JP2019002137A - Waterproof sheet and waterproof construction method - Google Patents

Abstract

SOLUTION: A waterproof sheet comprises an adhesive layer stacked on a base material layer. The adhesive layer comprises: (A) an organopolysiloxane containing two or more alkenyl groups; (B) a resinous copolymer comprising mainly of RSiOunits and SiOunits; (C) an organohydrogenpolysiloxane containing two or more SiH groups; and (D) a cured product of addition reaction-curable silicone composition containing addition reaction catalyst. The hardness after curing is 3 to 20 measured by a CSR-2 type hardness tester. The base material layer is made of a cured product of an elastomer composition which does not contain silicone as a main component polymer and contains the above-mentioned components (C) and (D).EFFECT: A waterproof sheet is laid for water intrusion in a boundary part between a bottom side of an outdoor tank and a foundation part, with stable adhesion characteristics maintained over a long period of time, as well as characteristics that can withstand impact of falling objects and the like, so that rainwater intrusion thereinto due to damage, would hardly occur to inhibit deterioration of the layered structure, thereby enabling long-term use.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a waterproof sheet and waterproof construction that are effectively used to prevent the intrusion of rainwater into the boundary between the bottom side and the base portion of a large tank that is often installed in outdoor tanks, particularly refineries. Regarding the method.

  Conventionally, outdoor tanks, mainly large tanks installed mainly in refineries, have had a problem in terms of rainwater intrusion into the boundary between the bottom side and the base part. As a countermeasure against this problem, it has been practiced to prevent the intrusion of rainwater by covering the boundary portion with a weakly viscous rubber sheet in which a sealant layer is laminated. However, weakly viscous rubber sheets are made of synthetic rubber such as natural rubber and unvulcanized butyl rubber, and have problems with weather resistance, heat resistance, and cold resistance. There was a risk of rusting at the bottom and damage to the tank (Patent Document 1).

  Further, as an example other than the silicone waterproof sheet, it has been proposed to use an EPDM vulcanized rubber as a sealing material. In the sealing material that stops water between the installation base and the bottom plate of the storage tank, a flexible member is provided with a letter-shaped folded part, and the folded part lower surface and the other lower surface of the flexible member are Each is provided with a self-adhesive layer of unvulcanized butyl rubber as a watertight attachment part to the installation base or the bottom of the storage tank (Patent Document 2). However, it has been confirmed that unvulcanized butyl rubber easily peels from the mortar application surface as a result of a water immersion test by the present inventor, and it is difficult to say that it has a satisfactory waterproof function.

  Further, a waterproof sheet is proposed in which a fiber reinforcing layer is sandwiched between butyl-based pressure-sensitive adhesives on an EPDM sheet having a thickness of 1 mm (Patent Document 3). Since these adhesive layers are butyl-based, it is difficult to say that they have a satisfactory waterproof function as described above.

  Aiming to prevent rainwater from entering by covering the boundary with a waterproof sheet in which a silicone rubber sheet is integrated into a silicone rubber sheet with a silicone rubber sheet that is excellent in weather resistance, heat resistance, and cold resistance. (Patent Document 4). Although this silicone rubber waterproof sheet is excellent in weather resistance, heat resistance, and cold resistance, it has been confirmed that there are a few cases of damage when actually constructed. As an example, when the upper part of a tank freezes in a cold area, the frozen thing falls and it was confirmed that it was damaged by impact. Several cases of damage from small animals have also been confirmed. They have been found to have been damaged by crowing. According to Utsunomiya University's Department of Agriculture ecology research of crows, it is a silicone rubber with less odor than synthetic rubber, with moderate elongation and hardness (100-500% elongation as a guide, hardness (durometer A) 50-80) Things may be of interest to crows who have tasted the touch and appear to be damaged.

Japanese Patent Laid-Open No. 8-198384 JP 2000-309394 A JP-A-3-190730 JP 2012-215057 A

  The present invention has been made in view of the above circumstances, and in a waterproof sheet laid for the purpose of intrusion of rainwater at the boundary portion between the bottom side of the outdoor tank and the base portion, while maintaining stable adhesion characteristics over a long period of time. An object of the present invention is to provide a waterproof sheet that can withstand the impact of falling objects and the damage of small animals. In addition, by laying a waterproof sheet with impact resistance as well as sticking properties, it is difficult for the waterproof sheet to peel or break for a long period of time, and to suppress deterioration due to moisture in the structure for a long period of time. It aims at providing the waterproof construction method which can do.

（式中、ｎは０〜１０の整数であり、Ｒ¹は水素原子又は炭素数１〜１０のアルキル基であり、Ｒ²は水素原子又は炭素数１〜５のアルキル基である。）

（式中、Ｒ³は水素原子又は炭素数１〜１０のアルキル基である。）
で示される少なくとも１種のノルボルネン化合物よりなる、エチレン・α−オレフィン・非共役ポリエンランダム共重合体ゴムを含む組成物である［１］記載の防水シート。
［３］
（Ａ）成分の配合量が、（Ａ）及び（Ｂ）成分の合計１００質量部に対して２０〜１００質量部であり、（Ｂ）成分の配合量が、（Ａ）及び（Ｂ）成分の合計１００質量部に対して０〜８０質量部である［１］又は［２］記載の防水シート。
［４］
付加反応硬化型シリコーン組成物における（Ｃ）成分の配合量が、（Ａ）及び（Ｂ）成分の合計１００質量部に対して０．５〜２０質量部である［１］〜［３］のいずれかに載の防水シート。
［５］
（Ｅ）成分において、（ａ）エチレン単位と（ｂ）α−オレフィン単位のモル比［（ａ）／（ｂ）］が４０／６０〜９５／５である［２］〜［４］のいずれかに記載の防水シート。
［６］
（Ｅ）成分のアルケニル基の含有量が０．０００１〜０．０１モル／ｇである［２］〜［５］のいずれかに記載の防水シート。
［７］
エラストマー組成物の硬化物のデュロメータータイプＡ硬さが３０〜９０である［１］〜［６］のいずれかに記載の防水シート。
［８］
エラストマー組成物に、更に、ゴム補強剤及び／又は無機充填剤を含有する［１］〜［７］のいずれかに記載の防水シート。
［９］
［１］〜［８］のいずれかに記載の複数の防水シートを併設して、水分の浸入を防止する箇所を含む部分を液密に被覆すると共に、互いに隣接する上記防水シートを重なり部分の幅を５ｍｍ以上として液密に重ね合せて貼着するようにした防水シートの防水施工方法。 In order to achieve the above object, the present invention provides the following elastomer waterproof sheet and waterproof construction method.
[1]
It is a waterproof sheet formed by laminating an adhesive layer on a base material layer, and the adhesive layer is
(A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule;
(B) R ² ₃ SiO _1/2 unit (wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group, but R ² contains an alkenyl group) and SiO ₂ unit as main components Resinous copolymer,
(C) an organohydrogenpolysiloxane containing at least two hydrogen atoms (SiH groups) bonded to silicon atoms,
(D) It consists of a cured product of an addition reaction curable silicone composition containing an addition reaction catalyst, and the hardness of the cured product is 3 to 20 by a CSR-2 type hardness meter,
A waterproof sheet, wherein the base material layer is made of a cured product of an elastomer composition containing no silicone in a main component polymer and containing the components (C) and (D).
[2]
In the elastomer composition, (E) the non-conjugated polyene is represented by the following general formula (1) or (2):

