JP2002371799A - Segment sealant and water sealing structure of segment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a segment sealant having high water sealing properties and providing good appearance after construction of segments. SOLUTION: A segment sealant in the form of a strip comprises a principal part I made of water-swelling rubber and fitted into the grooved part of a segment, and an attached part II made of nonwater-swelling rubber and approximately radially connected to the principal part to serve as an open face side when the segments mate with each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-stop material to be installed in a segment groove of a shield tunnel used for a subway, a common conduit for electric wires, a rainwater storage tank, a water supply and a sewage system, and a water-stop structure of a segment using the same. It is about.

[0002]

2. Description of the Related Art Conventionally, the sectional shape of a seal groove of a shield tunnel segment is basically trapezoidal, and a sealing material used for this is a band-shaped unvulcanized rubber molded into a rectangular sectional shape, vulcanized rubber, or the like. For example, vulcanized rubber, sponge rubber, or water-swellable rubber is used. In recent years, segment productivity,
In order to improve the workability and durability, the seal groove of the segment has a semicircular cross-sectional shape (Japanese Patent Application Laid-Open No. Hei 9-195).
No. 692, hereinafter referred to as NM segment) has been proposed and put into practical use.

[0003]

Since the seal groove of the NM segment is smaller than the conventional seal groove, when water is stopped by the water-swellable sealing material, the water-swelling sealing material having excellent shape stability at the time of water expansion is used. , It is necessary to maintain water stoppage. As a sealing material for the NM segment, a core having a hollow portion and made of a non-water-swellable rubber and a water-stopping material made of a water-swellable rubber, and a core made of a non-water-swellable foamed rubber and a water-swellable rubber Water stopping material (Japanese Unexamined Patent Publication No. 9-195692)
Has been proposed. However, the sealing material may not be able to obtain a high water-stopping property due to a change in shape at the time of segment joining, a large dimensional change due to water absorption expansion, and poor shape stability. There was something.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied a segment sealing material having a high water-stopping property and a good appearance after the segment has been applied. Reached. That is, the present invention is the following three inventions. (1) A belt-shaped segment sealing material, which is made of a water-expandable rubber (A), and is composed of a main part (I) fitted into a groove of a segment and a non-water-expandable rubber (B), A segment seal material consisting of an attachment part (II) that is connected almost radially to the opening side when the segments meet. (2) A strip-shaped segment sealing material having a (partial) circular part and a quadrilateral part in cross section, and a solid non-water from the substantially center of the (partial) circular part to the end of the quadrilateral part. A segment sealing material comprising an expandable rubber (B) and a water-expandable rubber (A) extending from the periphery of the (partial) circular portion (B) to the end of the quadrilateral portion. (3) A segment water stopping structure in which any one of the above segment sealing materials is mounted in a segment concave groove having a semicircular or semielliptical cross-sectional shape.

[0005]

FIG. 1 is a sectional view showing an embodiment of a segment sealing material of the first invention, and FIG. 2 is a perspective view showing an embodiment of an NM segment. FIG.
Shows the segment sealing material of the first invention shown in FIG.
It is the perspective view represented in the disassembled state for explaining the water stop structure applied to the M segment. 4 to 11 are sectional views showing other embodiments of the segment sealing material of the first invention.

First, the NM segment in which the segment sealing material of the present invention is used will be described. The segment (6) has a shape as shown in FIGS. 2 and 3, and the material of the segment is not particularly limited. For example, RC
Segment, steel segment and the like. N
As shown in FIGS. 2 and 3, the M-segment includes a step (7) at each joint edge and a plate extending to the step (7) such that the segments (6) are combined with each other. (8) are formed, and at the joint portion between the step (7) and the plate (8), the segment (6) faces the tip end surface of the plate (8) when the segments (6) are connected to each other. A concave groove (9) having a semicircular or semielliptical cross section is formed on the surface. As shown in FIGS. 2 and 3, the segment sealing material (1) of the present invention is mounted in a concave groove (9) formed in the segment (6).

