JP2020066931A - Resin composition for waterproof sheet and waterproof sheet - Google Patents
Resin composition for waterproof sheet and waterproof sheet Download PDFInfo
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Abstract
Description
本発明は、止水シート用樹脂組成物および止水シートに関する。 The present invention relates to a resin composition for a waterproof sheet and a waterproof sheet.
従来、トンネル用の止水シート（防水シートまたは遮水シートともいう。以下、止水シート、防水シートおよび遮水シートを同義として扱う。）として、エチレン−酢酸ビニル共重合体の押出成形によるシートが用いられてきた。たとえば、特許文献１には、酢酸ビニル含量が異なる２種以上のエチレン−酢酸ビニル共重合体の混合物を主成分としてなるトンネル用防水シートが開示されている。 Conventionally, as a waterproof sheet for a tunnel (also referred to as a waterproof sheet or a waterproof sheet; hereinafter, a waterproof sheet, a waterproof sheet and a waterproof sheet are synonymously used), a sheet formed by extrusion molding of an ethylene-vinyl acetate copolymer. Has been used. For example, Patent Document 1 discloses a waterproofing sheet for tunnels containing a mixture of two or more kinds of ethylene-vinyl acetate copolymers having different vinyl acetate contents as a main component.
止水シートに要求される特性として、粘着性、破断強度および伸びが良好であることがある。ただし、伸びに関しては、特許文献１に記載されているように、室温レベルの温度（２０℃）での改良が進められていた。近年、上述した止水シートの各種特性について、低温（たとえば、−１０℃）においても良好であることが求められるようになり、従来の止水シートでは要求を満たすことができなくなっている。 The properties required of the waterproof sheet include good adhesiveness, breaking strength and elongation. However, regarding the elongation, as described in Patent Document 1, improvement at a room temperature level (20 ° C.) has been advanced. In recent years, various characteristics of the above-mentioned waterproof sheet are required to be good even at low temperatures (for example, -10 ° C), and the conventional waterproof sheet cannot satisfy the requirements.
そこで、本発明は、止水シートを形成したときに、優れた粘着性を発揮しつつ、低温下において良好な破断強度と伸びをバランス良く発揮させる止水シート用樹脂組成物を提供する。 Therefore, the present invention provides a resin composition for a waterproof sheet, which exerts excellent adhesiveness at the time of forming a waterproof sheet and exhibits good breaking strength and elongation at a low temperature in a well-balanced manner.
本発明によれば、１種類以上のエチレン−酢酸ビニル共重合体を含み、前記エチレン・酢酸ビニル共重合体の総質量を１００質量％としたとき、酢酸ビニルを由来とする構造単位の総含有率が２０質量％以上３２質量％以下であり、下記条件で測定される引張破断伸度が５００％以上である止水シート用樹脂組成物が提供される。
（引張破断伸度測定条件）
（１）厚さ１ｍｍのシート状にした前記止水シート用樹脂組成物を用いて、試料裁断機により、厚さ１ｍｍ、長さ６０ｍｍ、幅３ｍｍの試験片を作製する。
（２）恒温槽付き引張試験機を用いて、恒温槽内設定温度−１０℃の環境下で、引張速度２００ｍｍ／ｍｉｎ、標線間距離１２ｍｍの条件で引張破断伸度を測定する。
According to the present invention, the total content of structural units derived from vinyl acetate is defined as including one or more kinds of ethylene-vinyl acetate copolymer, and the total mass of the ethylene-vinyl acetate copolymer is 100% by mass. Provided is a resin composition for a waterproof sheet, which has a rate of 20% by mass or more and 32% by mass or less and a tensile elongation at break of 500% or more measured under the following conditions.
(Tensile rupture elongation measurement conditions)
(1) A test piece having a thickness of 1 mm, a length of 60 mm, and a width of 3 mm is prepared by using a sample cutting machine, using the resin composition for a waterproof sheet having a thickness of 1 mm.
(2) Using a tensile tester with a constant temperature bath, the tensile elongation at break is measured under the conditions of a set temperature in the constant temperature bath of −10 ° C., a tensile speed of 200 mm / min, and a distance between marked lines of 12 mm.
また、本発明によれば、上述した止水シート用樹脂組成物で形成された止水シートが提供される。 Further, according to the present invention, there is provided a waterproof sheet formed of the resin composition for a waterproof sheet described above.
本発明によれば、シートを形成したときに、優れた粘着性を発揮しつつ、低温下において良好な破断強度と伸びをバランス良く発揮させる止水シート用樹脂組成物に関する技術を提供することができる。 According to the present invention, when a sheet is formed, while providing excellent adhesiveness, it is possible to provide a technique relating to a resin composition for a waterproof sheet, which exhibits good breaking strength and elongation at low temperature in a well-balanced manner. it can.
以下、本発明の実施形態について、詳細に説明する。なお、本明細書中、数値範囲の説明における「ａ〜ｂ」との表記は、特に断らない限り、ａ以上ｂ以下であることを表す。 Hereinafter, embodiments of the present invention will be described in detail. In addition, in the present specification, the notation “a to b” in the description of the numerical range indicates that the value is a or more and b or less, unless otherwise specified.