(In the formula, n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

(In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The waterproof sheet according to [1], which is a composition comprising an ethylene / α-olefin / non-conjugated polyene random copolymer rubber comprising at least one norbornene compound represented by the formula:
[3]
The blending amount of the component (A) is 20 to 100 parts by mass with respect to 100 parts by mass in total of the components (A) and (B), and the blending amount of the component (B) is the components (A) and (B). The waterproof sheet according to [1] or [2], which is 0 to 80 parts by mass with respect to 100 parts by mass in total.
[4]
[1] to [3] in which the blending amount of the component (C) in the addition reaction curable silicone composition is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). One of the waterproof sheets.
[5]
In the component (E), any one of [2] to [4], wherein the molar ratio [(a) / (b)] of (a) ethylene unit and (b) α-olefin unit is 40/60 to 95/5 The tarpaulin according to crab.
[6]
(E) The waterproof sheet in any one of [2]-[5] whose content of the alkenyl group of a component is 0.0001-0.01 mol / g.
[7]
The waterproof sheet according to any one of [1] to [6], wherein the durometer type A hardness of the cured product of the elastomer composition is 30 to 90.
[8]
The waterproof sheet according to any one of [1] to [7], wherein the elastomer composition further contains a rubber reinforcing agent and / or an inorganic filler.
[9]
A plurality of waterproof sheets according to any one of [1] to [8] are provided side by side to liquid-tightly cover a portion including a portion that prevents moisture from entering, and the adjacent waterproof sheets are overlapped with each other. A waterproof construction method for a waterproof sheet that has a width of 5 mm or more and is adhered in a liquid-tight manner.

  The waterproof sheet of the present invention is laid for the purpose of intrusion of rainwater at the boundary between the bottom side of the outdoor tank and the base part, and maintains stable sticking characteristics over a long period of time. Therefore, it is difficult for rainwater to enter due to breakage, and the deterioration of the laid structure is suppressed, thereby enabling long-term use. In addition, the waterproof construction method according to the present invention can effectively suppress deterioration of a laid structure, and enables long-term use.

It is sectional drawing which shows one Example of the waterproof sheet which concerns on this invention. It is a schematic sectional drawing which shows the installation state of an outdoor tank. It is sectional drawing to which the boundary part of the base in FIG. 2 and an outdoor tank was expanded. 1 shows an embodiment of a waterproof construction method for a waterproof sheet according to the present invention, and is a schematic cross-sectional view showing a state where the waterproof sheet of FIG. 1 is adhered to a boundary portion between a bottom portion (annular plate) and a base portion of an outdoor tank. It is. In the Example shown in FIG. 4, it is the top view which expanded a part of construction part which stuck the some waterproof sheet to the boundary part of the bottom part side (annular board) of an outdoor tank, and a base part.

The present invention will be described in further detail below.
In FIG. 1, sectional drawing explaining the structure of the waterproof sheet of this invention is shown. As shown in FIG. 1, the waterproof sheet 10 of the present invention is formed by laminating an adhesive layer 12 on one side of a base material layer 11, and a protective film 13 is usually laminated on the adhesive layer 12 in a peelable manner. Is done. At the time of use, the protective film 13 is peeled off, and the adhesive layer 12 is adhered to a required place.

The adhesive layer 12 uses a cured product of an addition reaction curable silicone composition. The silicone composition is
(A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule;
(B) R ² ₃ SiO _1/2 unit (wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group, but R ² contains an alkenyl group) and SiO ₂ unit as main components Resinous copolymer,
(C) an organohydrogenpolysiloxane containing at least two hydrogen atoms (SiH groups) bonded to silicon atoms,
(D) It is an addition reaction curable silicone composition containing an addition reaction catalyst, and the hardness after curing is 3 to 20 by a CSR-2 type hardness meter.

The component (A) of the addition reaction curable silicone composition is an organopolysiloxane having an average of at least two alkenyl groups in one molecule, and the organopolysiloxane of the component (A) includes the following average composition formula: (I)
R ¹ _a SiO _{(4-a) / 2} (I)
What is shown by is used.
In the formula, R ¹ is an identical or different monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and a is 1.5 to 2.8, preferably 1. It is a positive number in the range of 8 to 2.5, more preferably 1.95 to 2.05. Here, as the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ¹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl Aralkyl groups such as groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups and other alkenyl groups, and some or all of the hydrogen atoms of these groups are fluorine. Substituted with halogen atoms such as bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropro Group, bromoethyl group, trifluoropropyl group, but cyanoethyl group and the like, Preferably, at least 90 mol% of all R ¹ is a methyl group.

In this case, at least two of R ¹ must be alkenyl groups (preferably having 2 to 8 carbon atoms, more preferably 2 to 6). The content of alkenyl group, the total organic groups (i.e., monovalent hydrocarbon radical unsubstituted or substituted above) in R ^1, 0.00001~0.05mol / g, preferably 0.00001 to 0. It is preferable to be 01 mol / g. This alkenyl group may be bonded to a silicon atom at the end of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain, or may be bonded to both. Those containing bonded alkenyl groups are preferred. If the alkenyl group content is less than 0.00001 mol / g, sufficient rubber-like physical properties cannot be obtained, and if it is more than 0.05 mol / g, the hardness becomes too high and the adhesive strength may be reduced. There is.

Although there is no restriction | limiting in particular about a polymerization degree, A liquid thing is preferable at normal temperature. Usually, those having an average degree of polymerization in terms of polystyrene by gel permeation chromatography (GPC) of 50 to 20,000, preferably 100 to 10,000, more preferably about 100 to 2,000 are preferably used.
The structure of this organopolysiloxane is basically composed of a repeating main chain consisting of diorganosiloxane units (R ¹ ₂ SiO _2/2 ), and both ends of the molecular chain are triorganosiloxy groups (R ¹ ₃ SiO _{1 / 2} ) or a linear structure blocked with a hydroxydiorganosiloxy group ((HO) R ¹ ₂ SiO _1/2 ), but may be partially a branched structure, a cyclic structure or the like.

The resinous copolymer (that is, a copolymer having a three-dimensional network structure) as the component (B) has R ² ₃ SiO _1/2 units and SiO ₂ units as main components. Here, R ² is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and examples of the monovalent hydrocarbon group represented by R ² include a methyl group, Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group Aryl groups such as xylyl group and naphthyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl Alkenyl groups such as groups, some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc. Examples thereof include chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group and the like.

