene block copolymer (SBR), a hydrogenated styrene-butadiene block copolymer (SEB, a styrene-ethylene / butylene block copolymer), and a styrene-butadiene-styrene block. Copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS, styrene-ethylene / butylene-styrene block copolymer), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene Block copolymer (SEP, styrene-ethylene / propylene block copolymer), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS, styrene-ethylene / propylene) -Sterene block copolymer) and the like, and one or more of these can be used.

− ポリウレタン系熱可塑性エラストマー −
ポリウレタン系熱可塑性エラストマーとしては、例えば、低分子のグリコール及びジイソシアネートからなるハードセグメントと、高分子（長鎖）ジオールおよびジイソシアネートからなるソフトセグメントとの構造単位を含むエラストマーなどが挙げられる。
高分子（長鎖）ジオールとしては、ポリプロピレングリコール、ポリテトラメチレンオキサイド、ポリ（１，４−ブチレンアジペート）、ポリ（エチレン・１，４−ブチレンアジペート）、ポリカプロラクトン、ポリ（１，６−ヘキシレンカーボネート）、ポリ（１，６−ヘキシレン・ネオペンチレンアジペート）などが挙げられる。高分子（長鎖）ジオールの数平均分子量は、５００以上１０，０００未満が好ましい。
低分子のグリコールとしては、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、ビスフェノールＡ等の短鎖ジオールを用いることができる。短鎖ジオールの数平均分子量は、４８以上〜５００未満が好ましい。
本発明の樹脂組成物は、ポリウレタン系熱可塑性エラストマーの１種又は２種以上を用いることができる。 − Polyurethane-based thermoplastic elastomer −
Examples of the polyurethane-based thermoplastic elastomer include an elastomer containing a structural unit of a hard segment composed of a low molecular weight glycol and a diisocyanate and a soft segment composed of a high molecular weight (long chain) diol and a diisocyanate.
Polymer (long chain) diols include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene 1,4-butylene adipate), polycaprolactone, and poly (1,6-he). Xylene carbonate), poly (1,6-hexylene / neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 or more and less than 10,000.
As the low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol and bisphenol A can be used. The number average molecular weight of the short chain diol is preferably 48 or more and less than 500.
As the resin composition of the present invention, one or more kinds of polyurethane-based thermoplastic elastomers can be used.

− ポリアミド系熱可塑性エラストマー −
ポリアミド系熱可塑性エラストマーとしては、例えば、ハードセグメントがポリアミドであり、ソフトセグメントがポリエーテルやポリエステルを用いたマルチブロックコポリマーを挙げることができる。ハードセグメントとしては、例えば、ポリアミド６，６６，６１０，１１，１２等が挙げられる。ソフトセグメントにおけるポリエーテルは、ポリエチレングリコール、ジオールポリ（オキシテトラメチレン）グリコール、ポリ（オキシプロピレン）グリコール等が挙げられ、ポリエステルは、ポリ（エチレンアジペート）グリコール、ポリ（ブチレン−１，４−アジペート）グリコール等が挙げられる。
本発明の樹脂組成物は、ポリアミド系熱可塑性エラストマーの１種又は２種以上を用いることができる。 − Polyamide-based thermoplastic elastomer −
Examples of the polyamide-based thermoplastic elastomer include a multi-block copolymer in which the hard segment is polyamide and the soft segment is a polyether or polyester. Examples of the hard segment include polyamides 6, 66, 610, 11, 12 and the like. Examples of the polyether in the soft segment include polyethylene glycol, diol poly (oxytetramethylene) glycol, poly (oxypropylene) glycol and the like, and the polyester includes poly (ethylene adipate) glycol and poly (butylene-1,4-adipate) glycol. And so on.
As the resin composition of the present invention, one or more kinds of polyamide-based thermoplastic elastomers can be used.

− ポリエステル系熱可塑性エラストマー −
ポリエステル系熱可塑性エラストマーとしては、例えば、特開平１１−９２６３６号公報などに記載された高融点ポリエステルセグメント（ハードセグメント）と分子量４００〜６，０００程度の低融点ポリマーセグメント（ソフトセグメント）とからなるブロックコポリマーを用いることができる。高融点ポリエステルセグメントとしては、例えば、ポリブチレンテレフタレート（ＰＢＴ）等を挙げることができる。また、低融点ポリマーセグメントとしては、例えば、ガラス転移温度が−７０℃の非晶性ポリエーテル、例えば、ポリテトラメチレンエーテルグリコール（ＰＴＭＧ）等を挙げることができる。
本発明の樹脂組成物は、ポリエステル系熱可塑性エラストマーの１種又は２種以上を用いることができる。 − Polyester-based thermoplastic elastomer −
The polyester-based thermoplastic elastomer includes, for example, a high melting point polyester segment (hard segment) described in JP-A-11-92636 and the like and a low melting point polymer segment (soft segment) having a molecular weight of about 400 to 6,000. Block copolymers can be used. Examples of the refractory polyester segment include polybutylene terephthalate (PBT) and the like. Further, examples of the low melting point polymer segment include an amorphous polyether having a glass transition temperature of −70 ° C., for example, polytetramethylene ether glycol (PTMG) and the like.
As the resin composition of the present invention, one or more kinds of polyester-based thermoplastic elastomers can be used.

なかでも本発明の樹脂組成物は、熱可塑性エラストマーを含み、当該熱可塑性エラストマーがスチレン系熱可塑性エラストマーを含むことが好ましい。本発明の樹脂組成物を構成する樹脂成分は、その５０質量％以上がスチレン系熱可塑性エラストマーで構成されていることが好ましく、より好ましくは、本発明の樹脂組成物を構成する樹脂成分の６０質量％以上、さらに好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量がスチレン系熱可塑性エラストマーで構成されていることが好ましい。本発明の樹脂組成物を構成する樹脂成分は、そのすべてがスチレン系熱可塑性エラストマーであってもよい。 Among them, the resin composition of the present invention preferably contains a thermoplastic elastomer, and the thermoplastic elastomer preferably contains a styrene-based thermoplastic elastomer. It is preferable that 50% by mass or more of the resin component constituting the resin composition of the present invention is composed of a styrene-based thermoplastic elastomer, and more preferably 60 of the resin components constituting the resin composition of the present invention. It is preferable that the mass% or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass, is composed of the styrene-based thermoplastic elastomer. All of the resin components constituting the resin composition of the present invention may be styrene-based thermoplastic elastomers.

本発明の樹脂組成物が、後述するように金属水酸化物を含有する形態である場合、本発明の樹脂組成物は、熱可塑性樹脂として酸変性樹脂を１種又は２種以上含むことも好ましい。その理由の詳細は後述する。
本発明において「酸変性」とは、酸基を導入した形態の他、酸無水物基を導入した形態を含む意味である。また、原料として用いた酸変性樹脂が、酸無水物基を導入された形態である場合、混練等を経て樹脂組成物を調製した後においては、当該組成物中において酸無水物基の少なくとも一部は空気中の水分により加水分解されて開環し、酸基となる。
酸変性は、酸化合物（酸基又は酸無水物基を有する化合物）をグラフト反応させたり、酸化合物をモノマーとして共重合したりして行われる。また、酸変性樹脂は、極性基として酸基や酸無水物基を有することに加え、他の極性基が導入されていてもよい。 When the resin composition of the present invention is in the form of containing a metal hydroxide as described later, it is also preferable that the resin composition of the present invention contains one or more acid-modified resins as the thermoplastic resin. .. The details of the reason will be described later.
In the present invention, "acid modification" means a form in which an acid anhydride group is introduced in addition to a form in which an acid group is introduced. When the acid-modified resin used as a raw material is in the form in which an acid anhydride group is introduced, at least one of the acid anhydride groups in the composition is prepared after the resin composition is prepared through kneading or the like. The portion is hydrolyzed by the moisture in the air to open the ring and become an acid group.
Acid modification is carried out by grafting an acid compound (a compound having an acid group or an acid anhydride group) or copolymerizing the acid compound as a monomer. Further, the acid-modified resin has an acid group or an acid anhydride group as a polar group, and other polar groups may be introduced.

樹脂の酸変性に用いる酸化合物は、有機の酸化合物又は酸無水物化合物が好ましく、ジカルボン酸無水物構造を有する化合物がより好ましい。
ジカルボン酸無水物構造を有する化合物は、芳香族多価カルボン酸や脂肪族多価カルボン酸の無水物が挙げられる。なかでもジカルボン酸無水物構造が環を形成した構造の化合物が好ましく、芳香族多価カルボン酸の隣接する２つのカルボキシ基が脱水縮合した構造の化合物がより好ましい。ジカルボン酸無水物構造が環を形成している場合、この環は５員環または６員環が好ましく、５員環がより好ましい。 The acid compound used for acid modification of the resin is preferably an organic acid compound or an acid anhydride compound, and more preferably a compound having a dicarboxylic acid anhydride structure.
Examples of the compound having a dicarboxylic acid anhydride structure include an anhydride of an aromatic polyvalent carboxylic acid and an aliphatic polyvalent carboxylic acid. Of these, a compound having a dicarboxylic acid anhydride structure forming a ring is preferable, and a compound having a structure in which two adjacent carboxy groups of an aromatic polyvalent carboxylic acid are dehydrated and condensed is more preferable. When the dicarboxylic acid anhydride structure forms a ring, the ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.