（止水シート用樹脂組成物）
実施形態に係る止水シート用樹脂組成物は、１種類以上のエチレン−酢酸ビニル共重合体を含む。止水シート用樹脂組成物の総質量を１００質量％としたとき、エチレン‐酢酸ビニル共重合体の含有率は８５質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が最も好ましい。
本実施形態の止水シート用樹脂組成物では、エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、酢酸ビニルを由来とする構造単位の総含有率の下限が２０質量％以上であり、好ましくは２５質量％以上である。また、エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、酢酸ビニルを由来とする構造単位の総含有率の上限が３２質量％以下であり、好ましくは３０質量％以下である。さらに、下記条件で測定される引張破断伸度が５００％以上である。酢酸ビニルを由来とする構造単位の総含有率の下限が２０質量％以上、当該総含有率の上限が３２質量％以下であることにより、優れた粘着性を発揮しつつ、低温下での破断強度と引張破断伸度のバランスをとることができる。当該引張破断伸度の上限は特に限定されないが、止水フィルムが薄くなりすぎ、強度が低下することを抑制する観点から６００％以下が好ましい。
（引張破断伸度測定条件）
（１）厚さ１ｍｍのシート状にした止水シート用樹脂組成物を用いて、試料裁断機により、長さ６０ｍｍ、幅３ｍｍの試験片を作製する。
（２）温槽付き引張試験機を用いて、恒温槽内設定温度−１０℃の環境下で、引張速度２００ｍｍ／ｍｉｎ、標線間距離１２ｍｍの条件で引張破断伸度を測定する。
(Resin composition for waterproof sheet)
The resin composition for a waterproof sheet according to the embodiment contains one or more kinds of ethylene-vinyl acetate copolymer. When the total mass of the resin composition for water blocking sheets is 100% by mass, the content of the ethylene-vinyl acetate copolymer is preferably 85% by mass or more, more preferably 90% by mass or more, most preferably 95% by mass or more. preferable.
In the resin composition for a water blocking sheet of the present embodiment, the lower limit of the total content of structural units derived from vinyl acetate is 20% by mass or more, when the total mass of the ethylene-vinyl acetate copolymer is 100% by mass. And preferably 25% by mass or more. Further, when the total mass of the ethylene-vinyl acetate copolymer is 100% by mass, the upper limit of the total content of structural units derived from vinyl acetate is 32% by mass or less, and preferably 30% by mass or less. . Furthermore, the tensile elongation at break measured under the following conditions is 500% or more. The lower limit of the total content of structural units derived from vinyl acetate is 20 mass% or more, and the upper limit of the total content is 32 mass% or less, thereby exhibiting excellent adhesiveness and breaking at low temperature. The strength and tensile elongation at break can be balanced. The upper limit of the tensile elongation at break is not particularly limited, but is preferably 600% or less from the viewpoint of preventing the waterproof film from becoming too thin and reducing the strength.
(Tensile rupture elongation measurement conditions)
(1) A test piece having a length of 60 mm and a width of 3 mm is produced by a sample cutting machine using the resin composition for a water blocking sheet, which is formed into a sheet having a thickness of 1 mm.
(2) Using a tensile tester with a temperature tank, the tensile elongation at break is measured under the conditions of a set temperature in the constant temperature tank of -10 ° C and a tensile speed of 200 mm / min and a marked line distance of 12 mm.
本実施形態に係る止水シート用樹脂組成物は、トンネルの防水に用いられる止水シートを形成する材料として好適に用いられる。 The resin composition for a waterproof sheet according to this embodiment is suitably used as a material for forming a waterproof sheet used for waterproofing a tunnel.
本実施形態の止水シート用樹脂組成物は、酢酸ビニルを由来とする構造単位の含有率が２５質量％以上３３質量％以下である１種類のエチレン−酢酸ビニル共重合体を含んでいてもよく、酢酸ビニルを由来とする構造単位の含有率が異なる２種類以上のエチレン−酢酸ビニル共重合体を含んでいてもよい。 The water-stop sheet resin composition of the present embodiment may contain one kind of ethylene-vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 25% by mass or more and 33% by mass or less. It may well contain two or more kinds of ethylene-vinyl acetate copolymers having different content ratios of structural units derived from vinyl acetate.
酢酸ビニルを由来とする構造単位の含有率が異なる２種類以上のエチレン−酢酸ビニル共重合体を主成分とする場合、酢酸ビニルの含有率が４０質量％以上６５質量％以下のエチレン−酢酸ビニル共重合体（Ａ）および酢酸ビニルの含有率が８質量％以上２５質量％以下のエチレン−酢酸ビニル共重合体（Ｂ）を含むことが好ましい。 When two or more kinds of ethylene-vinyl acetate copolymers having different content ratios of vinyl acetate-derived structural units are the main components, the content ratio of vinyl acetate is 40% by mass or more and 65% by mass or less. It is preferable that the copolymer (A) and the ethylene-vinyl acetate copolymer (B) have a vinyl acetate content of 8% by mass or more and 25% by mass or less.
本実施形態の止水シート用樹脂組成物において、エチレン−酢酸ビニル共重合体（Ａ）は、主に粘着性や低温下での引張破断伸度を高める役割を担い、エチレン−酢酸ビニル共重合体（Ｂ）は、主に低温下での引張破断伸度や破断強度を高める役割を担うと推察される。本発明者は、止水シート用樹脂組成物において、エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、酢酸ビニルを由来とする構造単位の総含有率Ｓを２０質量％以上３２質量％以下としつつ、酢酸ビニルを由来とする構造単位の含有率が当該総含有率Ｓより高いエチレン−酢酸ビニル共重合体（Ａ）と、酢酸ビニルを由来とする構造単位の含有率がエチレン−酢酸ビニル共重合体（Ａ）より低いエチレン−酢酸ビニル共重合体（Ｂ）とを下記に記載する適量含むことにより、当該止水シート用樹脂組成物で止水シートを形成したとき、破断強度および低温下での伸びをより一層バランス良く発揮させることができることを見出した。 In the resin composition for a waterproof sheet of the present embodiment, the ethylene-vinyl acetate copolymer (A) mainly plays a role of increasing the adhesive strength and the tensile elongation at break at low temperature, and the ethylene-vinyl acetate copolymer It is presumed that the combined body (B) mainly plays a role of increasing tensile breaking elongation and breaking strength at low temperatures. The present inventor, in the resin composition for water blocking sheets, when the total mass of the ethylene-vinyl acetate copolymer is 100% by mass, the total content S of structural units derived from vinyl acetate is 20% by mass or more. While the content of the structural unit derived from vinyl acetate is 32% by mass or less, the content of the ethylene-vinyl acetate copolymer (A) in which the content of the structural unit derived from vinyl acetate is higher than the total content S and the content of the structural unit derived from vinyl acetate are When a water blocking sheet is formed with the resin composition for a water blocking sheet by including an appropriate amount of the ethylene-vinyl acetate copolymer (B) lower than the ethylene-vinyl acetate copolymer (A) described below, It has been found that the breaking strength and the elongation at low temperature can be exhibited in a better balance.