The resinous copolymer of component (B) may be composed only of the above R ² SiO _1/2 units and SiO ₂ units, and if necessary, R ² ₂ SiO units or R ² SiO _{3 / 2} units (R ² are as defined above) as the total amount of these with respect to the total copolymer mass, 50% or less, and preferably may comprise from 40% or less, R ² ₃ SiO _1/2 units And the SiO ₂ unit molar ratio [R ² ₃ SiO _1/2 / SiO ₂ ] is preferably 0.5 to 1.5, particularly preferably 0.5 to 1.3. Even if this molar ratio is smaller than 0.5 or larger than 1.5, sufficient hardness and strength cannot be obtained. Furthermore, the resinous copolymer of component (B) preferably has at least two alkenyl groups in one molecule, and the content of alkenyl groups is 0.0001 mol / g or more, preferably 0.0001. It is -0.003 mol / g, More preferably, it is the range of 0.0002-0.002 mol / g. If the alkenyl group content is less than 0.0001 mol / g, sufficient rubber-like physical properties cannot be obtained, and if it exceeds 0.003 mol / g, the hardness becomes too high and the adhesive force may be reduced. There is.
The resinous copolymer may be a liquid (for example, 10 mPa · s or more, preferably 50 mPa · s or more) having fluidity at room temperature (25 ° C.) or a solid having no fluidity. . In the case of a solid, it may be in a state dissolved in an organic solvent such as toluene. This resinous copolymer can be usually produced by hydrolyzing an appropriate chlorosilane or alkoxysilane by a method well known in the art.

  The blending amount of the components (A) and (B) is 20 to 100 parts by mass, preferably 20 to 90 parts by mass, with the component (A) being 100 parts by mass when the total of the components (A) and (B) is 100 parts by mass. In particular, the range of 30 to 90 parts by mass, and the component (B) is 0 to 80 parts by mass, preferably 10 to 80 parts by mass, and particularly preferably 10 to 70 parts by mass. When there are too few (A) components, ie, there are too many (B) components, rubber-like physical property will fall remarkably. From the viewpoint of adhesiveness and strength, it is preferable to use the component (B) in combination with the component (A).

The component (C) is an organohydrogenpolysiloxane having at least 2, preferably 3 or more hydrogen atoms (SiH groups) bonded to silicon atoms, and the SiH group in the molecule is the above (A). The alkenyl group bonded to the silicon atom in the component and component (B) is cross-linked by a hydrosilylation addition reaction, and acts as a curing agent for curing the composition. The organohydrogenpolysiloxane of component (C) has the following average composition formula (II)
R ³ _b H _c SiO _{(4-bc) / 2} (II)
(Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, b is 0.7 to 2.1, c is 0.001 to 1.0, and b + c is a positive number satisfying 0.8 to 3.0.)
And those having at least 2 (usually 2 to 200), preferably 3 to 100, more preferably 3 to 50 silicon atom-bonded hydrogen atoms in one molecule are suitably used. Here, examples of the monovalent hydrocarbon group for R ³ include the same groups as those exemplified for R ¹ , but those having no aliphatic unsaturated group are preferred. Further, b is preferably 0.8 to 2.0, c is preferably 0.01 to 1.0, b + c is preferably 1.0 to 2.5, and the molecular structure of the organohydrogenpolysiloxane is: The structure may be any of linear, cyclic, branched, and three-dimensional network. In this case, the number of silicon atoms in one molecule (or the degree of polymerization) is preferably 2 to 300, particularly about 4 to 150 at room temperature (25 ° C.). In addition, the hydrogen atom bonded to the silicon atom may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both, but at the molecular chain end where the reaction rate is fast Is preferred. That is, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group Blocked dimethylsiloxane / methylhydrogensiloxane copolymer, a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units and SiO _{4/2 Examples} thereof include a copolymer comprising units and (C ₆ H ₅ ) SiO _3/2 units.

The compounding amount of the organohydrogenpolysiloxane of the component (C) is 0.5 to 20 parts by mass, particularly 1.0 to 10 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). . If the amount is too small or too large, sufficient strength cannot be obtained. The organohydrogenpolysiloxane of component (C) is composed of hydrogen atoms (SiH bonded to silicon atoms in component (C) with respect to alkenyl groups bonded to silicon atoms included in components (A) and (B). The amount of the group) is 0.5 to 1.1, more preferably 0.6 to 1.0 in terms of molar ratio. And when it assumes that 100% addition crosslinking reaction advances, it is preferable to mix | blend the quantity whose organohydrogenpolysiloxane will be 0.005-0.01 mol / g.
Here, the molar ratio of SiH groups of component (C) to the amount of alkenyl groups present in the system is shown as H / Vi, and the theoretical amount of cross-linking is the amount of (C) component added in the system. This is the amount of crosslinking when a hydrogen atom (SiH group) bonded to a silicon atom and an alkenyl group present in the system react 100%. That is, when H / Vi is 1 or less, the amount of SiH groups is the theoretical crosslinking amount, and when H / Vi is 1 or more, the amount of alkenyl groups is the theoretical crosslinking amount. The amount of these functional groups may be an amount based on a calculation formula at the time of designing the composition, but it is more preferable to use an actual measurement value. The actual measurement of the amount of functional groups is carried out by measuring the amount of hydrogen gas generated or unsaturated groups, analysis by NMR, etc. by a known analysis method. The amount of functional groups in the system is represented by X × Y mol / g when the amount of functional groups in the molecule is X mol / g and the amount added is Y parts by mass.

  The component (D) may be a conventionally known one, and is usually a platinum group metal-based addition reaction catalyst represented by platinum or a platinum compound (usually the total alkenyl group-containing organopolysiloxane of the components (A) and (B)). 1 to 1,000 ppm) is used.

  The pressure-sensitive adhesive layer 12 exhibits pressure-sensitive adhesiveness even in an unvulcanized state, but it is preferable that the change with time is less when it is assumed to be used for a long time. The change with time is less when the adhesive layer is vulcanized. The vulcanization method is not particularly limited, but a type in which an adhesive layer is already vulcanized to form an adhesive layer is preferable to a type that is cured at the work site.

  The hardness of the pressure-sensitive adhesive layer 12 obtained by using the silicone composition is smaller than the hardness of the base material layer 11, and is preferably less than 10 in Asker C hardness. If the hardness exceeds 10, the adhesiveness may decrease. More preferably, it is preferably 3 to 20, more preferably 10 to 18 by an Asker CSR-2 type hardness meter suitable for measuring hardness lower than Asker C hardness.

  Further, in accordance with JIS Z 0237, it is preferable that the adhesive strength is 5 N / 25 mm or more when adhered to a mortar test piece and subjected to a 180 degree peel test at a peeling rate of 300 mm / min. Preferably it is the range of 5-30 N / 25mm. If it is less than 5 N / 25 mm, when the adhesive layer is stuck to the desired adherend, the adhesive strength to the adherend is low and there is a problem with sticking. If it exceeds 30 N / 25 mm, reworkability and reattachability May cause problems.