樹脂の酸変性に用いる酸化合物の好ましい例として、例えば、無水マレイン酸、無水イタコン酸、無水シトラコン酸、テトラヒドロ無水フタル酸、ビシクロ［２，２，１］ヘプトー２−エン−５，６−ジカルボン酸無水物、無水フタル酸、無水４−メチルフタル酸、無水４−クロロフタル酸、無水４−ｔｅｒｔ−ブチルフタル酸、無水４，５−ジクロロフタル酸、無水テトラクロロフタル酸、無水テトラフルオロフタル酸、無水テトラブロモフタル酸、無水トリメリット酸、及び無水ピロメリット酸などが挙げられる。なかでも、無水マレイン酸、４，４’−カルボニルジフタル酸無水物、４，４’−オキシジフタル酸無水物、４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、及び４，４’−ビフタル酸無水物から選ばれる酸化合物が好ましい。 Preferred examples of the acid compound used for acid modification of the resin include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2,2,1] hepto-2-ene-5,6-dicarboxylic. Acid anhydride, phthalic anhydride, 4-methylphthalic anhydride, 4-chlorophthalic anhydride, 4-tert-butylphthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, tetrafluorophthalic anhydride, anhydrous Examples thereof include tetrabromophthalic acid, trimellitic anhydride, and pyromellitic anhydride. Among them, maleic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropyridene) diphthalic anhydride, and 4,4'. -Acid compounds selected from biphthalic anhydride are preferred.

酸変性樹脂のベースとなる樹脂（酸変性される前の樹脂）は、本発明の効果を損なわない限り限定されない。例えば、弾性率の高いエラストマー樹脂（例えば、上述した熱可塑性エラストマー樹脂）を好適に用いることができる。また、弾性率の低いポリオレフィン樹脂を用いることもできる。 The resin that is the base of the acid-modified resin (the resin before acid-modified) is not limited as long as the effects of the present invention are not impaired. For example, an elastomer resin having a high elastic modulus (for example, the above-mentioned thermoplastic elastomer resin) can be preferably used. Further, a polyolefin resin having a low elastic modulus can also be used.

酸変性樹脂の好ましい例として、酸変性ポリオレフィン樹脂が挙げられる。酸変性ポリオレフィン樹脂の具体例としては、例えば、酸変性ポリエチレン、酸変性ポリプロピレン等が挙げられる。
また、酸変性のエチレン−プロピレン共重合体、酸変性のエチレン−α−オレフィン共重合体（エチレン−酢酸ビニル共重合体、エチレン−ヘキセン共重合体、エチレン−オクテン共重合体など）等も好適に用いることができる。
また、酸変性樹脂の別の好ましい例として、酸変性ポリスチレン樹脂が挙げられる。酸変性ポリスチレン樹脂は、酸変性スチレン系熱可塑性エラストマーが好ましい。具体例として酸変性スチレン−エチレン／ブチレン−スチレンブロック共重合体（以下、酸変性ＳＥＢＳと記す）、酸変性スチレン−ブタジエン−スチレンブロック共重合体（以下、酸変性ＳＢＳと記す）等が挙げられる。
酸変性樹脂のなかでも特に好ましいのは、酸変性ＳＥＢＳや、酸変性ＳＢＳ等の酸変性スチレン系熱可塑性エラストマーである。
酸変性ＳＥＢＳは、スチレン−エチレン／ブチレン−スチレンブロック共重合体中のエチレン／ブチレンブロックを酸化合物によって変性させたものである。また、酸変性ＳＢＳは、スチレン−ブタジエン−スチレンブロック共重合体中のブタジエン成分を酸化合物によって変性させたものである。
酸変性樹脂は、未変性の樹脂と比較して、金属水酸化物との相互作用が大きい。このような酸変性樹脂は常法により合成することができ、市販品を用いることもできる。例えば酸変性ＳＥＢＳとしては、タフテックＭ１９１１（商品名、旭化成ケミカルズ社製）等が市販されている。 A preferable example of the acid-modified resin is an acid-modified polyolefin resin. Specific examples of the acid-modified polyolefin resin include acid-modified polyethylene and acid-modified polypropylene.
Further, an acid-modified ethylene-propylene copolymer, an acid-modified ethylene-α-olefin copolymer (ethylene-vinyl acetate copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, etc.) and the like are also suitable. Can be used for.
Further, another preferable example of the acid-modified resin is an acid-modified polystyrene resin. The acid-modified polystyrene resin is preferably an acid-modified styrene-based thermoplastic elastomer. Specific examples thereof include acid-modified styrene-ethylene / butylene-styrene block copolymers (hereinafter referred to as acid-modified SEBS), acid-modified styrene-butadiene-styrene block copolymers (hereinafter referred to as acid-modified SBS), and the like. ..
Among the acid-modified resins, acid-modified styrene-based thermoplastic elastomers such as acid-modified SEBS and acid-modified SBS are particularly preferable.
The acid-modified SEBS is obtained by modifying the ethylene / butylene block in the styrene-ethylene / butylene-styrene block copolymer with an acid compound. Further, the acid-modified SBS is obtained by modifying the butadiene component in the styrene-butadiene-styrene block copolymer with an acid compound.
The acid-modified resin has a greater interaction with the metal hydroxide than the unmodified resin. Such an acid-modified resin can be synthesized by a conventional method, and a commercially available product can also be used. For example, as an acid-modified SEBS, Tough Tech M1911 (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like are commercially available.

（金属水酸化物）
本発明の樹脂組成物は、金属水酸化物を含有することができる。金属水酸化物を含有させることにより、樹脂組成物の応力緩和を抑制することが可能となる。この金属水酸化物による応力緩和抑制作用は、樹脂組成物に酸変性樹脂を含有させることでより顕在化する。これは、酸変性樹脂が有する酸基と金属水酸化物が有する水酸基とが相互作用（水素結合性相互作用ないしはエステル結合の形成）をし、酸変性樹脂が金属酸化物により物理的、化学的に架橋されたような状態となり、酸変性樹脂の分子運動が拘束されることが一因と考えられる。この観点からは、金属水酸化物を構成する金属は多価金属であることが好ましく、より好ましくは２価又は３価の金属であり、より好ましくは２価の金属である。
このような応力緩和抑制作用をより効果的に発現させる観点から、本発明の樹脂組成物を構成する樹脂成分の合計に占める酸変性樹脂の割合を１０〜４０質量％（好ましくは１５〜３５質量％）とし、本発明の樹脂組成物を構成する樹脂成分の含有量の合計１００質量部に対する上記の金属水酸化物の含有量を８０〜３１０質量部とすることが好ましい。金属水酸化物の量を上記範囲内とすることによって、より伸びやすく、また、より高い強度の物性とすることができる。本発明の樹脂組成物を構成する樹脂成分に占める酸変性樹脂以外の樹脂は、上記で説明した熱可塑性樹脂（酸変性されていないもの）であることが好ましい。 (Metal hydroxide)
The resin composition of the present invention can contain a metal hydroxide. By containing the metal hydroxide, stress relaxation of the resin composition can be suppressed. The stress relaxation suppressing effect of the metal hydroxide becomes more apparent by including the acid-modified resin in the resin composition. This is because the acid group of the acid-modified resin and the hydroxyl group of the metal hydroxide interact (hydrogen-bonding interaction or formation of ester bond), and the acid-modified resin is physically and chemically formed by the metal oxide. It is considered that one of the causes is that the molecular movement of the acid-modified resin is constrained due to the state of being cross-linked to the acid-modified resin. From this point of view, the metal constituting the metal hydroxide is preferably a polyvalent metal, more preferably a divalent or trivalent metal, and more preferably a divalent metal.
From the viewpoint of more effectively exhibiting such stress relaxation suppressing action, the ratio of the acid-modified resin to the total of the resin components constituting the resin composition of the present invention is 10 to 40% by mass (preferably 15 to 35% by mass). %), And the content of the above metal hydroxide is preferably 80 to 310 parts by mass with respect to the total content of 100 parts by mass of the resin components constituting the resin composition of the present invention. By setting the amount of the metal hydroxide within the above range, it is possible to obtain physical properties that are more easily stretched and have higher strength. The resin other than the acid-modified resin in the resin components constituting the resin composition of the present invention is preferably the thermoplastic resin (not acid-modified) described above.