The segment sealing material (1) according to the first aspect of the present invention is a long band-shaped member made of a water-expandable rubber (A), and has a main portion (2) fitted into a groove of a segment. ) And a non-water-swellable rubber (B), which is substantially radially connected to the main part and has an attachment part (3) which is open at the time of segment association. The ratio of the sectional area of the attachment part (3) to the sectional area of the main part (2) is preferably 1: 0.05 to 1: 0.8, more preferably 1: 0.
1-1: 0.5. The cross-sectional shape of the main part (2) is such that the cross-sectional shape is fitted into the groove of the semicircular or semi-elliptical segment, so that one side of the circle or partial circle (2a) or the quadrilateral part (2b) Part) The shape in which the circular portions (2a) are connected is preferable, and the cross-sectional shape of the attachment portion (3) is preferably a quadrilateral in which at least one pair of opposing sides (upper surface and lower surface) are parallel. Here, the circle is used to include an ellipse and its similar shape. In the case of an ellipse, the ratio of the minor axis to the major axis is preferably from 1: 1 to 1: 1.2.

The (partial) circular portion (2a) is shown in FIGS.
As shown in FIG. 11, a circle or an ellipse or one or more (preferably 1 to 3) straight lines are cut out and substantially the same as the concave groove (9) of the segment (6). Is formed by a circle or an ellipse having a curvature of. The angle of the arc of the (partial) circular portion (2a) as viewed from the center of the circle or ellipse is preferably 180 ° or more (semicircle or more). Quadrilateral (2
b) is in contact with the notched portion of the (partial) circular portion (2a) as shown in FIGS. 1, 8 and 11, and at least one pair of opposing sides including the side contacting the partial circle has A parallelogram is preferable, and any shape such as a rectangle, trapezoid, parallelogram, and square may be used, but a rectangle is more preferable. (Part) It is preferable that the cutout portion of the circular portion (2a) and the contact portion of the quadrilateral portion (2b) have the same length. The thickness of the quadrilateral portion (2b) is preferably smaller than the diameter of the (partial) circular portion (particularly 10 to 60%), and the ratio of the thickness to the length is preferably 1: 1.2 to 1: 4. . More preferable cross-sectional shapes of the main part (2) include a partial circle [angle of an arc part from the center: 180 ° (semicircle) to 340 °] and a rectangle (preferably a thickness: length ratio of 1). : 1.2 to 1: 4) with a partial circle connected to the long side. Preferably, one side of the rectangle is on an extension of one side of the quadrilateral of the attachment part.

As shown in FIGS. 6 to 11, the main part (2) is provided with a hollow part (1) substantially at the center of the main part (2) as necessary.
1) can be formed. The cross-sectional shape of the hollow portion (11) is not particularly limited, but is preferably a circle or an ellipse. The number of hollow portions (11) is plural (for example, 2 to 5).
), But one is preferred. The cross-sectional area of the hollow portion with respect to the total cross-sectional area of the main portion is preferably 40%.
Hereinafter, the ratio is more preferably 1 to 30%, and the ratio of the major axis of the hollow portion to the diameter of the partial circle is preferably 50% or less, more preferably 1 to 45%. Here, the approximate center means that the center is a radius of 20 from the center of the (partial) circle.
%. The attachment part (3) is formed in the shape of a quadrilateral in contact with the main part (2), and extends in a substantially radial direction from the main part. The direction is preferably radial, but may be slightly distorted. Examples of the quadrilateral include those similar to the above, and the ratio of the (average) thickness to the (average) length of the quadrilateral is preferably from 4: 1 to 1: 4. The attachment part (3) is, as shown in FIGS.
The (partial) portion may be in contact with the circular portion (2a), or may be in contact with the quadrilateral portion (2b) as shown in FIGS. Also, the facing part of the attachment part (3) that is in contact with the main part (2) becomes an open face (3a) at the time of the segment association.

The segment sealing material of the first invention (1)
Has an attached portion (3) made of a non-water-swellable rubber (5), so that it has a small dimensional change due to expansion and has excellent shape stability to maintain water-stopping. Further, when the non-water-swellable rubber (5) is formed in a quadrilateral in the attachment part (3), the water-swellable rubber (4) expanded from the joint part (10) in the connected state does not protrude, The appearance is particularly good.