（エチレン−酢酸ビニル共重合体（Ａ））
エチレン−酢酸ビニル共重合体（Ａ）における酢酸ビニルの含有率の下限は４０質量％以上が好ましく、４３質量％以上がより好ましく、４５質量％以上がさらに好ましい。一方、エチレン−酢酸ビニル共重合体（Ａ）における酢酸ビニルの含有率の上限は、６５質量％以下が好ましく、６０質量％以下がより好ましい。エチレン−酢酸ビニル共重合体（Ａ）における酢酸ビニルの含有率を上記範囲とすることにより、エチレン−酢酸ビニル共重合体を用いてシートを形成したとき、粘着性や低温下での引張破断伸度を高めることができると推察される。本実施形態の止水シート用樹脂組成物は、酢酸ビニルの含有率が異なるエチレン−酢酸ビニル共重合体（Ａ）を２種以上含有していてもよい。
(Ethylene-vinyl acetate copolymer (A))
The lower limit of the content of vinyl acetate in the ethylene-vinyl acetate copolymer (A) is preferably 40% by mass or more, more preferably 43% by mass or more, and further preferably 45% by mass or more. On the other hand, the upper limit of the content of vinyl acetate in the ethylene-vinyl acetate copolymer (A) is preferably 65% by mass or less, and more preferably 60% by mass or less. By setting the content of vinyl acetate in the ethylene-vinyl acetate copolymer (A) within the above range, when a sheet is formed using the ethylene-vinyl acetate copolymer, the adhesiveness and the tensile rupture elongation at low temperature are formed. It is presumed that the degree can be increased. The water-stop sheet resin composition of the present embodiment may contain two or more ethylene-vinyl acetate copolymers (A) having different vinyl acetate contents.
エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、エチレン−酢酸ビニル共重合体（Ａ）の含有率の下限は４０質量％以上が好ましく、４２質量％以上がより好ましく、４４質量％以上がさらに好ましい。エチレン−酢酸ビニル共重合体（Ａ）の含有率の上限は、５３質量％以下が好ましく、５１質量％以下がより好ましく、４９質量％以下がさらに好ましい。 When the total mass of the ethylene-vinyl acetate copolymer is 100% by mass, the lower limit of the content of the ethylene-vinyl acetate copolymer (A) is preferably 40% by mass or more, more preferably 42% by mass or more, and 44 It is more preferably at least mass%. The upper limit of the content of the ethylene-vinyl acetate copolymer (A) is preferably 53% by mass or less, more preferably 51% by mass or less, and further preferably 49% by mass or less.
エチレン−酢酸ビニル共重合体の総質量に対するエチレン−酢酸ビニル共重合体（Ａ）の含有率を上記範囲とすることにより、本実施形態の止水シート用樹脂組成物を用いてシートを形成したとき、粘着性や低温下での引張破断伸度を高めることができる。本実施形態の止水シート用樹脂組成物が酢酸ビニルの含有率の異なるエチレン−酢酸ビニル共重合体（Ａ）を２種以上含む場合は、エチレン−酢酸ビニル共重合体（Ａ）の総含有率が上記の範囲にあればよい。 By setting the content rate of the ethylene-vinyl acetate copolymer (A) with respect to the total mass of the ethylene-vinyl acetate copolymer within the above range, a sheet was formed using the resin composition for a waterproof sheet of the present embodiment. At this time, the adhesiveness and the tensile elongation at break under low temperature can be increased. When the resin composition for a waterproof sheet of the present embodiment contains two or more ethylene-vinyl acetate copolymers (A) having different vinyl acetate contents, the total content of the ethylene-vinyl acetate copolymer (A) is included. The rate may be in the above range.
エチレン−酢酸ビニル共重合体（Ａ）のメルトフローレート（ＭＦＲ）の下限は０．５ｇ／１０分以上が好ましく、１．０ｇ／１０分以上がより好ましく、１．５ｇ／１０分以上がさらに好ましい。エチレン−酢酸ビニル共重合体（Ａ）のＭＦＲの上限は１００ｇ／１０分以下が好ましく、７０ｇ／１０分以下がより好ましく、６０ｇ／１０分以下がさらに好ましい。本実施形態の止水シート用樹脂組成物が酢酸ビニルの含有率の異なる２種以上のエチレン−酢酸ビニル共重合体（Ａ）を含む場合には、混合物としてのエチレン−酢酸ビニル共重合体（Ａ）のＭＦＲが上記の範囲にあればよい。 The lower limit of the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer (A) is preferably 0.5 g / 10 minutes or more, more preferably 1.0 g / 10 minutes or more, and even more preferably 1.5 g / 10 minutes or more. preferable. The upper limit of the MFR of the ethylene-vinyl acetate copolymer (A) is preferably 100 g / 10 minutes or less, more preferably 70 g / 10 minutes or less, and further preferably 60 g / 10 minutes or less. When the resin composition for a waterproof sheet of the present embodiment contains two or more kinds of ethylene-vinyl acetate copolymers (A) having different vinyl acetate contents, an ethylene-vinyl acetate copolymer (as a mixture ( The MFR of A) may be in the above range.