上記金水酸化物としては、例えば、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、水酸化マンガン、水酸化亜鉛、水酸化銅(II)、水酸化鉄(II)、水酸化鉄(III)等を挙げることができ、これらの１種又は２種以上を用いることができる。 Examples of the gold hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, manganese hydroxide, zinc hydroxide, copper (II) hydroxide, iron (II) hydroxide, iron (III) hydroxide and the like. These can be mentioned, and one or more of these can be used.

（軟化剤）
本発明の樹脂組成物は、軟化剤を含有することも好ましい。軟化剤を含有することにより、本発明の樹脂組成物の凹凸追従性をより高めることができる。なかでも、樹脂組成物が酸変性樹脂と金属水酸化物を含有する形態である場合には、応力緩和が抑制されて上昇した弾性率を、軟化剤がほどよく抑え込み、弾性と柔軟性の両特性を、より高いレベルで兼ね備えた物性の樹脂組成物とすることができる。
本発明に用い得る軟化剤に特に制限はない。例えば、一般的なゴム・エラストマー類の軟化剤として使用されるものを広く用いることができる。軟化剤の好ましい例としてはオイルを挙げることができる。このオイルは、後述する実施例に記載されるように、クロロホルムに対して相溶性を示し、且つ、エタノールに対しても相溶性を示す成分である。本発明において「Ｘ（溶媒）に対して相溶性を示す」とは、Ｘに対する溶解度が２５℃において「５０ｇ／１００ｇ−Ｘ」以上であることを意味する。
オイルとしては、パラフィン系オイル、ナフテン系オイル、芳香族系オイル、シリコーン系オイル、ポリブテン系オイル、植物由来系オイルが挙げられ、これらの１種又は２種以上を用いることができる。これらの中でも、樹脂成分との相溶性の観点から、パラフィン系オイル、ナフテン系オイル、芳香族系オイル、ポリブテン系オイル、又は植物由来系（中でも特にテルペン系）オイルが好ましく、特にパラフィン系オイル、ポリブテン系オイル、及びテルペン系オイルから選ばれるものが好ましい。これらは１種を単独で使用してもよいし、２種以上を併用してもよい。
本発明の樹脂組成物中、軟化剤の含有量は、本発明の樹脂組成物を構成する樹脂成分の合計含有量１００質量部に対して１５０〜５００質量部であることが好ましく、より好ましくは１６０〜４６０質量部、さらに好ましくは１９０〜４００質量部、さらに好ましくは２００〜３５０質量部である。 (Softener)
The resin composition of the present invention also preferably contains a softening agent. By containing the softening agent, the unevenness-following property of the resin composition of the present invention can be further enhanced. In particular, when the resin composition is in the form of containing an acid-modified resin and a metal hydroxide, the softening agent moderately suppresses the increased elastic modulus due to the suppression of stress relaxation, and both elasticity and flexibility. A resin composition having physical properties having characteristics at a higher level can be obtained.
The softener that can be used in the present invention is not particularly limited. For example, those used as softeners for general rubber / elastomers can be widely used. Oil can be mentioned as a preferable example of the softener. This oil is a component that is compatible with chloroform and also with ethanol, as described in Examples described later. In the present invention, "showing compatibility with X (solvent)" means that the solubility with respect to X is "50 g / 100 g-X" or more at 25 ° C.
Examples of the oil include paraffin-based oils, naphthen-based oils, aromatic oils, silicone-based oils, polybutene-based oils, and plant-derived oils, and one or more of these can be used. Among these, paraffin-based oils, naphthen-based oils, aromatic oils, polybutene-based oils, or plant-derived (particularly terpene-based) oils are preferable, and paraffin-based oils are particularly preferable, from the viewpoint of compatibility with resin components. Those selected from polybutene-based oils and terpen-based oils are preferable. One of these may be used alone, or two or more thereof may be used in combination.
The content of the softening agent in the resin composition of the present invention is preferably 150 to 500 parts by mass, more preferably 150 parts by mass, based on 100 parts by mass of the total content of the resin components constituting the resin composition of the present invention. It is 160 to 460 parts by mass, more preferably 190 to 400 parts by mass, and further preferably 200 to 350 parts by mass.

＜樹脂組成物の形状＞
本発明の樹脂組成物は、各成分を均質に含有する形態であれば、その形状に特に制限はない。例えば、各成分を混練して得た混練物の状態でもよいし、ペレットの状態でもよいし、成形品の形態でもよい。また、本発明の樹脂組成物は溶媒を含み、この溶媒中に樹脂成分等が溶解した状態であってもよい。
本発明の樹脂組成物が成形品の形態である場合、好ましい形状の一例として、ドーナツ状に成形された形態が挙げられる。このドーナツ状の成形品は、例えば、住宅外壁等の貫通部に設置する貫通パイプに用いる止水材として好適に用いることができる。ドーナツ状成形体は、円形であってもよく、多角形状であってもよく、また楕円状でもよい。つまり、本発明においてドーナツ状とは、中心部に孔（貫通孔）を有する形態であれば特に制限されない。ドーナツ状の成形品のサイズは、適用する貫通孔等の大きさを考慮して適宜に調整すればよい。ドーナツ状成形品は中央に孔を有する平板状であることが好ましく、その厚さは通常は３〜１５ｍｍであり、好ましくは５．５〜１０．０ｍｍである。 <Shape of resin composition>
The shape of the resin composition of the present invention is not particularly limited as long as it is in a form in which each component is homogeneously contained. For example, it may be in the form of a kneaded product obtained by kneading each component, in the form of pellets, or in the form of a molded product. Further, the resin composition of the present invention may contain a solvent, and the resin component or the like may be dissolved in the solvent.
When the resin composition of the present invention is in the form of a molded product, a donut-shaped molded form can be mentioned as an example of a preferable shape. This donut-shaped molded product can be suitably used, for example, as a water blocking material used for a penetrating pipe installed in a penetrating portion such as an outer wall of a house. The donut-shaped molded product may be circular, polygonal, or elliptical. That is, in the present invention, the donut shape is not particularly limited as long as it has a hole (through hole) in the center. The size of the donut-shaped molded product may be appropriately adjusted in consideration of the size of the through hole or the like to be applied. The donut-shaped molded product is preferably in the shape of a flat plate having a hole in the center, and its thickness is usually 3 to 15 mm, preferably 5.5 to 10.0 mm.

＜樹脂組成物の止水性能＞
本発明の樹脂組成物は、所望の止水性能を示すことが好ましい。より詳細には、次の条件（Ｉ）及び／又は（II）で行う止水性試験において、３０℃で、３０分以上の間、水漏れを生じないことが好ましい。 <Water-stopping performance of resin composition>
The resin composition of the present invention preferably exhibits a desired water blocking performance. More specifically, in the water stopping test performed under the following conditions (I) and / or (II), it is preferable that water leakage does not occur at 30 ° C. for 30 minutes or more.

（条件（Ｉ））
樹脂組成物を、孔径４０ｍｍ、外径６０ｍｍ、厚さ６．７ｍｍのドーナツ状に成形し、該ドーナツ状成形品を、孔径３７．１ｍｍの円筒型パイプが円筒軸方向端部に有する外径１０５ｍｍのステンレス製フランジ表面に、該ドーナツ状試験片の孔の中央部に前記円筒型パイプの孔が位置するように配し、該ドーナツ状成形品の前記フランジ側とは反対の側にはサイディング板を、該サイディング板の凹凸面が該ドーナツ状成形品側となるように配し、前記サイディング板の凹凸面と前記フランジ表面との最短距離が２．０ｍｍとなるまで該フランジと該サイディング板とをねじ締めした状態とし、前記パイプ内に高さ１０ｃｍまで２５℃の水を入れた条件。 (Condition (I))
The resin composition is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product has an outer diameter of 105 mm at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. The cylindrical pipe is arranged on the surface of the stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the siding plate is on the side opposite to the flange side of the donut-shaped molded product. Is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product, and the flange and the siding plate are arranged until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. Is in a screw-tightened state, and water at 25 ° C. is filled in the pipe up to a height of 10 cm.

（条件（II））
樹脂組成物を、孔径４０ｍｍ、外径６０ｍｍ、厚さ６．７ｍｍのドーナツ状に成形し、該ドーナツ状成形品を、孔径３７．１ｍｍの円筒型パイプが円筒軸方向端部に有する外径１０５ｍｍのステンレス製フランジ表面に、該ドーナツ状試験片の孔の中央部に前記円筒型パイプの孔が位置するように配し、該ドーナツ状成形品の前記フランジ側とは反対の側にはサイディング板を、該サイディング板の凹凸面が該ドーナツ状成形品側となるように配し、前記サイディング板の凹凸面と前記フランジ表面との最短距離が２．０ｍｍとなるまで該フランジと該サイディング板とをねじ締めした状態とし、３０℃で１２５時間静置し、その後、前記パイプ内に高さ１０ｃｍまで２５℃の水を入れた条件。 (Condition (II))
The resin composition is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product has an outer diameter of 105 mm at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. The cylindrical pipe is arranged on the surface of the stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the siding plate is on the side opposite to the flange side of the donut-shaped molded product. Is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product, and the flange and the siding plate are arranged until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. The condition was that the pipe was screwed and allowed to stand at 30 ° C. for 125 hours, and then water at 25 ° C. was poured into the pipe to a height of 10 cm.