The main part (2) is a (partial) circular part (2a) made of a water-swellable rubber (4), or a (partial) circular part (2a) on one side of a quadrilateral part (2b). Is connected, the main part (2) is made of the water-swellable rubber (4), so that the water stoppage can be effectively maintained. When the hollow portion (11) is formed substantially at the center of the water-swellable rubber (4), excessive pressure during water expansion is suppressed, and the adhesion between the main portion (2) and the segment (6) is reduced. Is improved.

FIG. 12 is a cross-sectional view showing one embodiment of the segment seal material of the second invention, and FIG. 13 is a stop where the segment seal material of the second invention of FIG. 12 is applied to the NM segment of FIG. It is the perspective view represented in the disassembled state for explaining the water structure. 14 to 24 are sectional views showing other embodiments of the segment sealing material of the second invention.

The segment sealing material (1 ') according to the second aspect of the present invention is a member formed in a long strip shape.
A solid non-water-swellable rubber (5) extending from substantially the center of the circle (2 ') to the end of the quadrilateral (3'), and a quadrilateral from the periphery of the (partial) circle (2 '). It is composed of a water-swellable rubber (4) extending to the end of (3 '). Here, a circle is used to include an ellipse and its similar shapes. The substantially center means that a layer of the non-water-swellable rubber (5) always exists within 20% of the radius from the center of the (partial) circle. In addition, solid means that the non-water-swellable rubber (5) does not have a hollow portion and a foamed portion. If the non-water-swellable rubber (5) has a hollow portion or a foamed portion, the segment sealing material is compressed at the time of segment joining, whereby the shape is not stabilized, and the water stopping performance is reduced. The ratio of the cross-sectional area of the quadrilateral portion (3 ′) to the cross-sectional area of the (partial) circular portion (2 ′) is preferably 1: 0.05 to 1: 0.8, more preferably 1: 0.1 to 1: 0.5.

The angle of the arc viewed from the center of the (partial) circle portion (2 ') is preferably 180 ° or more (semicircle or more).
As shown in FIGS. 12 and 14 to 24, the upper half (2c) of the (partial) circular portion (2 ′) may be a circle or an ellipse or one or more (preferably 1 to 3) The lower half (2d) is formed as a circle or an ellipse having substantially the same curvature as the concave groove (9) of the segment (6). As shown in FIGS. 19 to 24, the (partial) circular portion (2 ′) is hollow between the substantially non-water-swellable rubber (5) and the water-swellable rubber (4) at the center as necessary. Department (1
1 ') can be formed, and its position may be either the upper half (2c) or the lower half (2d) of the (partial) circular portion (2'). Here, “substantially at the center” means that the center of the hollow portion (11 ′) is within 30% of the radius from the center of the (partial) circle (2 ′). The cross section of the hollow part (11 ')
A partial circle or a partial ellipse spread from the solid non-water-swellable rubber (5) (preferably, the ratio of the minor axis to the major axis is from 1: 1 to 1: 3)
Is preferred. The area ratio of a partial circle (including an ellipse) to a perfect circle is preferably 30% or more, and more preferably 40% or more.
% Or more. The number of hollow portions (11 ') may be plural (for example, 2 to 5), but is preferably one.
The cross-sectional area of the hollow portion (11 ') is preferably 40% or less, more preferably 1 to 30%, with respect to the total cross-sectional area of the (partial) circular portion (2').

The quadrilateral (3 ') is shown in FIGS.
As shown in FIG. 24, from the (partial) circular portion (2 ′) composed of the solid non-water-swellable rubber (5) and the water-swellable rubber (4) to the end of the quadrilateral portion (3 ′). The upper surface (3b) and / or the lower surface (3c) of the quadrilateral portion (3 ') is layered and formed of a water-swellable rubber (4). Further, as the quadrilateral, a quadrilateral in which at least one pair of opposing sides (upper and lower surfaces) is parallel is preferable, and a rectangle, a trapezoid, a parallelogram,
Any shape such as a square may be used, but a rectangle is more preferable. The ratio of the (average) thickness to the (average) length of the quadrilateral (3 ') is preferably from 4: 1 to 1: 4. Also, a solid non-water-swellable rubber (5) with respect to the total thickness of the quadrilateral (3 ′)
The (average) ratio occupied by the thickness is preferably 10 to 90.
%, More preferably 20 to 80%.