（エチレン−酢酸ビニル共重合体（Ｂ））
エチレン−酢酸ビニル共重合体（Ｂ）における酢酸ビニルの含有率の下限は８質量％以上が好ましく、１０質量％以上がより好ましく、１４質量％以上がさらに好ましい。一方、エチレン−酢酸ビニル共重合体（Ｂ）における酢酸ビニルの含有率の上限は、２５質量％以下が好ましく、２３質量％以下がより好ましく、２０質量％以下がさらに好ましい。エチレン−酢酸ビニル共重合体（Ｂ）における酢酸ビニルの含有率を上記範囲とすることにより、本実施形態の止水シート用樹脂組成物を用いてシートを形成したとき、低温下での破断強度や引張破断伸度を高めることができる。本実施形態の止水シート用樹脂組成物は、酢酸ビニルの含有率が異なるエチレン−酢酸ビニル共重合体（Ｂ）を２種以上含有していてもよい。
(Ethylene-vinyl acetate copolymer (B))
The lower limit of the content of vinyl acetate in the ethylene-vinyl acetate copolymer (B) is preferably 8% by mass or more, more preferably 10% by mass or more, and further preferably 14% by mass or more. On the other hand, the upper limit of the content of vinyl acetate in the ethylene-vinyl acetate copolymer (B) is preferably 25% by mass or less, more preferably 23% by mass or less, and further preferably 20% by mass or less. When the content of vinyl acetate in the ethylene-vinyl acetate copolymer (B) is within the above range, when a sheet is formed using the resin composition for a waterproof sheet of the present embodiment, the breaking strength at low temperature is low. And the tensile elongation at break can be increased. The water-stop sheet resin composition of the present embodiment may contain two or more kinds of ethylene-vinyl acetate copolymers (B) having different vinyl acetate contents.
エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、エチレン−酢酸ビニル共重合体（Ｂ）の含有率の下限は３５質量％以上が好ましく、３７質量％以上がより好ましく、３９質量％以上がさらに好ましい。エチレン−酢酸ビニル共重合体（Ｂ）の含有率の上限は、６０質量％以下が好ましく、５８質量％以下がより好ましく、５６質量％以下がさらに好ましい。 When the total mass of the ethylene-vinyl acetate copolymer is 100 mass%, the lower limit of the content of the ethylene-vinyl acetate copolymer (B) is preferably 35 mass% or more, more preferably 37 mass% or more, and 39 It is more preferably at least mass%. The upper limit of the content of the ethylene-vinyl acetate copolymer (B) is preferably 60% by mass or less, more preferably 58% by mass or less, and further preferably 56% by mass or less.
エチレン−酢酸ビニル共重合体の総質量に対するエチレン−酢酸ビニル共重合体（Ｂ）の含有率を上記範囲とすることにより、本実施形態の止水シート用樹脂組成物を用いてシートを形成したとき、低温下での破断強度や引張破断伸度を高めることができる。本実施形態の止水シート用樹脂組成物が酢酸ビニルの含有率の異なるエチレン−酢酸ビニル共重合体（Ｂ）を２種以上含む場合は、エチレン−酢酸ビニル共重合体（Ｂ）の総含有率が上記の範囲にあればよい。 By setting the content rate of the ethylene-vinyl acetate copolymer (B) with respect to the total mass of the ethylene-vinyl acetate copolymer within the above range, a sheet was formed using the resin composition for a waterproof sheet of the present embodiment. At this time, the breaking strength and tensile breaking elongation at low temperatures can be increased. When the resin composition for a waterproof sheet of the present embodiment contains two or more kinds of ethylene-vinyl acetate copolymers (B) having different vinyl acetate contents, the total content of the ethylene-vinyl acetate copolymer (B). The rate may be in the above range.
エチレン−酢酸ビニル共重合体（Ｂ）のＭＦＲの下限は０．５ｇ／１０分以上が好ましく、１．０ｇ／１０分以上がより好ましく、１．５ｇ／１０分以上がさらに好ましい。エチレン−酢酸ビニル共重合体（Ｂ）のＭＦＲの上限は３０ｇ／１０分以下が好ましく、２０ｇ／１０分以下がより好ましく、１０ｇ／１０分以下がさらに好ましい。本実施形態の止水シート用樹脂組成物が酢酸ビニルの含有率の異なる２種以上のエチレン−酢酸ビニル共重合体（Ｂ）を含む場合には、混合物としてのエチレン−酢酸ビニル共重合体（Ｂ）のＭＦＲが上記の範囲にあればよい。 The lower limit of the MFR of the ethylene-vinyl acetate copolymer (B) is preferably 0.5 g / 10 minutes or more, more preferably 1.0 g / 10 minutes or more, still more preferably 1.5 g / 10 minutes or more. The upper limit of the MFR of the ethylene-vinyl acetate copolymer (B) is preferably 30 g / 10 minutes or less, more preferably 20 g / 10 minutes or less, still more preferably 10 g / 10 minutes or less. When the resin composition for a waterproof sheet of the present embodiment contains two or more kinds of ethylene-vinyl acetate copolymers (B) having different vinyl acetate contents, an ethylene-vinyl acetate copolymer (as a mixture ( The MFR of B) may be in the above range.