  In addition to the above-described components, the composition forming the adhesive layer 12 includes, as necessary, other components such as fumed silica, precipitated silica, quartz powder, diatomaceous earth, and calcium carbonate. Further, a filler such as carbon black, conductive zinc white, conductive agent such as metal powder, and heat-resistant agent such as iron oxide and cerium oxide may be blended. Furthermore, hydrosilylation reaction control agents such as nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, sulfur compounds, internal mold release agents such as dimethyl silicone oil, adhesion imparting agents, thixotropes It is optional to add a property-imparting agent or the like.

The base material layer 11 is preferably made of a composition containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber as an elastomer that is excellent in cold resistance, heat resistance and weather resistance and can withstand impact.
The base material layer 11 does not contain silicone as a main component polymer, includes the following component (E) as a main component, and uses an elastomer composition including the above components (C) and (D). It is formed.

The component (E) includes a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from at least one non-conjugated polyene.
More specifically, the non-conjugated polyene includes an ethylene / α-olefin / non-conjugated polyene random copolymer rubber made of at least one norbornene compound represented by the following general formula (1) or (2).

（式中、ｎは０〜１０の整数であり、Ｒ¹は水素原子又は炭素数１〜１０のアルキル基であり、Ｒ²は水素原子又は炭素数１〜５のアルキル基である。）

（式中、Ｒ³は水素原子又は炭素数１〜１０のアルキル基である。）

(In the formula, n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

(In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

  In the ethylene / α-olefin / non-conjugated polyene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter also simply referred to as “α-olefin”) is flexible to the component (E) (low crystal Sex). The carbon number of the α-olefin is preferably 3 to 8 from the viewpoints of raw material costs, mechanical properties of the copolymer of the present invention, and rubber elasticity of a molded product obtained from the composition containing the copolymer. Examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1 -Tetradecene, 1-hexadecene, 1-eicosene and the like. Of these, propylene, 1-butene, 1-hexene and 1-octene are preferable. These α-olefins may be used singly or in combination of two or more.

The ratio of the structural unit derived from the α-olefin in the entire structural unit of the copolymer of the present invention can be measured by various known methods, and can be determined, for example, by measuring ¹ H-NMR spectrum.

  The structural unit derived from the non-conjugated polyene imparts crosslinking reactivity to the component (E). The non-conjugated polyene is not particularly limited as long as it has two or more double bonds and the double bonds are not conjugated to each other, but from the viewpoint of cost, a non-conjugated diene having 5 to 20 carbon atoms is preferable, and carbon A non-conjugated diene having a number of 5 to 15 is more preferable. Examples of such non-conjugated dienes include 5-ethylidene-2-norbornene (hereinafter referred to as ENB), dicyclopentadiene, 5-vinyl-2-norbornene (hereinafter referred to as VNB), norbornadiene and methyltetrahydroindene. Examples of chain non-conjugated dienes include 1,4-hexadiene and 7-methyl-1,6-octadiene. Of these, ENB and VNB are preferred. These non-conjugated polyenes may be used singly or in combination of two or more.

The ratio of the structural unit derived from the non-conjugated polyene in the total structural unit of the copolymer of the present invention can be measured by various known methods, and can be determined, for example, by measuring ¹ H-NMR spectrum.

  The component (E) has a molar ratio [(a) / (b)] of (a) ethylene units to (b) α-olefin units of 40/60 to 95/5, preferably 50/50 to 90/10. More preferably, it is contained at a ratio of 55/45 to 85/15. When this molar ratio is within the above range, an elastomer composition that provides the base material layer 11 that is particularly excellent in heat resistance, strength characteristics, rubber elasticity, and in cold resistance and processability is obtained.

  In addition, the content of the non-conjugated polyene-derived alkenyl group (terminal vinyl group) in the copolymerized ethylene / α-olefin / non-conjugated polyene random copolymer rubber is 0.0001-0. It is preferably blended at a rate of 01 mol / g, particularly 0.0002 to 0.005 mol / g. If the alkenyl group (terminal vinyl group) content is too small, a cured product having sufficient rubber properties may not be obtained, and if it is too large, the cured product may be hard and brittle.

  Moreover, 0.5-50 (g / 100g) is preferable, as for the iodine value of (E) component, 0.8-40 (g / 100g) is more preferable, and 1-30 (g / 100g) is still more preferable. If the iodine value is less than 0.5 (g / 100 g), the degree of crosslinking may be reduced, and the rubber physical properties may be insufficient. If the iodine value exceeds 50 (g / 100 g), the fluidity will deteriorate. As a result, there may be a problem in workability.

  Examples of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber include Keltan series (manufactured by LANXESS), which is an ethylene / propylene / ENB copolymer. Among them, Keltan 2650 (125 ° C Mooney viscosity 25, ethylene content 53 mass%, ENB amount 6.0 mass%), Keltan 2450 (125 ° C Mooney viscosity 28, ethylene content 48 mass%, ENB amount 4.1 mass%) ) And the like, but are not particularly limited thereto.

As the component (C), the same components as those which can be used in the addition reaction curable silicone composition can be used.
1-20 mass parts is preferable with respect to 100 mass parts of (E) component mentioned later, and, as for the compounding quantity of the said (C) component organohydrogen polysiloxane in an elastomer composition, 1-10 mass parts is more preferable. If the blending amount is too small or too large, sufficient rubber properties cannot be obtained.

  The component (D) can be the same as that used in the above addition reaction curable silicone composition, and is usually a platinum group metal addition reaction catalyst represented by platinum or a platinum compound (usually ( C) and a component containing (E) about 1 to 1,000 ppm).

  In the composition for forming the base material layer 11, conventionally known additives such as rubber reinforcing agents, inorganic fillers, softeners, anti-aging agents, colorants, dispersants, flame retardants, and the like are used for the purpose of the present invention. It can mix | blend in the range which is not impaired.

The rubber reinforcing agent has an effect of increasing mechanical strength such as tensile strength, tear strength, and wear resistance of the crosslinked rubber. Specific examples of such rubber reinforcing agents include carbons such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT, and those carbons that have been surface-treated with a silane coupling agent. Examples thereof include black, finely divided silicic acid, and silica. Specific examples of silica include fumed silica and precipitated silica. These silicas may be surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane. The specific surface area of silica (BET method) is preferably 50 m ² / g or more, more preferably 100 to 400 m ² / g.
The type and blending amount of these rubber reinforcing agents can be appropriately selected. The blending amount of the rubber reinforcing agent is 300 parts by mass or less with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber. Is preferable, and 200 parts by mass or less is more preferable. The lower limit is not particularly limited, but when a rubber reinforcing agent is blended, the blending amount is preferably 10 parts by mass or more with respect to 100 parts by mass of ethylene / α-olefin / non-conjugated polyene random copolymer rubber, and 20 masses. Part or more is more preferable.