＜用途＞
本発明の樹脂組成物は、止水材として好適である。本発明において「止水材」は、目地材を含む意味に用いる。
本発明の樹脂組成物は、例えば、住宅用貫通部材の止水材として、アルミサッシ周りの止水材として、キッチン周りの目地材として、また外壁サイディング環の目地材として、好ましく適用することができる。 <Use>
The resin composition of the present invention is suitable as a water blocking material. In the present invention, "water blocking material" is used to mean including a joint material.
The resin composition of the present invention can be preferably applied, for example, as a water blocking material for a penetrating member for a house, as a water blocking material around an aluminum sash, as a joint material around a kitchen, and as a joint material for an outer wall siding ring. can.

続いて本発明の止水材について説明する。 Subsequently, the water blocking material of the present invention will be described.

［止水材］
本発明の止水材は、熱可塑性エラストマーと、酸変性樹脂と、金属酸化物と、軟化剤とを含有する樹脂組成物からなる。止水材を構成する樹脂組成物において、熱可塑性エラストマー及び酸変性樹脂の合計１００質量部に対し、金属酸化物の含有量は８０〜３１０質量部であり、軟化剤の含有量１６０〜４６０質量部である。本発明の止水材を構成する樹脂組成物に含まれる熱可塑性エラストマー、酸変性樹脂、金属酸化物、及び軟化剤の好ましい形態は、上述の本発明の樹脂組成物において説明した熱可塑性エラストマー、酸変性樹脂、金属酸化物、及び軟化剤の好ましい形態と同義であり、これらの止水材中（樹脂組成物中）の好ましい含有量も、本発明の樹脂組成物において説明した樹脂組成物中の好ましい含有量と同義である。本発明の止水材において、単に「熱可塑性エラストマー」という場合、特段の断りのない限り、酸変性されていない熱可塑性エラストマーを意味する。 [Water blocking material]
The water blocking material of the present invention comprises a resin composition containing a thermoplastic elastomer, an acid-modified resin, a metal oxide, and a softening agent. In the resin composition constituting the water blocking material, the content of the metal oxide is 80 to 310 parts by mass with respect to a total of 100 parts by mass of the thermoplastic elastomer and the acid-modified resin, and the content of the softener is 160 to 460 parts by mass. It is a department. Preferred forms of the thermoplastic elastomer, acid-modified resin, metal oxide, and softener contained in the resin composition constituting the water blocking material of the present invention are the thermoplastic elastomer described in the above-mentioned resin composition of the present invention. It is synonymous with the preferable forms of the acid-modified resin, the metal oxide, and the softening agent, and the preferable content of these in the water blocking material (in the resin composition) is also in the resin composition described in the resin composition of the present invention. Is synonymous with the preferred content of. In the water blocking material of the present invention, the term "thermoplastic elastomer" simply means a thermoplastic elastomer that has not been acid-modified unless otherwise specified.

本発明の止水材を構成する樹脂組成物は、２５％圧縮応力が３００ｋＰａ以下であることが好ましい。本発明の止水材を構成する樹脂組成物の組成であれば、当該樹脂組成物を２５％圧縮応力が３００ｋＰａ以下である物性としても、緩和弾性率については十分に高い状態とすることができる。すなわち、２５％圧縮応力が小さく一定の柔らかさを有しながら、圧力変形状態における経時的な応力緩和も抑えられた物性の樹脂組成物とすることができ、止水材として、より好適な物性とすることができる。本発明の止水材を構成する樹脂組成物は、２５％圧縮応力が２７０ｋＰａ以下が好ましく、２５０ｋＰａ以下がより好ましく、２３０ｋＰａ以下がさらに好ましい。また、上記２５％圧縮応力は通常は３０ｋＰａ以上であり、４０ｋＰａ以上が実際的である。
The resin composition constituting the water blocking material of the present invention preferably has a 25% compressive stress of 300 kPa or less. With the composition of the resin composition constituting the water blocking material of the present invention, even if the resin composition has a physical property of 25% compressive stress of 300 kPa or less, the relaxation elastic modulus can be sufficiently high. .. That is, it is possible to obtain a resin composition having physical properties such that 25% compressive stress is small and constant softness is suppressed, and stress relaxation over time in a pressure deformation state is suppressed, which is more suitable as a water blocking material. Can be. The resin composition constituting the water blocking material of the present invention preferably has a 25% compressive stress of 270 kPa or less, more preferably 250 kPa or less, and even more preferably 230 kPa or less. The 25% compressive stress is usually 30 kPa or more, and 40 kPa or more is practical.

また、本発明の止水材は、所望の止水性能を示すことが好ましい。より詳細には、上述した条件（Ｉ）及び／又は（II）で行う止水性試験において、３０℃で、３０分以上の間、水漏れを生じないことが好ましい。 Moreover, it is preferable that the water blocking material of the present invention exhibits a desired water stopping performance. More specifically, in the water stopping test performed under the above-mentioned conditions (I) and / or (II), it is preferable that water leakage does not occur at 30 ° C. for 30 minutes or more.

本発明の止水材の形状は特に制限されない。例えば、各成分を混練して得た混練物の状態でもよいし、ペレットの状態でもよいし、成形品の形態でもよい。また、本発明の止水材は溶媒を含み、この溶媒中に樹脂成分等が溶解した状態にあってもよい。本発明の止水材は、上述したドーナツ状に成形された形態であることも好ましい。 The shape of the water blocking material of the present invention is not particularly limited. For example, it may be in the form of a kneaded product obtained by kneading each component, in the form of pellets, or in the form of a molded product. Further, the water blocking material of the present invention may contain a solvent, and the resin component or the like may be dissolved in the solvent. The water blocking material of the present invention is also preferably in the form of the above-mentioned donut shape.

本発明の止水材は、例えば、住宅用貫通部材の止水材として、アルミサッシ周りの止水材として、キッチン周りの目地材として、また外壁サイディング環の目地材として、好ましく適用することができる。 The water blocking material of the present invention can be preferably applied, for example, as a water blocking material for a penetrating member for a house, as a water blocking material around an aluminum sash, as a joint material around a kitchen, and as a joint material for an outer wall siding ring. can.

本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

［材料］
＜ベース樹脂製剤＞
（非酸変性樹脂）
・スチレン系熱可塑性エラストマー製剤（アロン化成社製、商品名：ＡＲ−ＳＣ−０（ＳＥＢＳ）
・スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ、水添スチレン−エチレン−α−オレフィン共重合体）
（酸変性樹脂）
・無水マレイン酸変性ＳＥＢＳ製剤（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１） [material]
<Base resin preparation>
(Non-acid-modified resin)
-Styrene-based thermoplastic elastomer preparation (manufactured by Aronkasei Co., Ltd., trade name: AR-SC-0 (SEBS))
-Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N, hydrogenated styrene-ethylene-α-olefin copolymer)
(Acid-modified resin)
-Maleic anhydride-modified SEBS preparation (manufactured by Asahi Kasei Chemicals, trade name: Tough Tech M1911)

＜軟化剤＞
・パラフィン系オイル（日本サン石油社製、商品名：ＳＵＮＰＡＲ２２８０）
・ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０） <Softener>
-Paraffin oil (manufactured by Nippon Sun Oil Co., Ltd., product name: SUNPAR2280)
-Polybutene oil (manufactured by JXTG Energy Co., Ltd., product name: LV-50)

＜フィラー＞
・水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）
・炭酸カルシウム（白石カルシウム社製、商品名：白艶華ＣＣ） <Filler>
-Magnesium hydroxide (manufactured by Konoshima Chemical Co., Ltd., product name: Magnesium N6)
・ Calcium carbonate (manufactured by Shiraishi Calcium, product name: Shiraishi Calcium CC)

［調製例］
＜樹脂組成物の調製＞
下表に示す成分組成（単位：質量部）となるように、ベース樹脂製剤、軟化剤、フィラーを混合し（全量７００ｇ）、混練して、実施例１〜７、比較例１〜５の各樹脂組成物を得た。この混練は、１５０℃に設定した１Ｌニーダー（モリヤマ製、ＭＳ式小型加圧ニーダー（容量１Ｌ））を用いて、１０分〜１５分間、各成分が均一になるまで行った。各実施例、比較例の樹脂組成物の調製について詳しく説明する。 [Preparation example]
<Preparation of resin composition>
The base resin preparation, softener, and filler are mixed (total amount 700 g) and kneaded so as to have the component composition (unit: parts by mass) shown in the table below, and each of Examples 1 to 7 and Comparative Examples 1 to 5 is obtained. A resin composition was obtained. This kneading was carried out for 10 minutes to 15 minutes using a 1 L kneader (manufactured by Moriyama, MS type small pressure kneader (capacity 1 L)) set at 150 ° C. until each component became uniform. The preparation of the resin composition of each Example and Comparative Example will be described in detail.