本実施形態の止水シート用樹脂組成物が２種類以上のエチレン−酢酸ビニル共重合体（Ｂ）を含む場合、エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、酢酸ビニルの含有率が８質量％以上１５質量％以下のエチレン−酢酸ビニル共重合体（Ｂ１）と、酢酸ビニルの含有率が１５質量％を超え２５質量％以下のエチレン−酢酸ビニル共重合体（Ｂ２）とを含むことが好ましい。エチレン−酢酸ビニル共重合体（Ｂ）がエチレン−酢酸ビニル共重合体（Ｂ１）およびエチレン−酢酸ビニル共重合体（Ｂ２）を含むことにより、エチレン−酢酸ビニル共重合体（Ａ）と、エチレン−酢酸ビニル共重合体（Ｂ）との相溶性を高め、本実施形態の止水シート用樹脂組成物で止水シートを形成したとき、クラックが生じることを抑制し、止水シートの止水性能や信頼性を高めることができる。 When the resin composition for a waterproof sheet of the present embodiment contains two or more kinds of ethylene-vinyl acetate copolymers (B), vinyl acetate is defined as 100 mass% of the total mass of the ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymer (B1) having a content of 8 mass% or more and 15 mass% or less, and an ethylene-vinyl acetate copolymer (B2) having a vinyl acetate content of more than 15 mass% and 25 mass% or less. ) And are preferably included. When the ethylene-vinyl acetate copolymer (B) contains the ethylene-vinyl acetate copolymer (B1) and the ethylene-vinyl acetate copolymer (B2), the ethylene-vinyl acetate copolymer (A) and ethylene -Increasing the compatibility with the vinyl acetate copolymer (B) and suppressing the occurrence of cracks when forming a waterproof sheet with the resin composition for a waterproof sheet of the present embodiment, and stopping the water of the waterproof sheet. Performance and reliability can be improved.
エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、エチレン−酢酸ビニル共重合体（Ｂ１）の含有率の下限は、３７質量％以上が好ましく、３８質量％以上がより好ましい。一方、エチレン−酢酸ビニル共重合体（Ｂ１）の含有率の上限は、５０質量％以下が好ましく、４７質量％以下がより好ましい。エチレン−酢酸ビニル共重合体（Ｂ２）の含有率の下限は、１０質量％以上が好ましく、１３質量％以上がより好ましい。一方、エチレン−酢酸ビニル共重合体（Ｂ２）の含有率の上限は、２３質量％以下が好ましく、２２質量％以下がより好ましい。ただし、エチレン−酢酸ビニル共重合体（Ｂ１）とエチレン−酢酸ビニル共重合体（Ｂ２）とを合計した総含有率は３５質量％以上６０質量％以下の範囲内である。 When the total mass of the ethylene-vinyl acetate copolymer is 100% by mass, the lower limit of the content of the ethylene-vinyl acetate copolymer (B1) is preferably 37% by mass or more, and more preferably 38% by mass or more. On the other hand, the upper limit of the content of the ethylene-vinyl acetate copolymer (B1) is preferably 50% by mass or less, and more preferably 47% by mass or less. The lower limit of the content of the ethylene-vinyl acetate copolymer (B2) is preferably 10% by mass or more, and more preferably 13% by mass or more. On the other hand, the upper limit of the content of the ethylene-vinyl acetate copolymer (B2) is preferably 23% by mass or less, and more preferably 22% by mass or less. However, the total content of the ethylene-vinyl acetate copolymer (B1) and the ethylene-vinyl acetate copolymer (B2) is in the range of 35% by mass or more and 60% by mass or less.
［メルトフローレート（ＭＦＲ）］
本実施形態の止水シート用樹脂組成物および当該止水シート用樹脂組成物に含まれるエチレン−酢酸ビニル共重合体のＭＦＲは、ＪＩＳ Ｋ７２１０−１９９９に準拠して温度１９０℃及び荷重２．１６ｋｇの条件で測定される値をいい、単位は「ｇ／１０分」で表される。ＭＦＲが高いほど熱溶融時の流動性は高く、ＭＦＲが低いほど熱溶融時の流動性は低い。
[Melt flow rate (MFR)]
The MFR of the water-stop sheet resin composition of the present embodiment and the ethylene-vinyl acetate copolymer contained in the water-stop sheet resin composition has a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210-1999. The unit is represented by "g / 10 minutes". The higher the MFR, the higher the fluidity during heat melting, and the lower the MFR, the lower the fluidity during heat melting.
本実施形態の止水シート用樹脂組成物のＭＦＲの下限は、０．５ｇ／１０分以上が好ましく、１．０ｇ／１０分以上がより好ましい。本実施形態の止水シート用樹脂組成物のＭＦＲの上限は、４０ｇ／１０分以下が好ましく、３０ｇ／１０分以下がより好ましい。止水シート用樹脂組成物のＭＦＲが０．５ｇ／１０分以上４０ｇ／１０分以下であることにより、止水シートの成形加工性を向上させることができる。 The lower limit of the MFR of the resin composition for water blocking sheets of the present embodiment is preferably 0.5 g / 10 minutes or more, more preferably 1.0 g / 10 minutes or more. The upper limit of the MFR of the resin composition for water blocking sheets of the present embodiment is preferably 40 g / 10 minutes or less, more preferably 30 g / 10 minutes or less. When the MFR of the resin composition for a waterproof sheet is 0.5 g / 10 minutes or more and 40 g / 10 minutes or less, the moldability of the waterproof sheet can be improved.
［破断強度］
本実施形態の止水シート用樹脂組成物は、以下の条件で測定される破断強度が３５ＭＰａ以上が好ましく、４０ＭＰａ以上がより好ましく、４５ＭＰａ以上がさらに好ましい。
（破断強度測定条件）
（１）厚さ１ｍｍのシート状にした前記止水シート用樹脂組成物を用いて、試料裁断機により、厚さ１ｍｍ、長さ６０ｍｍ、幅３ｍｍの試験片を作製する。
（２）恒温槽付き引張試験機を用いて、恒温槽内設定温度−１０℃の環境下で、引張速度２００ｍｍ／ｍｉｎ条件で破断強度を測定する。
[Breaking strength]
The resin composition for a waterproof sheet according to the present embodiment has a breaking strength measured under the following conditions of preferably 35 MPa or more, more preferably 40 MPa or more, and further preferably 45 MPa or more.