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.
Although the kind and compounding quantity of these inorganic fillers can be selected suitably, the compounding quantity of an inorganic filler is 300 mass parts or less with respect to 100 mass parts of ethylene, alpha-olefin, and nonconjugated polyene random copolymer rubber. Is preferable, and 200 parts by mass or less is more preferable. Although a minimum in particular is not restrict | limited, When mix | blending an inorganic filler, 30 mass parts or more are preferable with respect to 100 mass parts of ethylene, alpha-olefin, and nonconjugated polyene random copolymer rubber, and 50 masses. Part or more is more preferable.

  As the softener, a softener usually used for rubber can be used. Specific examples include process oil, lubricating oil, paraffin, liquid paraffin, and the like. The blending amount of these softeners is appropriately selected depending on the use of the crosslinked product.

  The anti-aging agent is preferably a hindered phenol-based anti-aging agent that hardly causes vulcanization inhibition.

  Since the elastomer composition is more excellent in rubber elasticity than being uncured, the elastomer composition is more likely to exhibit its characteristics. Usually, ethylene / α-olefin / non-conjugated polyene random copolymer rubbers are cured by sulfur vulcanization or organic peroxide vulcanization. It is difficult to stack as a layer, and the object of the present invention cannot be achieved.

  In addition to the ethylene / α-olefin / non-conjugated polyene random copolymer rubber, the elastomer composition includes an organohydrogenpolysiloxane having at least two SiH groups in one molecule, and an addition reaction catalyst, A cured product is obtained by addition reaction containing a reaction control agent. As described above, additives such as conventionally known rubber reinforcing agents, inorganic fillers, softeners, anti-aging agents, colorants, dispersants, flame retardants, and the like can be blended within a range that does not impair the object of the present invention. . The reaction inhibitor may be a known one, but an unsaturated group-containing compound is preferred. Of these, vinyl group-containing organopolysiloxanes such as cyclic vinylmethylsiloxane (V-4) and ethynyl group-containing alcohols such as ethynylcyclohexanol are preferably used.

  The elastomer composition can be cross-linked by extrusion molding, calender molding, press molding, injection molding, transfer molding, or dissolved in an arbitrary solvent and coating molding. Usually, the composition is cured by heating at a temperature of 100 to 300 ° C. for 1 to 30 minutes. In this curing, molding by atmospheric pressure hot air vulcanization (HAV) or steam vulcanization is also possible. In the present invention, since it is desirable to form into a sheet, calendar molding and coating molding are particularly preferable. This sheet-like molded product is used as a base material layer.

  Although the rubber physical property after hardening of the said elastomer composition is not specifically limited, What is necessary is just to show a rubber characteristic in the hardened state. As a guideline, it is preferable that the touch is not extremely sticky. The rubber physical property is preferably a durometer type A hardness of 30 to 90, more preferably 50 to 85, in a measuring method based on JIS K 6249. The tensile strength is preferably 2 MPa or more, and more preferably 3 MPa or more. The elongation is preferably 50 to 800%, more preferably 100 to 600%. The tear strength is preferably 10 kN / m or more, and more preferably 15 kN / m or more. If these physical properties are out of the range, the surface of the waterproof sheet may be easily damaged or damaged.

  In addition to the above-described components, the composition for forming the base material layer 11 includes, as necessary, other components such as fumed silica, precipitated silica, quartz powder, diatomaceous earth, and calcium carbonate. Alternatively, a filler such as carbon black, conductive zinc white, conductive agent such as metal powder, and heat-resistant agent such as iron oxide and cerium oxide may be blended. Furthermore, it is optional to add a hydrosilylation reaction control agent such as a nitrogen-containing compound, an acetylene compound, a phosphorus compound, a nitrile compound, a carboxylate, a tin compound, a mercury compound, or a sulfur compound.

  The thickness of the waterproof sheet 10 is preferably 0.7 to 6 mm. Among these, the thickness of the base material layer 11 is 0.2-3 mm, Preferably it is 0.2-1.5 mm. If the thickness of the base material layer 11 is less than 0.2 mm, it may be insufficient for taking advantage of the elasticity of the sheet. If the thickness exceeds 3 mm, the weight increases, affecting the attachment, and disadvantageous in terms of cost. May occur. Moreover, the thickness of the adhesion layer 12 has the preferable range of 0.5-3 mm, More preferably, it is the range of 0.5-2 mm. If the thickness of the pressure-sensitive adhesive layer 12 is less than 0.5 mm, the pressure-sensitive adhesive layer 12 cannot absorb the surface irregularities of the adherend, and if it exceeds 3 mm, the rubber strength of the sticking surface depends on the strength of the pressure-sensitive adhesive layer 12. It may cause rubber destruction.

In the waterproof sheet 10 of the present invention, the adhesive layer 12 is laminated on the base material layer 11, and the adhesive layer 12 is formed after the composition forming the base material layer is cured to form the base material layer 11. Alternatively, the composition for forming the base material layer is calendered on a film of polyethylene terephthalate (PET) or the like and dispensed, and the composition for forming the adhesive layer in an unvulcanized state is laminated. May be.
The composition for forming the adhesive layer is preferable because there is a method for obtaining a laminated sheet by a method such as dipping, coating or screen printing on the composition for forming the base material layer, and coating molding can be suitably used. In addition, as these hardening conditions, the range of 10 second-1 hour is preferable at 80-250 degreeC. Further, after-curing may be performed at 120 to 250 ° C. for about 1 to 100 hours for the purpose of removing low molecular components.

  Here, the waterproof sheet of the present invention is used by laying mainly for the purpose of intrusion of rainwater at the boundary between the bottom side of the outdoor tank and the base portion. An example of the method will be described.

  FIG. 2 is a schematic cross-sectional view showing an installation state of the outdoor tank. In the figure, the outdoor tank 30 is supported and installed on a concrete base 20. The outdoor tank 30 contains contents such as petroleum, asphalt, and various gases. The outdoor tank 30 has a generally cylindrical shape, and generally has a diameter of 10 to 80 m and a height of 10 to 50 m. In FIG. 2, reference numeral 21 denotes the ground, and reference numeral 40 denotes icing matter adhering to the upper part of the outdoor tank 30. The tank bottom of the outdoor tank 30 is constituted by an annular plate 31, and it is possible to prevent the intrusion of rainwater for a long time by completely covering with a waterproof sheet without exposing the boundary portion 32 between the base 20 and the annular plate 31. it can. The base is made of concrete, mortar, asphalt concrete, asphalt mortar, asphalt sand, or a combination thereof. Reference numeral 33 denotes a side surface of the tank.

  FIG. 3 is an enlarged view of the boundary portion 32 between the base 20 and the outdoor tank 30 in FIG. 2. In such a case, rainwater or the like may enter from the boundary portion 32 exposed to the outside, and if rainwater enters here, rust is generated in the tank 30.