（実施例１）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ製剤（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）４０．０質量部および水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）５０．０質量部を配合し、上述した通り混練し、実施例１の樹脂組成物を得た。得られた樹脂組成物中の成分含有量は次のように決定した（実施例２〜７、比較例１〜５の樹脂組成物についても同様に、成分含有量を決定した。）。 (Example 1)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS preparation (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911) 10.0 parts by mass, polybutene-based 40.0 parts by mass of oil (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 50.0 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) are mixed and kneaded as described above. , The resin composition of Example 1 was obtained. The component content in the obtained resin composition was determined as follows (the component content was similarly determined for the resin compositions of Examples 2 to 7 and Comparative Examples 1 to 5).

− 成分含有量の決定方法 −
−− 軟化剤成分の含有量 −−
樹脂組成物２．７２７ｇを、２０ｍＬのクロロホルムに浸し、クロロホルム溶解性成分（フィラー以外の成分）が完全に溶解するまで放置した。その後、このクロロホルム溶液を十分量（１．０Ｌ以上）のエタノールに滴下し、樹脂成分及びフィラー成分を凝集・沈殿させた。この沈殿物を、濾紙を使って減圧濾過して分離した後、エタノールを沈殿物に流しかけて沈殿物を洗浄した。その後、乾燥してエタノールを除去し、沈殿物の質量を測定したところ、１．３８０ｇであった。
出発時点の樹脂組成物の量は上記の通り２．７２７ｇであるから、［２．７２７ｇ］−［１．３８０ｇ］＝［１．３４７ｇ］が、軟化剤（オイル）の量となる。

−− 樹脂成分の含有量 −−
上記沈殿物１．３８０ｇを再度クロロホルムに浸し、クロロホルム溶解性成分が完全に溶解した後、シリンジフィルター（孔径０．８０μｍ→孔径０．４５μｍ、各々１回ずつ濾過）によりフィラー成分を除去した。得られた濾液を乾燥してクロロホルムを除去したところ、揮発せずに残留した成分は０．６６０ｇであった。この残留成分０．６６０ｇが樹脂成分の量となる。

−− フィラー成分の含有量 −−
出発時点の樹脂組成物２．７２７ｇから、軟化材成分１．３４７ｇと樹脂成分０．６６０ｇとを差し引いた０．７２０ｇが、フィラー成分の量となる。

−− 樹脂成分中に占める酸変性樹脂と非酸変性樹脂の比 −−
実施例１において、樹脂成分中のスチレン系熱可塑性エラストマー樹脂と酸変性ＳＥＢＳの量は、次のように決定した。
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）３．４９８ｇを、クロロホルムに完全溶解し、次いで十分量のエタノール中に滴下して沈殿物を得た。この沈殿物を、濾紙を使って減圧濾過して分離した後、エタノールを沈殿物に流しかけて沈殿物を洗浄した。その後、乾燥してエタノールを除去し、沈殿物の質量を測定したところ、１．４０４ｇであった。したがって、軟化材成分は［３．４９８ｇ］−［１．４０４ｇ］＝［２．０９４ｇ］となる（スチレン系熱可塑性エラストマー樹脂：軟化剤＝２：３（質量比））。
ここで、実施例１の樹脂組成物中には、スチレン系熱可塑性エラストマー製剤を９０質量部に対し、無水マレイン酸変性ＳＥＢＳ製剤を１０質量部配合している。
スチレン系熱可塑性エラストマー製剤は、上記の通り、スチレン系熱可塑性エラストマー樹脂：軟化剤＝２：３（質量比）であるから、スチレン系熱可塑性エラストマー製剤９０質量部のうち、３６質量部が非酸変性樹脂であるスチレン系熱可塑性エラストマーとなり、残る５４質量部が軟化剤成分となる。一方、樹脂組成物中に配合した無水マレイン酸変性ＳＥＢＳ製剤は軟化剤を含んでいない。
したがって、樹脂成分全体（３６質量部＋１０質量部）で１００質量部となるように換算すると、非酸変性樹脂が７８．３質量部、酸変性樹脂が２１．７質量部と算出される。 -Method of determining component content-
--Content of softener component ---
2.727 g of the resin composition was immersed in 20 mL of chloroform and left to stand until the chloroform-soluble components (components other than the filler) were completely dissolved. Then, this chloroform solution was added dropwise to a sufficient amount (1.0 L or more) of ethanol to aggregate and precipitate the resin component and the filler component. The precipitate was separated by filtration under reduced pressure using a filter paper, and then ethanol was poured over the precipitate to wash the precipitate. Then, it was dried to remove ethanol, and the mass of the precipitate was measured and found to be 1.380 g.
Since the amount of the resin composition at the starting point is 2.727 g as described above, [2.727 g]-[1.380 g] = [1.347 g] is the amount of the softener (oil).

--Content of resin component ---
1.380 g of the above-mentioned precipitate was immersed in chloroform again, and after the chloroform-soluble component was completely dissolved, the filler component was removed by a syringe filter (pore size 0.80 μm → pore size 0.45 μm, each filtered once). When the obtained filtrate was dried to remove chloroform, the amount of the remaining component without volatilization was 0.660 g. 0.660 g of this residual component is the amount of the resin component.

--Content of filler component ---
The amount of the filler component is 0.720 g, which is obtained by subtracting 1.347 g of the softener component and 0.660 g of the resin component from 2.727 g of the resin composition at the time of departure.

--Ratio of acid-modified resin and non-acid-modified resin in the resin component ---
In Example 1, the amounts of the styrene-based thermoplastic elastomer resin and the acid-modified SEBS in the resin component were determined as follows.
3.498 g of a styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N) was completely dissolved in chloroform, and then added dropwise to a sufficient amount of ethanol to obtain a precipitate. The precipitate was separated by filtration under reduced pressure using a filter paper, and then ethanol was poured over the precipitate to wash the precipitate. Then, it was dried to remove ethanol, and the mass of the precipitate was measured and found to be 1.404 g. Therefore, the softener component is [3.498 g]-[1.404 g] = [2.094 g] (styrene-based thermoplastic elastomer resin: softener = 2: 3 (mass ratio)).
Here, in the resin composition of Example 1, 90 parts by mass of the styrene-based thermoplastic elastomer preparation and 10 parts by mass of the maleic anhydride-modified SEBS preparation are blended.
As described above, the styrene-based thermoplastic elastomer preparation has a styrene-based thermoplastic elastomer resin: softener = 2: 3 (mass ratio), so 36 parts by mass of the 90 parts by mass of the styrene-based thermoplastic elastomer preparation is non-. It becomes a styrene-based thermoplastic elastomer which is an acid-modified resin, and the remaining 54 parts by mass becomes a softening agent component. On the other hand, the maleic anhydride-modified SEBS preparation blended in the resin composition does not contain a softening agent.
Therefore, when converted so that the total amount of the resin component (36 parts by mass + 10 parts by mass) is 100 parts by mass, the non-acid-modified resin is calculated to be 78.3 parts by mass and the acid-modified resin is calculated to be 21.7 parts by mass.

（実施例２）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）２８．８質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）３６．８質量部を配合したこと以外は、実施例１と同様にして実施例２の樹脂組成物を調製した。 (Example 2)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS (manufactured by Asahi Kasei Chemicals, trade name: Tuftec M1911) 10.0 parts by mass, polybutene-based oil Example 1 except that 28.8 parts by mass of (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 36.8 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) were blended. The resin composition of Example 2 was prepared in the same manner as in the above.

（実施例３）
スチレン系熱可塑性エラストマー製剤（アロン化成社製、商品名：ＡＲ−ＳＣ−０）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、パラフィン系オイル（日本サン石油社製、商品名：ＳＵＮＰＡＲ２２８０）７８．８質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）１００．８質量部を配合したこと以外は、実施例１と同様にして実施例３の樹脂組成物を調製した。 (Example 3)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tough Tech M1911) with respect to 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Aron Kasei Co., Ltd., trade name: AR-SC-0). , Paraffin oil (manufactured by Nippon Sun Oil Co., Ltd., trade name: SUNPAR2280) 78.8 parts by mass, magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) 100.8 parts by mass, except that The resin composition of Example 3 was prepared in the same manner as in Example 1.

（実施例４）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）３８．０質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）９２．０質量部を配合したこと以外は、実施例１と同様にして実施例４の樹脂組成物を調製した。 (Example 4)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS (manufactured by Asahi Kasei Chemicals, trade name: Tough Tech M1911) 10.0 parts by mass, polybutene-based oil Example 1 except that 38.0 parts by mass of (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 92.0 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) were blended. The resin composition of Example 4 was prepared in the same manner as in the above.