(Conditions for measuring breaking strength)
(1) A test piece having a thickness of 1 mm, a length of 60 mm, and a width of 3 mm is prepared by using a sample cutting machine, using the resin composition for a waterproof sheet having a thickness of 1 mm.
(2) Using a tensile tester with a constant temperature bath, the breaking strength is measured under the condition of a preset temperature in the constant temperature bath of −10 ° C. and a pulling speed of 200 mm / min.
以上説明した止水シート用樹脂組成物によれば、止水シートを形成したとき、低温下での破断強度および伸びをバランス良く発揮させることができる。
［添加剤］
本実施形態の止水シート用樹脂組成物は、止水シートを形成したときの特性を損なわない範囲でその他の樹脂や添加剤を含んでいてもよい。
添加剤としては、たとえば、シリカ、炭酸カルシウムなどの無機充填剤が挙げられる。コンクリートなどの水硬性材料に対する止水用途で止水シート用樹脂組成物を用いる場合、当該止水シート用樹脂組成物に含まれる無機充填剤が水硬性材料中の無機成分と相互作用を起こすことにより、水硬性材料を硬化して得られる水硬物と止水シートとの接着性の向上を図ることができる。また本実施形態の止水シート用樹脂組成物は、シリコーン系滑剤などの添加剤を含有していてもよい。
According to the resin composition for a water blocking sheet described above, when the water blocking sheet is formed, the breaking strength and elongation at low temperature can be exhibited in a well-balanced manner.
[Additive]
The resin composition for a water blocking sheet of the present embodiment may contain other resins and additives within a range that does not impair the properties when the water blocking sheet is formed.
Examples of the additive include inorganic fillers such as silica and calcium carbonate. When the resin composition for a waterproof sheet is used for waterproofing a hydraulic material such as concrete, the inorganic filler contained in the resin composition for a waterproof sheet interacts with the inorganic component in the hydraulic material. As a result, it is possible to improve the adhesiveness between the hydraulic material obtained by curing the hydraulic material and the waterproof sheet. Further, the resin composition for a water blocking sheet of the present embodiment may contain an additive such as a silicone lubricant.
（止水シート）
上述した止水シート用樹脂組成物をシート状に加工することにより、止水シートが形成される。シート加工の方法は特に限定されないが、単軸押出機、二軸押出機などを用いて止水シート用樹脂組成物からペレットを作製し、当該ペレットをカレンダー成形法、押出成形法などにより止水シートを形成する方法が挙げられる。止水シートの厚さは特に限定されないが、典型的には４００μｍ以上２０００μｍ以下である。
(Water stop sheet)
A water blocking sheet is formed by processing the resin composition for a water blocking sheet described above into a sheet shape. The method of sheet processing is not particularly limited, but pellets are produced from the resin composition for a water-stop sheet using a single-screw extruder, a twin-screw extruder, etc. The method of forming a sheet is mentioned. The thickness of the water blocking sheet is not particularly limited, but is typically 400 μm or more and 2000 μm or less.
本実施形態の止水シート用樹脂組成物からなる止水シートは、その形態は制限されず、たとえば、止水シート全体が本実施形態の止水シート用樹脂組成物よりなるシートから形成されていても、または、一方または両面の表面部分のみが本実施形態の止水シート用樹脂組成物で形成されていてもよい。 The form of the waterproof sheet made of the resin composition for a waterproof sheet of the present embodiment is not limited, and for example, the entire waterproof sheet is formed of a sheet made of the resin composition for a waterproof sheet of the present embodiment. Alternatively, or only one or both surface portions may be formed by the resin composition for a waterproof sheet of the present embodiment.
本実施形態の止水シート用樹脂組成物からなる止水シートの用途として、トンネル用の止水シートの他に、廃棄物処分場、糞尿貯留槽、雨水貯留槽の遮水、ダム、河川、用水路、仮設水路の遮水、建築物における屋上防水、プール・タンク等の構造物の外壁防水などが挙げられる。 As the application of the waterproof sheet made of the resin composition for the waterproof sheet of the present embodiment, in addition to the waterproof sheet for tunnels, a waste disposal site, a manure storage tank, a water shield of a rainwater storage tank, a dam, a river, Examples include water canals, temporary water canals, waterproof rooftops in buildings, and outer walls of structures such as pools and tanks.
本実施形態の止水シートは、優れた粘着性を発揮しつつ、低温下で破断強度および伸びをバランス良く発揮する。 The water blocking sheet of the present embodiment exerts a good balance of breaking strength and elongation at low temperature while exhibiting excellent adhesiveness.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
以下、本発明を実施例および比較例により説明するが、本発明はこれらに限定されるものではない。
実施例１〜５、比較例１〜３の各止水シート用樹脂組成物を表１に示すエチレン−酢酸ビニル共重合体の種類および配合にて作製した。
表１中のエチレン−酢酸ビニル共重合体Ａ−１〜Ａ−４、エチレン−酢酸ビニル共重合体Ｂ１−１、Ｂ１−２およびエチレン−酢酸ビニル共重合体Ｂ２−１〜Ｂ２−３に関し、酢酸ビニルに由来する構造単位の含有率（質量％）およびＭＦＲ（ｇ／１０分）を表１に示す。
Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
The resin compositions for water blocking sheets of Examples 1 to 5 and Comparative Examples 1 to 3 were produced with the types and blending of the ethylene-vinyl acetate copolymers shown in Table 1.
Regarding the ethylene-vinyl acetate copolymers A-1 to A-4, the ethylene-vinyl acetate copolymers B1-1 and B1-2 and the ethylene-vinyl acetate copolymers B2-1 to B2-3 in Table 1, Table 1 shows the content (% by mass) of structural units derived from vinyl acetate and the MFR (g / 10 min).