4 and 5 show a state where the waterproof sheet 10 of the present invention is laid and waterproofed.
FIG. 4 is a cross-sectional view showing a state in which the waterproof sheet 10 of the present invention is laid and covers the boundary portion 32, and FIG. 5 is a construction in which a plurality of waterproof sheets 10 are adhered to the boundary portion 32. It is a top view which shows a part.

As shown in FIG. 4, the waterproof sheet 10 is placed in close contact with the base 20 and the outdoor tank 30 so as to cover the boundary portion 32. As shown in FIG. 5, normally, a plurality of waterproof sheets 10 are used, these plural sheets are juxtaposed along the boundary portion 32, and the entire boundary portion is covered with the waterproof sheet 10. In this case, the adjacent sheets 10 and 10 are preferably overlapped with each other, and the width of the overlapping portion is preferably 5 to 50 mm, and more preferably 10 to 20 mm. If the width of the overlapping portion is smaller than 5 mm, peeling may occur during construction, the boundary portion cannot be completely covered, and the waterproof function may not be achieved. If it is 50 mm or more, the necessary amount of the waterproof sheet for covering the boundary portion increases, resulting in high cost.
In the present invention, by using the waterproof sheet 10 having the above-described configuration, the iced product 40 shown in FIG. 2 is not easily dropped or damaged by a small animal, and the waterproof performance is maintained for a long time. .

  The sealing material is not necessarily used when the waterproof sheet is attached, but a sealing material may be used at the boundary portion of the sheet or the overlapping portion of the sheet in order to adhere more firmly. In addition, there is no restriction | limiting in particular as a sealing material, Although any things, such as a well-known silicone type, polysulfide type, and a polyurethane type, can be used, A silicone sealing material is used suitably. A commercially available product may be used as such a sealant. For example, as a silicone sealant, sealant master 300, sealant 70, sealant 701 and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Polymer Ace HJ-14S and HJ-1588L manufactured by Shin-Etsu Polymer Co., Ltd. can also be used as a sealing material. About these, even if it used for the waterproof sheet of this invention, it confirmed that there was no special problem in sclerosis | hardenability and sealing property.

  The sticking of the waterproof sheet may be performed by pre-processing the sticking construction part so that the sheet is easy to stick. Since the waterproof sheet is sticky, pretreatment with a primer or the like is not required for the purpose of improving the stickiness of the pasting part. Adhesion is performed with the adhesive side as the adhesive side. Moreover, when it is assumed that a level | step difference arises in a boundary part and an excessive stress is applied to a sticking surface, it is preferable to implement the means for level | step difference elimination. As the means, for example, there is a method of laying mortar at the level difference or using a backup material.

  By using an adhesive waterproof sheet as the waterproof sheet of the present invention, it becomes possible to perform primer-less construction, and the construction period can be greatly shortened. In addition, it is a great feature that the waterproof function can be exhibited by the adhesive force again.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Example 1]
[Preparation of waterproof sheet A]
As a polyolefin-based synthetic polymer, 100 parts by mass of Keltan 2650 (supra), which is an ethylene / propylene / ENB copolymer, was kneaded for 2 minutes with a pressure kneader (paste kneading step). Thereafter, 15 parts by mass of Nipsil-VN3 (manufactured by Tosoh Silica Co., Ltd.) which is wet silica, 18 parts by mass of Diana Process Oil PW-380 (manufactured by Idemitsu Kosan Co., Ltd.), and a hydroxy having an average polymerization degree of 20-30 as a dispersant 5 parts by mass of terminal methyl vinyl siloxane and hindered phenol antioxidant Irganox-1010 / 1 part by mass were added to a pressure kneader and kneaded for 2 minutes. Thereafter, Nipsil-VN3 was added in 15 parts by mass and kneaded for 2 minutes, and after 60 parts by mass of Nipsil-VN3 had been kneaded, kneaded for another 2 minutes to obtain rubber compound A. The kneading was performed at a preset temperature of the pressure kneader at 120 ° C., and the tap temperature of the rubber compound A at the end of the kneading was 135 ° C.
X-93-1410P-70 / 0.14 parts by mass as an addition reaction catalyst, X-93-1122P-70 / 0.10 parts by mass as a reaction inhibitor, and an addition reaction crosslinking agent were added to the obtained rubber compound A. A certain X-93-1346P-70 / 3.11 parts by mass (both manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed with two rolls, and then heated at 150 ° C. for 10 minutes by press molding to have an average thickness of 0. A base material layer A having a thickness of 7 mm was obtained.

On the other hand, 92.5 parts by mass of dimethylpolysiloxane having an average degree of polymerization of 1,000 having both ends blocked with dimethylvinylsiloxy groups and solid (CH ₂ ═CH) (CH ₃ ) ₂ SiO ₁ at room temperature (25 ° C.) Resin unit copolymer consisting of _{/ 2} units, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units [((CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2 units + (CH ₃ ) ₃ SiO _1/2 unit) / SiO ₂ unit (molar ratio) = 0.85, CH ₂ ═CH—group content: 0.0008 mol / g] A 50% toluene solution containing 7.5 parts by mass was placed in a stirring mixer. After mixing for 30 minutes, toluene was completely distilled off (alkenyl group amount 0.00865 mol / g). A resinous copolymer (SiH group amount 0.0013 mol / g) having SiH groups mainly composed of (CH ₃ ) ₂ HSiO _1/2 units and SiO ₂ units as a crosslinking agent is added to 100 parts by mass of this silicone base. 6.0 parts by mass and 0.1 part by mass of ethynylcyclohexanol as a reaction control agent were added and stirring was continued for 15 minutes to obtain a silicone composition A. The silicone composition A was mixed with 0.2 parts by mass of a platinum catalyst (Pt concentration: 1% by mass) to obtain an adhesive composition A.

  The above base material layer A is laminated and coated with the above-mentioned adhesive composition A to a thickness of 1.0 mm using a desktop coater, and heated and cured in a heating furnace at 140 ° C. for 5 minutes for two layers of waterproofing. A laminated cured sheet A was obtained. The average thickness of the waterproof laminated cured sheet A obtained was 1.7 mm.

[Example 2]
[Preparation of waterproof sheet B]
As a polyolefin-based synthetic polymer, 100 parts by mass of Keltan 2650 (supra), which is an ethylene / propylene / ENB copolymer, was kneaded for 2 minutes with a pressure kneader (paste kneading step). Thereafter, 10 parts by mass of AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.) which is a dry-treated silica, 28 parts by mass of Diana Process Oil PW-380 (manufactured by Idemitsu Kosan Co., Ltd.), and a hydroxy terminal having an average polymerization degree of 20 to 30 as a dispersant 8 parts by mass of methyl vinyl siloxane and hindered phenol antioxidant Irganox-1010 / 1 part by mass were added to a pressure kneader and kneaded for 2 minutes. Thereafter, 10 parts by mass of AEROSIL R972 was added in portions and kneaded for 2 minutes, and after 80 parts by mass of AEROSIL R972 had been kneaded, the mixture was further kneaded for 2 minutes to obtain rubber compound B. The kneading was performed at a preset temperature of the pressure kneader at 120 ° C., and the tap temperature of the rubber compound B at the end of the kneading was 140 ° C.