（実施例５）
スチレン系熱可塑性エラストマー製剤（アロン化成社製、商品名：ＡＲ−ＳＣ−０）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、パラフィン系オイル（日本サン石油社製、商品名：ＳＵＮＰＡＲ２２８０）３３．３質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）９７．５質量部を配合したこと以外は、実施例１と同様にして実施例５の樹脂組成物を調製した。 (Example 5)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tough Tech M1911) with respect to 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Aron Kasei Co., Ltd., trade name: AR-SC-0). , Paraffin oil (manufactured by Nippon Sun Oil Co., Ltd., trade name: SUNPAR2280) 33.3 parts by mass, magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magces N6) 97.5 parts by mass, except that The resin composition of Example 5 was prepared in the same manner as in Example 1.

（実施例６）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）６１．０質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）３６．８質量部を配合したこと以外は、実施例１と同様にして実施例５の樹脂組成物を調製した。 (Example 6)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS (manufactured by Asahi Kasei Chemicals, trade name: Tuftec M1911) 10.0 parts by mass, polybutene-based oil Example 1 except that 61.0 parts by mass of (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 36.8 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) were blended. The resin composition of Example 5 was prepared in the same manner as in the above.

（実施例７）
スチレン系熱可塑性エラストマー製剤（アロン化成社製、商品名：ＡＲ−ＳＣ−０）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、パラフィン系オイル（日本サン石油社製、商品名：ＳＵＮＰＡＲ２２８０）７８．８質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）８１．３質量部を配合したこと以外は、実施例１と同様にして実施例５の樹脂組成物を調製した。 (Example 7)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tough Tech M1911) with respect to 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Aron Kasei Co., Ltd., trade name: AR-SC-0). , Paraffin oil (manufactured by Nippon Sun Oil Co., Ltd., trade name: SUNPAR2280) 78.8 parts by mass, magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) 81.3 parts by mass, except that The resin composition of Example 5 was prepared in the same manner as in Example 1.

（比較例１）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）１５．０質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）５０．６質量部を配合したこと以外は、実施例１と同様にして比較例１の樹脂組成物を調製した。 (Comparative Example 1)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS (manufactured by Asahi Kasei Chemicals, trade name: Tuftec M1911) 10.0 parts by mass, polybutene-based oil Example 1 except that 15.0 parts by mass of (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 50.6 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) were blended. The resin composition of Comparative Example 1 was prepared in the same manner as in the above.

（比較例２）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）２８．８質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）２３．０質量部を配合したこと以外は、実施例１と同様にして比較例２の樹脂組成物を調製した。 (Comparative Example 2)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS (manufactured by Asahi Kasei Chemicals, trade name: Tuftec M1911) 10.0 parts by mass, polybutene-based oil Example 1 except that 28.8 parts by mass of (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 23.0 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) were blended. The resin composition of Comparative Example 2 was prepared in the same manner as in the above.

（比較例３）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）１００質量部に対して、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）１２０．０質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）３２．０質量部を配合したこと以外は、実施例１と同様にして比較例３の樹脂組成物を調製した。 (Comparative Example 3)
Styrene-based thermoplastic elastomer preparation (manufactured by Liken Technos, trade name: TPE LQR7466N) 100 parts by mass, polybutene-based oil (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) 120.0 parts by mass, magnesium hydroxide ( A resin composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that 32.0 parts by mass of Magceeds N6) manufactured by Kamishima Chemical Industry Co., Ltd. was blended.

（比較例４）
スチレン系熱可塑性エラストマー製剤（アロン化成社製、商品名：ＡＲ−ＳＣ−０）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、パラフィン系オイル（日本サン石油社製、商品名：ＳＵＮＰＡＲ２２８０）８８．５質量部、水酸化マグネシウム（神島化学工業社製、商品名：マグシーズＮ６）１００．８質量部を配合したこと以外は、実施例１と同様にして比較例４の樹脂組成物を調製した。 (Comparative Example 4)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tough Tech M1911) with respect to 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Aron Kasei Co., Ltd., trade name: AR-SC-0). , Paraffin oil (manufactured by Nippon Sun Oil Co., Ltd., trade name: SUNPAR2280) 88.5 parts by mass, magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd., trade name: Magsees N6) 100.8 parts by mass, except that The resin composition of Comparative Example 4 was prepared in the same manner as in Example 1.

（比較例５）
スチレン系熱可塑性エラストマー製剤（リケンテクノス社製、商品名：ＴＰＥＬＱＲ７４６６Ｎ）９０．０質量部に対して、酸変性ＳＥＢＳ（旭化成ケミカルズ社製、商品名：タフテックＭ１９１１）１０．０質量部、ポリブテン系オイル（ＪＸＴＧエネルギー社製、商品名：ＬＶ−５０）４０．０質量部、炭酸カルシウム（白石カルシウム社製、商品名：白艶華ＣＣ）５０．０質量部を配合したこと以外は、実施例１と同様にして比較例６の樹脂組成物を調製した。 (Comparative Example 5)
Styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N) 90.0 parts by mass, acid-modified SEBS (manufactured by Asahi Kasei Chemicals, trade name: Tough Tech M1911) 10.0 parts by mass, polybutene-based oil Same as Example 1 except that 40.0 parts by mass of (manufactured by JXTG Energy Co., Ltd., trade name: LV-50) and 50.0 parts by mass of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Shiroshinka CC) were blended. The resin composition of Comparative Example 6 was prepared.

［樹脂組成物の物性測定］
得られた各実施例ないし比較例の樹脂組成物を、縦１６０×横２００×高さ２ｍｍ（緩和弾性率測定用）、縦１６０×横２００×高さ７ｍｍ（止水性試験用）、及び縦１６０×横２００×高さ１３ｍｍ（２５％圧縮応力測定用）の各モールドに投入し、これを予めプレス板温度を１６０℃に設定したプレス機に投入し、５ＭＰａの圧力で５分間プレスした。プレスした状態でそのまま３０℃以下まで冷却し、各実施例、比較例の樹脂組成物について、厚み１．９ｍｍ（緩和弾性率測定用）、６．７ｍｍ（止水性試験用）、１２．５ｍｍ（２５％圧縮応力測定用）の試験用シートを作製した。
[Measurement of physical properties of resin composition]
The obtained resin compositions of Examples or Comparative Examples were subjected to length 160 × width 200 × height 2 mm (for measuring relaxation elastic modulus), length 160 × width 200 × height 7 mm (for water stopping test), and length. It was put into each mold of 160 × width 200 × height 13 mm ( for measuring 25% compressive stress ), put into a press machine in which the press plate temperature was set to 160 ° C. in advance, and pressed at a pressure of 5 MPa for 5 minutes. The resin composition of each Example and Comparative Example was cooled to 30 ° C. or lower as it was in the pressed state, and the thickness was 1.9 mm (for measuring the relaxation elastic modulus), 6.7 mm (for the water stopping test), and 12.5 mm (for the water stopping test). A test sheet for measuring 25% compressive stress) was prepared.

＜２５％圧縮応力の測定＞
ＪＩＳＫ６２５４のＣ法に準拠して、２５％圧縮応力を測定した。万能引張試験機（島津試験器社製、オートグラフＡＧＳ−１ｋＮＸ）に、金属製圧縮治具を取り付け、厚さ１２．５ｍｍの試験用シートを直径３０ｍｍ（実測径２９．８ｍｍ）に打ち抜いた円盤状サンプルを治具中央に設置した。１０ｍｍ／ｍｉｎの速度でひずみ量２５％まで圧縮し、直ちに１０ｍｍ／ｍｉｎで荷重を取り除く、という操作を３回繰り返し、２５％まで圧縮した状態の応力を測定した。得られた３回の測定値の平均値を、樹脂組成物の２５％圧縮応力とした。
結果を下表に示す。
<Measurement of 25% compressive stress>
The 25% compressive stress was measured according to the C method of JIS K 6254. A disk with a metal compression jig attached to a universal tensile tester (Shimadzu Tester, Autograph AGS-1kNX) and a 12.5 mm thick test sheet punched to a diameter of 30 mm (actual diameter 29.8 mm). The shape sample was placed in the center of the jig. The operation of compressing to a strain amount of 25% at a speed of 10 mm / min and immediately removing the load at 10 mm / min was repeated three times, and the stress in the state of being compressed to 25% was measured. The average value of the obtained three measured values was taken as the 25% compressive stress of the resin composition.
The results are shown in the table below.