［引張試験］
実施例１〜５、比較例１〜３の各止水シート用樹脂組成物について、以下に説明する引張試験を実施した。
ＪＩＳ Ｋ−７１１３に準拠して、恒温槽付き引張試験機を用いて、恒温槽内設定温度−１０℃の環境下で、引張速度２００ｍｍ／ｍｉｎ、試験片の形状：２号半（長さ６０ｍｍ、幅３ｍｍ）、標線間距離１２ｍｍの条件で引張破断伸度および破断強度を測定した。引張試験機として、株式会社島津製作所社製、オートグラフＡＧ−Ｘ Ｐｌｕｓを使用した。なお、試験片は株式会社ダンベル社製ＳＤ型試料裁断機により作製した。
引張破断伸度および破断強度の測定結果を表１に示す。
[Tensile test]
Tensile tests described below were performed on the resin compositions for water blocking sheets of Examples 1 to 5 and Comparative Examples 1 to 3.
According to JIS K-7113, using a tensile tester with a constant temperature bath, under an environment of a set temperature in the constant temperature bath of -10 ° C, a pulling speed of 200 mm / min, a shape of a test piece: No. 2 and a half (length 60 mm , Width 3 mm), and the distance between marked lines was 12 mm, and the tensile breaking elongation and breaking strength were measured. As a tensile tester, Shimadzu Corporation Autograph AG-X Plus was used. In addition, the test piece was produced by SD type sample cutter manufactured by Dumbbell Co., Ltd.
Table 1 shows the measurement results of tensile elongation at break and breaking strength.
表１に示すように、実施例１〜５の各止水シート用樹脂組成物は、止水シートを形成したときに、低温下で破断強度および引張破断伸度をバランス良く発揮させることが確認された。
As shown in Table 1, it was confirmed that each of the resin compositions for water blocking sheets of Examples 1 to 5 exhibited a well-balanced breaking strength and tensile elongation at low temperature when the water blocking sheet was formed. Was done.
［剥離強度測定］
実施例２、３および参考例１、２の各止水シート用樹脂組成物について剥離強度を測定した。なお、参考例１は、実施例２の止水シート用樹脂組成物での酢酸ビニルを由来とする構造単位の含有率（２７．６質量％）と近い、酢酸ビニルを由来とする構造単位の含有率（２８質量％）であるエチレン・酢酸ビニル共重合体Ｃ−１を１００質量％含有する。また、参考例２は、実施例３の止水シート用樹脂組成物での酢酸ビニルを由来とする構造単位の含有率（３０．０質量％）と近い、酢酸ビニルを由来とする構造単位の含有率（３３質量％）であるエチレン・酢酸ビニル共重合体Ｃ−２を１００質量％含有する。
[Peel strength measurement]
The peel strengths of the resin compositions for water blocking sheets of Examples 2 and 3 and Reference Examples 1 and 2 were measured. In addition, in Reference Example 1, the content of the structural unit derived from vinyl acetate (27.6% by mass) in the resin composition for a waterproof sheet of Example 2 is close to that of the structural unit derived from vinyl acetate. 100% by mass of ethylene-vinyl acetate copolymer C-1 having a content rate (28% by mass) is contained. In addition, in Reference Example 2, a structural unit derived from vinyl acetate, which is close to the content rate (30.0% by mass) of the structural unit derived from vinyl acetate in the resin composition for a waterproof sheet of Example 3, is used. 100% by mass of ethylene-vinyl acetate copolymer C-2 having a content rate (33% by mass) is contained.
剥離強度の測定条件を以下に記載する。剥離強度の測定結果を表２に示す。
（試験片の作製）
ＰＥＴフィルム厚:５０μｍ
止水シート用樹脂組成物シート厚:１０００μｍ（１ｍｍ）
試験片作成条件:温度１６０℃、熱圧着時間５分
（剥離試験条件）
剥離試験装置：株式会社島津製作所社製、オートグラフＡＧ−Ｘ
剥離速度:１００ｍｍ／分
温度：２３℃
湿度：５０％ＲＨ
(Preparation of test piece)
PET film thickness: 50 μm
Resin composition for waterproof sheet Sheet thickness: 1000 μm (1 mm)
Test piece preparation conditions: temperature 160 ° C, thermocompression bonding time 5 minutes (peeling test condition)
Peel tester: Shimadzu Corporation, Autograph AG-X
Peeling speed: 100 mm / min Temperature: 23 ° C
Humidity: 50% RH
止水シート用樹脂組成物全体における酢酸ビニルを由来とする構造単位の含有率が同様である、実施例２の止水シート用樹脂組成物と参考例１の止水シート用樹脂組成物、実施例３の止水シート用樹脂組成物と参考例２の止水シート用樹脂組成物とをそれぞれ比較すると、酢酸ビニルに由来する構造単位の含有率が比較的高いエチレン−酢酸ビニル共重合体を有する場合に、酢酸ビニルを由来とする構造単位の含有率が単一のエチレン−酢酸ビニル共重合体で構成した場合より、２３℃の環境下で剥離強度、換言すると粘着性が高まることが確認され、低温下でも優れた粘着性を示すことが示唆された。 The resin composition for a waterproof sheet of Example 2 and the resin composition for a waterproof sheet of Reference Example 1, in which the content of the structural unit derived from vinyl acetate in the entire resin composition for a waterproof sheet is similar. Comparing the water-stop sheet resin composition of Example 3 and the water-stop sheet resin composition of Reference Example 2, respectively, an ethylene-vinyl acetate copolymer having a relatively high content of structural units derived from vinyl acetate was obtained. When it has, it is confirmed that the peel strength, in other words, the tackiness is increased under the environment of 23 ° C., as compared with the case where the structural unit derived from vinyl acetate is composed of a single ethylene-vinyl acetate copolymer. Therefore, it was suggested that the composition exhibits excellent tackiness even at low temperatures.