X-93-1410P-70 / 0.14 parts by mass, X-93-1122P-70 / 0.10 parts by mass, X-93-1346P-70 / 2.32 parts by mass (whichever was obtained) (Shin-Etsu Chemical Co., Ltd.) was added and mixed with two rolls, and then heated at 150 ° C. for 10 minutes by HAV vulcanization to obtain a base layer B having an average thickness of 0.9 mm.
The above-mentioned base material layer B is laminated and coated with the above-mentioned adhesive composition A so as to be 1.0 mm by using a table coater, and is heated and cured in a heating furnace at 140 ° C. for 5 minutes for waterproofing of two layers. A laminated cured sheet B was obtained. The average thickness of the waterproof laminated cured sheet B obtained was 1.9 mm.

[Example 3]
[Preparation of waterproof sheet C]
100 parts by weight of the above rubber compound B is kneaded with a pressure kneader for 1 minute, and then 100 parts by weight of diatomaceous earth (trade name Celite SF, Tokyo Kogyo Shokai Co., Ltd.) and a hydroxy-terminated methyl having an average polymerization degree of 20 to 30 as a dispersant. 6 parts by mass of vinyl siloxane was added with a pressure kneader and kneaded for 2 minutes, and further kneaded for 2 minutes to obtain rubber compound C. The kneading was performed at a preset temperature of the pressure kneader at 120 ° C., and the tap temperature of the rubber compound A at the end of the kneading was 135 ° C.

  X-93-1410P-70 / 0.14 parts by mass, X-93-1122P-70 / 0.10 parts by mass, X-93-1346P-70 / 1.16 parts by mass (whichever is necessary) (Shin-Etsu Chemical Co., Ltd.) was added and mixed with two rolls, and then heated at 150 ° C. for 10 minutes by press molding to obtain a base material layer C having an average thickness of 0.8 mm.

  Using the comma coater, the adhesive composition A was laminated and coated to 1.0 mm on the base material layer C in the same manner as in Example 1, and heated and cured in a heating furnace at 140 ° C. for 5 minutes. A two-layer waterproof laminated cured sheet C was obtained. The average thickness of the waterproof laminated cured sheet C thus obtained was 1.8 mm.

[Example 4]
[Preparation of waterproof sheet D]
As a polyolefin-based synthetic polymer, 100 parts by mass of Keltan 2650 (supra), which is an ethylene / propylene / ENB copolymer, was kneaded for 2 minutes with a pressure kneader (paste kneading step). Thereafter, 65 parts by mass of FEF grade carbon # 60 (manufactured by Asahi Carbon Co., Ltd.), 60 parts by mass of Diana Process Oil PW-380 (manufactured by Idemitsu Kosan Co., Ltd.), 5 masses of vinyl-terminated methylphenylsiloxane having a viscosity of 700 Pa · s. Part, 5 parts by mass of calcium oxide VESTA-20 (manufactured by Inoue Lime Co., Ltd.) was added to the pressure kneader and kneaded for 2 minutes. Thereafter, the above # 60/60 parts by mass were added and kneaded for 2 minutes, and after kneading a total of 125 parts by mass of # 60, the mixture was further kneaded for 2 minutes to obtain a rubber compound D. The kneading was performed at a preset temperature of the pressure kneader at 120 ° C., and the tap temperature of the rubber compound D at the end of the kneading was 125 ° C.
X-93-1410P-70 / 0.14 parts by mass, X-93-1122P-70 / 0.10 parts by mass, and X-93-1346P-70 / 2.39 parts by mass (as a result) (Shin-Etsu Chemical Co., Ltd.) was added and mixed with two rolls and then heated at 150 ° C. for 10 minutes by press molding to obtain a base material layer D having an average thickness of 0.7 mm.

  The base material layer D is coated with the adhesive composition A to a thickness of 1.0 mm using a tabletop coater in the same manner as in Example 1, and is heated and cured in a heating furnace at 140 ° C. for 5 minutes. Thus, a two-layer waterproof laminated cured sheet D was obtained. The average thickness of the waterproof laminated sheet D for waterproofing was 1.7 mm.

[Comparative Example 1]
(Preparation of cured silicone sheet E)
Millable silicone rubber composition KE-675-U (manufactured by Shin-Etsu Chemical Co., Ltd.) as an addition reaction curing agent as a vulcanizing agent C-19A / 1.0 parts by mass, C-19B / 2.5 parts by mass (Both manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed with two rolls, and then formed into a sheet of 0.8 mm thickness on a 100 μm embossed PET film by calendering and continuously heated. Was heated and cured at 140 ° C. for 10 minutes to obtain a base material layer E in a state of being laminated on the PET film.

  Using a comma coater, the adhesive composition A obtained in the same manner as in Example 1 was laminated and coated to 1.0 mm on the base material layer E, and heated in a heating furnace at 140 ° C. for 5 minutes. Curing was conducted to obtain a two-layer waterproof laminated cured sheet E. The average thickness of the waterproof laminated cured sheet E thus obtained was 1.8 mm.

[Comparative Example 2]
(Preparation of cured silicone sheet F)
Addition reaction curable liquid silicone rubber composition KE-1950-60A / KE-1950-60B = 1/1 on IPC spec 1080 glass cloth (thickness 0.055 mm, manufactured by Nittobo Co., Ltd.) A mixed dispersion of Kogyo Kogyo Co., Ltd. was applied to both surfaces of the glass cloth with a coater device, and a base layer F having an average thickness of 0.5 mm was obtained by heat curing in a vulcanizing furnace at 150 ° C. for 15 minutes.

  In the same manner as in Comparative Example 1, the adhesive composition A was laminated and coated on the base material layer F so as to have a thickness of 1.0 mm using a comma coater, and heated and cured in a heating furnace at 140 ° C. for 5 minutes. A four-layer waterproof laminated cured sheet F was obtained. The average thickness of the waterproof laminated cured sheet F obtained was 1.5 mm.

[Comparative Example 3]
The silicone adhesive layer A of Example 1 was tried to be laminated on a commercially available EPDM sheet (Irumagawa Rubber Co., Ltd .: trade name EP-5065, thickness 1 mm), but the adhesive layer was cured at 140 ° C. for 5 minutes. As a result, the target sheet was not obtained.

[Comparative Example 4]
An attempt was made to laminate the silicone adhesive layer A of Example 1 on a commercially available EPDM sheet (manufactured by Irumagawa Rubber Co., Ltd .: trade name EP-5065PO, thickness 1 mm). The adhesive layer was cured at 140 ° C. for 5 minutes. As a result, the target sheet was not obtained.