＜緩和弾性率の測定＞
試験片を平板治具に固定して、下記の動的粘弾性試験条件にて、貯蔵弾性率（Ｇ’）、損失弾性率（Ｇ’’）、及び損失正接値（ｔａｎδ）測定した。
測定条件は、温度範囲３０℃〜２２０℃で１０℃ステップ、５種類の周波数（０．５〜２０Ｈｚ）、歪量０．５％とし、回転モードにて、上記の厚み１．９ｍｍのシートを直径２５ｍｍポンチで打ち抜いた直径２５ｍｍ×厚さ１．９ｍｍの試験片を用いて、連続的な昇温プロセスの中での歪に対する応答を測定した。周波数や歪量が大きすぎると試験片が捩れてしまうなど、データが不安定になってしまうため、上記条件で貯蔵弾性率（Ｇ’）の測定を行った。
各温度の貯蔵弾性率データに対し、次の操作を行った。
まず、時間−温度換算則（Ｔｉｍｅ−Ｔｅｍｐｅｒａｔｕｒｅ−Ｓｕｐｅｒｐｏｓｉｔｉｏｎ［ＴＴＳ］＝時間と温度は等価に扱うことができるという実験則）に従い、下記のＷ．Ｌ．Ｆ式（Ｗｉｌｌｉａｍｓ，Ｌａｎｄｅｌ，Ｆｅｒｒｙ式）を参照し、基準温度３０℃としたときのシフトファクターＬｏｇａ_Ｔ（各温度のデータを周波数軸に沿って水平移動させる量）を、下記の手順で定義した。
横軸を周波数、縦軸を弾性率とした両対数グラフ上で、３０℃の測定温度にて周波数を変えて測定した粘弾性データ（貯蔵弾性率）を固定とし、このデータ曲線と、４０℃で測定した同データ曲線がスムーズに繋がるように、４０℃データ曲線を周波数側に沿ってシフトさせる。同様の操作を、５０℃〜２２０℃までのデータ曲線について行い、最終的に１本の曲線として合成した。各温度における水平移動量からａ_Ｔ（シフトファクター)ならびに、Ｃ１、Ｃ２を回帰的に求め、これらが決定した状態の合成曲線を、マスターカーブとした。さらに、横軸(周波数)の逆数を取ることで横軸を時間単位に換算したものが、本発明において緩和弾性率曲線と定義するものである。
この曲線上で、３０℃で１２５日（３０００時間）後の値を読み取り、緩和後弾性率とした。
なお、測定には、動的粘弾性試験装置（ＴＡインスツルメント社製製品名：ＡＲＥＳ−Ｇ２）を使用した。また、上記一連の操作（手順）は、ソフトウェア（製品名：ＴＲＩＯＳ、ＴＡインスツルメント社製）を用いて自動で行った。その際、シフトさせるパラメーターとして貯蔵弾性率を選択し、Ｘ軸方向（周波数軸）の水平移動のみを許可するよう設定し、マスターカーブを決定した。
結果を下表に示す。 <Measurement of relaxation elastic modulus>
The test piece was fixed to a flat plate jig, and the storage elastic modulus (G'), the loss elastic modulus (G''), and the loss tangent value (tan δ) were measured under the following dynamic viscoelasticity test conditions.
The measurement conditions are a temperature range of 30 ° C. to 220 ° C. in a 10 ° C. step, 5 types of frequencies (0.5 to 20 Hz), and a strain amount of 0.5%. Responses to strain during a continuous heating process were measured using 25 mm diameter x 1.9 mm thick test pieces punched with a 25 mm diameter punch. If the frequency and the amount of strain are too large, the test piece will be twisted and the data will become unstable. Therefore, the storage elastic modulus (G') was measured under the above conditions.
The following operation was performed on the storage elastic modulus data at each temperature.
First, according to the time-temperature conversion rule (Time-Temperature-Superposition [TTS] = experimental rule that time and temperature can be treated equivalently), the following W. L. With reference to the F equation (Williams, Landel, Ferry equation), the shift factor Loga _T (the amount of horizontal movement of each temperature data along the frequency axis) when the reference temperature is 30 ° C. is defined by the following procedure. ..
On a log-log graph with frequency on the horizontal axis and elastic modulus on the vertical axis, the viscoelastic data (storage elastic modulus) measured by changing the frequency at a measurement temperature of 30 ° C is fixed, and this data curve and 40 ° C. The 40 ° C. data curve is shifted along the frequency side so that the same data curves measured in step 2 are smoothly connected. The same operation was performed on the data curves from 50 ° C. to 220 ° C., and finally synthesized as one curve. _{A T} (shift factor) and C1 and C2 were recursively obtained from the amount of horizontal movement at each temperature, and the composite curve in the state determined by these was used as the master curve. Further, the relaxation elastic modulus curve is defined in the present invention as the one in which the horizontal axis is converted into time units by taking the reciprocal of the horizontal axis (frequency).
On this curve, the value after 125 days (3000 hours) at 30 ° C. was read and used as the elastic modulus after relaxation.
A dynamic viscoelasticity test device (product name: ARES-G2 manufactured by TA Instruments) was used for the measurement. Further, the above series of operations (procedures) were automatically performed using software (product name: TRIOS, manufactured by TA Instruments). At that time, the storage elastic modulus was selected as a parameter to be shifted, and it was set to allow only horizontal movement in the X-axis direction (frequency axis), and the master curve was determined.
The results are shown in the table below.

［止水性試験］
＜用意した試験具＞
・サイディング板（ニチハ社製、商品名：モエンエクセラード１６ニューグランドールシリーズＩＥＰＢ３１１Ｎ、凹部の底部から凸部の頂部までの高さの差は最大４．２ｍｍ）
・両端溶接真空管ＮＷフランジ×ＶＦフランジ（ミスミ社製、型番：ＦＲＮＲＦＲ４０、材質：ＳＵＳ３０４、高さ５０ｍｍ、管内径３７．１ｍｍ）
・ＮＷ／ＫＦ規格ロングフランジ（コスモ・テック社製、型番：ＮＷ４０ＬＦ７０Ｌ、材質：ＳＵＳ３０４、高さ７０ｍｍ、管内径３７．１ｍｍ）
・ＭＰＣ真空配管ＫＦセンターリング（ミラプロ社製、型番：ＭＣＫ−２０４０）
・ＮＷクランプ（ＩＳＯ−ＫＦフランジタイプ、ミラプロ社製、型番：ＭＣＫ−１０４０）
・Ｍ１０ボルトおよびナット４組（サイディングとＶＦフランジとの固定に用いる） [Water stoppage test]
<Prepared test equipment>
・ Siding board (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N, the maximum height difference from the bottom of the concave part to the top of the convex part is 4.2 mm)
-Both ends welded vacuum tube NW flange x VF flange (manufactured by Misumi, model number: FRNRFR40, material: SUS304, height 50 mm, pipe inner diameter 37.1 mm)
・ NW / KF standard long flange (manufactured by Cosmo Tech, model number: NW40LF70L, material: SUS304, height 70 mm, pipe inner diameter 37.1 mm)
・ MPC vacuum piping KF center ring (manufactured by Mirapro, model number: MCK-2040)
-NW clamp (ISO-KF flange type, manufactured by Mirapro, model number: MCK-1040)
・ 4 sets of M10 bolts and nuts (used for fixing the siding and VF flange)

＜試験具の処理＞
両端溶接真空管（ＦＲＮＲＦＲ４０）のＶＦフランジのボルト孔に合わせ、サイディング側にも孔開けし、Ｍ１０ボルトでサイディング板に両端溶接真空管（ＦＲＮＲＦＲ４０）のＶＦフランジを固定できるようにした。ＶＦフランジの取付け位置は、サイディング板に存在する柄（凹凸）に対して任意の位置である。
厚さ６．７ｍｍの試験シートから、直径６０ｍｍの円形シートを切り取り、得られた円盤状シートの中央部に直径４０ｍｍの孔を空けたドーナツ状試験片を作製した。 <Processing of test tools>
A hole was also made on the siding side in line with the bolt hole of the VF flange of the double-ended welded vacuum tube (FRNRFR40) so that the VF flange of the double-ended welded vacuum tube (FRNRFR40) could be fixed to the siding plate with M10 bolts. The mounting position of the VF flange is an arbitrary position with respect to the handle (unevenness) existing on the siding plate.
A circular sheet having a diameter of 60 mm was cut out from the test sheet having a thickness of 6.7 mm, and a donut-shaped test piece having a hole having a diameter of 40 mm was prepared in the central portion of the obtained disk-shaped sheet.