Claims (4)
前記エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、酢酸ビニルを由来とする構造単位の総含有率が２０質量％以上３２質量％以下であり、
下記条件で測定される引張破断伸度が５００％以上である止水シート用樹脂組成物。
（引張破断伸度測定条件）
（１）前記止水シート用樹脂組成物を用いて、試料裁断機により、厚さ１ｍｍ、長さ６０ｍｍ、幅３ｍｍの試験片を作製する。
（２）恒温槽付き引張試験機を用いて、恒温槽内設定温度−１０℃の環境下で、引張速度２００ｍｍ／ｍｉｎ、標線間距離１２ｍｍの条件で引張破断伸度を測定する。 Contains one or more ethylene-vinyl acetate copolymers,
When the total mass of the ethylene-vinyl acetate copolymer is 100% by mass, the total content of structural units derived from vinyl acetate is 20% by mass or more and 32% by mass or less,
A resin composition for a waterproof sheet having a tensile elongation at break of 500% or more measured under the following conditions.
(Tensile rupture elongation measurement conditions)
(1) Using the resin composition for a water blocking sheet, a test piece having a thickness of 1 mm, a length of 60 mm and a width of 3 mm is produced by a sample cutting machine.
(2) Using a tensile tester with a constant temperature bath, the tensile elongation at break is measured under the conditions of a set temperature in the constant temperature bath of −10 ° C., a tensile speed of 200 mm / min, and a distance between marked lines of 12 mm.
酢酸ビニルを由来とする構造単位の含有率が８質量％以上２５質量％以下であるエチレン−酢酸ビニル共重合体（Ｂ）と、
を含み、
前記エチレン−酢酸ビニル共重合体の総質量を１００質量％としたとき、前記エチレン−酢酸ビニル共重合体（Ａ）の含有率が４０質量％以上５３質量％以下であり、前記エチレン−酢酸ビニル共重合体（Ｂ）の含有率が３５質量％以上６０質量％以下である請求項１に記載の止水シート用樹脂組成物。 An ethylene-vinyl acetate copolymer (A) having a content of structural units derived from vinyl acetate of 40% by mass or more and 65% by mass or less;
An ethylene-vinyl acetate copolymer (B) in which the content of structural units derived from vinyl acetate is 8% by mass or more and 25% by mass or less;
Including,
When the total mass of the ethylene-vinyl acetate copolymer is 100% by mass, the content of the ethylene-vinyl acetate copolymer (A) is 40% by mass or more and 53% by mass or less, and the ethylene-vinyl acetate is The resin composition for a waterproof sheet according to claim 1, wherein the content of the copolymer (B) is 35% by mass or more and 60% by mass or less.
（破断強度測定条件）
（１）前記止水シート用樹脂組成物を用いて、試料裁断機により、厚さ１ｍｍ、長さ６０ｍｍ、幅３ｍｍの試験片を作製する。
（２）恒温槽付き引張試験機を用いて、恒温槽内設定温度−１０℃の環境下で、引張速度２００ｍｍ／ｍｉｎ条件で破断強度を測定する。 The resin composition for a waterproof sheet according to claim 1 or 2, which has a breaking strength of 35 MPa or more measured under the following conditions.
(Conditions for measuring breaking strength)
(1) Using the resin composition for a water blocking sheet, a test piece having a thickness of 1 mm, a length of 60 mm and a width of 3 mm is produced by a sample cutting machine.
(2) Using a tensile tester with a constant temperature bath, the breaking strength is measured under the condition of a preset temperature in the constant temperature bath of −10 ° C. and a pulling speed of 200 mm / min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117487282A (en) * | 2023-12-29 | 2024-02-02 | 潍坊市兴源防水材料股份有限公司 | Ageing-resistant chlorinated polyethylene waterproof coiled material |
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| JP2001115791A (en) * | 1999-10-18 | 2001-04-24 | Fujimori Kogyo Co Ltd | Waterproof sheet for tunnel |
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| JP2008019664A (en) * | 2006-07-14 | 2008-01-31 | Fujimori Kogyo Co Ltd | Repairing sheet and repairing method |
| JP2010215762A (en) * | 2009-03-16 | 2010-09-30 | Mitsubishi Plastics Inc | Ethylene-vinyl acetate copolymer composition and tarpaulin |
| JP2012102593A (en) * | 2010-11-12 | 2012-05-31 | C I Kasei Co Ltd | Civil engineering sheet |
| JP2015143316A (en) * | 2013-04-22 | 2015-08-06 | 三菱化学株式会社 | Polycarbonate diol and method of producing the same, and polyurethane using the same |
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|---|---|---|---|---|
| JP2001115791A (en) * | 1999-10-18 | 2001-04-24 | Fujimori Kogyo Co Ltd | Waterproof sheet for tunnel |
| JP2002294015A (en) * | 2001-04-02 | 2002-10-09 | Kuraray Co Ltd | Water shut off sheet for civil engineering use |
| JP2008019664A (en) * | 2006-07-14 | 2008-01-31 | Fujimori Kogyo Co Ltd | Repairing sheet and repairing method |
| JP2010215762A (en) * | 2009-03-16 | 2010-09-30 | Mitsubishi Plastics Inc | Ethylene-vinyl acetate copolymer composition and tarpaulin |
| JP2012102593A (en) * | 2010-11-12 | 2012-05-31 | C I Kasei Co Ltd | Civil engineering sheet |
| JP2015143316A (en) * | 2013-04-22 | 2015-08-06 | 三菱化学株式会社 | Polycarbonate diol and method of producing the same, and polyurethane using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117487282A (en) * | 2023-12-29 | 2024-02-02 | 潍坊市兴源防水材料股份有限公司 | Ageing-resistant chlorinated polyethylene waterproof coiled material |
| CN117487282B (en) * | 2023-12-29 | 2024-03-26 | 潍坊市兴源防水材料股份有限公司 | Ageing-resistant chlorinated polyethylene waterproof coiled material |
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