[Comparative Example 5]
A sealant 45 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a commercially available EPDM sheet (manufactured by Irumagawa Rubber Co., Ltd .: trade name EP-5065, thickness 1 mm). Since 14-15 g of sealant 45 was used on a 15 cm square sheet, the average thickness was calculated to be 0.5 mm from the specific gravity conversion. On top of that, the non-adhesive layer of the sheet E of Comparative Example 1 was laminated within 10 minutes after the sealant 45 was applied. The adhesion was confirmed after standing at room temperature for 24 hours, but the cured sheet of the sealant 45 and EP-5065 were peeled off at the interface, so the target sheet was not obtained.

[Comparative Example 6]
Sealant 45 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a commercially available EPDM sheet (manufactured by Irumagawa Rubber Co., Ltd .: trade name EP-5065PO, thickness 1 mm). Since 14-15 g of sealant 45 was used on a 15 cm square sheet, the average thickness was calculated to be 0.5 mm from the specific gravity conversion. On top of that, the non-adhesive layer of the sheet E of Comparative Example 1 was laminated within 10 minutes after the sealant 45 was applied. Adhesiveness was confirmed after standing at room temperature for 24 hours, but the cured sheet of sealant 45 and EP-5065PO were peeled off at the interface, and the target sheet was not obtained.

  About the obtained waterproof sheet, it tested about each item according to the following procedure. The evaluation results are shown in Tables 1 and 2.

(Hardness of adhesive layer)
About the adhesion layer of the obtained sheet | seat, hardness was measured using the Asker C type hardness meter (The high molecular meter Co., Ltd. make, JISK7312 conformity). In addition, when the C-type hardness meter shows a hardness of less than 1, using a CSR-2 type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.), which is suitable for measuring the hardness in the lower hardness region, It was measured.

(Hardness of base material layer)
About the base material layer of the obtained sheet | seat, the hardness was measured using the durometer type A in the measuring method based on JISK6249.

(Tensile strength, tear strength, elongation at break)
Using the prepared sheet, the tensile strength, tear strength and elongation at break were measured according to JIS K 6249.

(Waterproof test)
Each laminated sheet cut to 200 mm × 25 mm was attached to the center of a mortar test piece having a size of 150 mm × 50 mm × thickness 10 mm, and pressed firmly by hand so that the adhesive layer fits into the mortar. After 1 day at room temperature, the test piece integrated with the mortar test piece was placed in a vat filled with tap water so that the entire test piece was immersed in water. After 7 days had elapsed at room temperature, the test piece was taken out, wiped off moisture on the surface, and then the adhesive strength was measured by a 180-degree peel test.
The measurement of adhesive force was performed at a test speed of 300 mm / min according to the JIS C 2107 adhesive tape test method for electrical insulation.
Device used: Autograph manufactured by Shimadzu Corporation Evaluation was judged to be sufficiently adhesive when it showed a numerical value of 5N or more together with the degree of adhesion by visual observation. When it is smaller than 5N, it peels easily when it is pulled by hand, and when it is 5N or more, a resistance sufficient for peeling by hand is felt, so 5N (/ 25 mm) was set as a threshold value.
○: Adhesive strength after immersion for 7 days at room temperature 5N / 25mm or more X: Adhesive strength after immersion for 7 days at room temperature is less than 5N / 25mm

(Impact resistance test)
This test is carried out by modeling how ice blocks fall from the upper part of the tank shown in FIG. Three mortar test pieces of 150 mm × 50 mm × thickness 10 mm were arranged in the width direction to form 150 mm squares. A sealant master 300 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied thereon to a thickness of 2 mm. The thickness was adjusted by providing a guide around the mortar test piece. Within 10 minutes after application, each laminated sheet cut into 150 mm squares was laminated, allowed to stand at room temperature for 24 hours, and then the guide was removed. Further 48 hours (72 hours in total) were allowed to elapse.
Carbon steel plate test pieces (150 mm × 50 mm × thickness 5 mm, 0.3 kg / sheet) were bundled with four vinyl tapes in the thickness direction to prepare a weight of 1.2 kg. The weight was dropped at an initial speed of zero so as to hit the laminated sheet attached from a position having a height of 2 m. The dropping was repeated up to 5 times, and the state of the sheet after dropping was observed.
○: Dropped 5 times, no damage such as cracks observed.
(Triangle | delta): Although it dropped 5 times and the damage of the sheet | seat surface is observed, the damage has not reached to the mortar.
X: It was dropped 5 times and the damage which reached the mortar was observed one or more places.

DESCRIPTION OF SYMBOLS 10 Waterproof sheet 11 Base material layer 12 Adhesive layer 13 Protective film 20 Base 30 Outdoor tank 31 Tank / annular board (bottom side)
33 Tank / Wall 40 Freeze

Claims (9)

It is a waterproof sheet formed by laminating an adhesive layer on a base material layer, and the adhesive layer is
(A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule;
(B) R ² ₃ SiO _1/2 unit (wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group, but R ² contains an alkenyl group) and SiO ₂ unit as main components Resinous copolymer,
(C) an organohydrogenpolysiloxane containing at least two hydrogen atoms (SiH groups) bonded to silicon atoms,
(D) It consists of a cured product of an addition reaction curable silicone composition containing an addition reaction catalyst, and the hardness of the cured product is 3 to 20 by a CSR-2 type hardness meter,
A waterproof sheet, wherein the base material layer is made of a cured product of an elastomer composition containing no silicone in a main component polymer and containing the components (C) and (D). In the elastomer composition, (E) the non-conjugated polyene is represented by the following general formula (1) or (2):

(In the formula, n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

(In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The waterproof sheet according to claim 1, which is a composition comprising an ethylene / α-olefin / non-conjugated polyene random copolymer rubber comprising at least one norbornene compound represented by the formula:   The blending amount of the component (A) is 20 to 100 parts by mass with respect to 100 parts by mass in total of the components (A) and (B), and the blending amount of the component (B) is the components (A) and (B). The waterproof sheet according to claim 1, wherein the waterproof sheet is 0 to 80 parts by mass with respect to 100 parts by mass in total.   The amount of the component (C) in the addition reaction curable silicone composition is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). 1. The waterproof sheet according to item 1.   The component (E) has a molar ratio [(a) / (b)] of (a) an ethylene unit and (b) an α-olefin unit of 40/60 to 95/5. The waterproof sheet according to item.   (E) The content of the alkenyl group of a component is 0.0001-0.01 mol / g, The waterproof sheet of any one of Claims 2-5.   The waterproof sheet according to any one of claims 1 to 6, wherein the cured product of the elastomer composition has a durometer type A hardness of 30 to 90.   The waterproof sheet according to any one of claims 1 to 7, further comprising a rubber reinforcing agent and / or an inorganic filler in the elastomer composition.   A plurality of waterproof sheets according to any one of claims 1 to 8 are provided side by side to liquid-tightly cover a portion including a portion that prevents moisture from entering, and the adjacent waterproof sheets are overlapped with each other in width. A waterproof construction method for a waterproof sheet in which the thickness is 5 mm or more and liquid-tightly overlapped and adhered.

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