＜試験具、試験片の組み立て＞
図１に示すように、下からサイディング板１、ドーナツ状試験片７、両端溶接真空管２（ＦＲＮＲＦＲ４０）、ＫＦセンターリング３（ＭＣＫ−２０４０）、ロングフランジ４（ＮＷ４０ＬＦ７０Ｌ）の順に積み重ねた。この際、ドーナツ状試験片７の孔（直径４０ｍｍ）の中央部に両端溶接真空管２（ＦＲＮＲＦＲ４０）の孔（直径：３７．１ｍｍ）が位置するようにした。
両端溶接真空管２（ＦＲＮＲＦＲ４０）とロングフランジ４（ＮＷ４０ＬＦ７０Ｌ）とを、ＫＦセンターリング３（ＭＣＫ−２０４０）を挟んでＮＷクランプ（ＩＳＯ−ＫＦフランジタイプ、ミラプロ社製、型番：ＭＣＫ−１０４０、図示せず）によりクランプした。
また、サイディング板１表面の凸部の最も高い部位と、両端溶接真空管２（ＦＲＮＲＦＲ４０）の、サイディング板表面に向き合う最下端（ＶＦフランジ最表面）との距離が２．０ｍｍになるまで（ドーナツ状試験片７の最小厚さが２ｍｍになるまで）ボルトを締めこんだ。この際、２．０ｍｍのスペーサーを使用し、サイディング板１とＶＦフランジ最表面との間のクリアランスが変動しないようにした。 <Assembly of test tools and test pieces>
As shown in FIG. 1, the siding plate 1, the donut-shaped test piece 7, the double-ended welded vacuum tube 2 (FRNRFR40), the KF center ring 3 (MCK-2040), and the long flange 4 (NW40LF70L) were stacked in this order from the bottom. At this time, the hole (diameter: 37.1 mm) of the double-ended welded vacuum tube 2 (FRNRFR40) was positioned at the center of the hole (diameter 40 mm) of the donut-shaped test piece 7.
NW clamp (ISO-KF flange type, manufactured by Mirapro, model number: MCK-1040, shown) with both ends welded vacuum tube 2 (FRNRFR40) and long flange 4 (NW40LF70L) sandwiched between KF center ring 3 (MCK-2040). It was clamped by.
Further, until the distance between the highest portion of the convex portion on the surface of the siding plate 1 and the lowermost end (the outermost surface of the VF flange) of the double-ended welded vacuum tube 2 (FRNRFR40) facing the surface of the siding plate becomes 2.0 mm (doughnut shape). The bolts were tightened (until the minimum thickness of the test piece 7 was 2 mm). At this time, a 2.0 mm spacer was used so that the clearance between the siding plate 1 and the outermost surface of the VF flange did not fluctuate.

＜止水性試験方法＞
条件（Ｉ）：
ロングフランジ４（ＮＷ４０ＬＦ７０Ｌ）の上部から管内に水（２５℃）を注ぎ、両端溶接真空管２（ＦＲＮＲＦＲ４０）のＶＦフランジ下端から高さ１０ｃｍの位置まで、管内に水を満たした。３０℃雰囲気下で３０分間経過後、水漏れの有無を目視で調べた。水漏れが生じていない場合を○、水漏れが生じた場合を×とした。
条件（II）：
試験具ないし試験片を組み立てた状態で、３０℃の恒温槽に１２５日間静置した。その後、上記条件（Ｉ）と同様にして管内に高さ１０ｃｍまで水（２５℃）を注ぎ、３０℃雰囲気下で３０分間経過後、水漏れの有無を目視で調べた。水漏れが生じていない場合を○、水漏れが生じた場合を×とした。 <Water stoppage test method>
Condition (I):
Water (25 ° C.) was poured into the pipe from the upper part of the long flange 4 (NW40LF70L), and the pipe was filled with water from the lower end of the VF flange of the double-ended welded vacuum tube 2 (FRNRFR40) to a height of 10 cm. After 30 minutes in an atmosphere of 30 ° C., the presence or absence of water leakage was visually inspected. The case where no water leak occurred was marked with ◯, and the case where water leak occurred was marked with x.
Condition (II):
With the test tool or test piece assembled, it was allowed to stand in a constant temperature bath at 30 ° C. for 125 days. Then, water (25 ° C.) was poured into the pipe to a height of 10 cm in the same manner as in the above condition (I), and after 30 minutes in an atmosphere of 30 ° C., the presence or absence of water leakage was visually inspected. The case where no water leak occurred was marked with ◯, and the case where water leak occurred was marked with x.

上記表に示されるように、樹脂組成物の２５％圧縮応力が本発明の規定よりも大きい場合には、凹凸面への追従性が十分でなく、止水性能に劣る結果となった（比較例１）。
また、樹脂組成物の２５％圧縮応力が本発明の規定内であっても、３０℃で１２５日後の緩和弾性率が本発明の規定よりも小さいと、圧力下において凹凸追従状態を長期間維持することができなかった（比較例２〜５）。
これに対し、樹脂組成物の２５％圧縮応力と３０℃で１２５日後の緩和弾性率の両物性が、いずれも本発明の規定を満たす場合には、凹凸面への追従性に優れ、この追従状態を長期間維持することができ、結果、長期に亘り優れた止水性を維持することができることがわかった（実施例１〜７）。

As shown in the above table, when the 25% compressive stress of the resin composition is larger than the specification of the present invention, the followability to the uneven surface is not sufficient, and the water stopping performance is inferior (comparison). Example 1).
Further, even if the 25% compressive stress of the resin composition is within the specification of the present invention, if the relaxation elastic modulus after 125 days at 30 ° C. is smaller than the specification of the present invention, the uneven follow-up state is maintained for a long period of time under pressure. Could not be done (Comparative Examples 2 to 5).
On the other hand, when both the 25% compressive stress of the resin composition and the relaxed elastic modulus after 125 days at 30 ° C. satisfy the provisions of the present invention, they are excellent in followability to uneven surfaces, and this follow-up It was found that the state can be maintained for a long period of time, and as a result, excellent water stopping property can be maintained for a long period of time (Examples 1 to 7).

１サイディング板
２両端溶接真空管
３センターリング
４ロングフランジ
５ボルト
６ナット
７樹脂組成物（止水材）

1 Siding plate 2 Welded vacuum tubes at both ends 3 Center ring 4 Long flange 5 Bolt 6 Nut 7 Resin composition (water blocking material)

Claims

Contains 80 to 310 parts by mass of metal hydroxide and 160 to 460 parts by mass of softening agent with respect to 100 parts by mass of the total of the thermoplastic elastomer, the acid-modified resin, and the thermoplastic elastomer and the acid-modified resin. to the resin composition.

Wherein the thermoplastic elastomer comprises a styrene-based thermoplastic elastomer, according to claim 1 resin composition.

Wherein the thermal ratio of the thermoplastic elastomer and the acid-modified resin to the total of the acid-modified resin is 10 to 40 mass%, according to claim 1 or 2 resin composition.

The resin composition according to any one of claims 1 to 3, wherein the 25% compressive stress measured according to the C method of JIS K 6254 is 300 kPa or less.

The resin composition according to any one of claims 1 to 4 , which is formed into a donut shape.

The resin composition is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. When the flange and the siding plate are screwed together until the shortest distance to the flange surface is 2.0 mm, and water at 25 ° C. is poured into the pipe to a height of 10 cm, the temperature is 30 ° C. The resin composition according to any one of claims 1 to 4 , which does not cause water leakage for 30 minutes or more.

The resin composition is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. The flange and the siding plate were screwed together until the shortest distance from the flange surface was 2.0 mm, allowed to stand at 30 ° C. for 125 hours, and then placed in the pipe at 25 ° C. up to a height of 10 cm. The resin composition according to any one of claims 1 to 4 , which does not cause water leakage at 30 ° C. for 30 minutes or more when water is added.

The resin composition according to any one of claims 1 to 7 , which is used as a water blocking material.

Contains 80 to 310 parts by mass of metal hydroxide and 160 to 460 parts by mass of softening agent with respect to 100 parts by mass of the total of the thermoplastic elastomer, the acid-modified resin, and the thermoplastic elastomer and the acid-modified resin. A water blocking material made of a resin composition.

The water blocking material according to claim 9 , wherein the thermoplastic elastomer contains a styrene-based thermoplastic elastomer.

The water blocking material according to claim 9 or 10, wherein the ratio of the acid-modified resin to the total of the thermoplastic elastomer and the acid-modified resin in the resin composition is 10 to 40% by mass.

The water blocking material according to any one of claims 9 to 11, wherein the 25% compressive stress of the resin composition measured in accordance with the C method of JIS K 6254 is 300 kPa or less.

The water blocking material according to any one of claims 9 to 12, which is formed into a donut shape.

The water blocking material is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. When the flange and the siding plate are screwed together until the shortest distance to the flange surface is 2.0 mm, and water at 25 ° C. is poured into the pipe to a height of 10 cm, the temperature is 30 ° C. The water blocking material according to any one of claims 9 to 12 , which does not cause water leakage for 30 minutes or more.

The water blocking material is molded into a flat plate donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the donut-shaped molded product is held at the end of a cylindrical pipe having a hole diameter of 37.1 mm in the cylindrical axial direction. On the surface of a stainless steel flange having a diameter of 105 mm, the hole of the cylindrical pipe is arranged so as to be located at the center of the hole of the donut-shaped test piece, and on the side opposite to the flange side of the donut-shaped molded product. A siding plate (manufactured by Nichiha Corporation, trade name: Moen Excelard 16 New Grandeur Series I EPB311N) is arranged so that the uneven surface of the siding plate is on the side of the donut-shaped molded product. The flange and the siding plate were screwed together until the shortest distance from the flange surface was 2.0 mm, allowed to stand at 30 ° C. for 125 hours, and then placed in the pipe at 25 ° C. up to a height of 10 cm. The water blocking material according to any one of claims 9 to 12 , which does not cause water leakage at 30 ° C. for 30 minutes or more when water is added.