The segment sealing material (1 ') of the second invention.
Is a solid non-water-swellable rubber (5) extending from substantially the center of the (partial) circular part (2 ') to the end of the quadrilateral part (3').
, The dimensional change in the strip direction is small due to the expansion, and the water-stopping property can be maintained due to the excellent shape stability. The thickness of the non-water-swellable rubber (5) in the (partial) circle portion (2 ') and the thickness in the quadrilateral portion (3') may be the same or different, but the molding is easy. Therefore, it is preferable that they have the same thickness. Further, the layer (5) may be linear or bent (“C” -shaped) at the connecting portion between (2 ′) and (3 ′), but may be bent. preferable. Also, the quadrilateral (3 ')
Since the solid non-water-swellable rubber (5) is formed in a layered shape, the water-swellable rubber (4) expanded from the joint portion (10) in a connected state does not protrude, and the appearance is good. . Furthermore, since the (partial) circular portion (2 ') has the water-swellable rubber (4) from the periphery of the solid non-water-swellable rubber (5) to the end of the quadrilateral portion (3'). , (Part) The ratio of the water-swellable rubber (4) in the circular portion (2 ′) is large, and the water stoppage can be effectively maintained. The ratio of the cross-sectional area of the water-swellable rubber (4) in (2 ′) to the total cross-sectional area of the (partial) circular portion (2 ′) is preferably 50% or more, and more preferably 60 to 95%. .

When the segments (6) are connected and joined, a solid non-water-swellable rubber (5) substantially at the center of the (partial) circular portion (2 ') is used as the segment sealing material (1'). When a rubber member having a hollow portion (11 ′) as shown in FIGS. 19 to 24 is used between the water-swellable rubbers (4), excessive pressure during water expansion is suppressed, and a (partial) circular portion is formed. The adhesion between (2 ′) and the segment (6) is improved.

The water-swellable rubber (A) used in the first invention and the second invention is formed of a water-swellable rubber which expands in volume in contact with water, and preferably has a saturated volume expansion ratio of 1.
It is 5 to 6 times, more preferably 2 to 5 times. When the saturated volume water expansion ratio is 1.5 times or more, the water stopping performance becomes good, and when it is 6 times or less, the shape stability becomes good. The volumetric water expansion ratio was determined by molding a band of water-swellable rubber (A),
A test piece of 0 × 2 mm is collected, the volume of the test piece when immersed in purified water at 23 ° C. is measured at regular intervals, and the volumetric water expansion ratio is calculated by the following formula. Volume water expansion ratio (times)
= Volume after expansion / Volume before expansion Further, the magnification at the time when the increase of the volume water expansion ratio per day becomes 0.01 times or less is defined as the saturated volume water expansion ratio of the test piece.

Examples of the water-swellable rubber (A) include, but are not limited to, a water-swellable polyurethane resin (c) having at least one ethylenically unsaturated bond, a vulcanizing agent (d), and a filler (e). It is preferable that the polymer elastic body (f) or a kneaded product of the modified polyolefin resin (g) and the modified polyolefin resin (g) are molded and heat-cured as necessary. When this is used, the entire resin is cross-linked, and the amount of elution is small even if the expansion and contraction are repeated, and a high water stopping property can be maintained. In addition, a water-swellable polyurethane resin generally used [for example, a polyoxyalkylene polyol (x) having at least 20% by mass of oxyethylene units, an organic polyisocyanate (y), and a low-molecular-weight active hydrogen-containing compound (if necessary) resin obtained from z)).

The water-swellable polyurethane resin (c) is
By having at least one ethylenically unsaturated bond, (c), (d), (e), and if necessary, (f) and (g) are kneaded, then extruded or press-molded, and heat-cured. (A). The number of ethylenically unsaturated bonds in (c) is preferably 1 to 4,
The number is more preferably one or two, and particularly preferably one.

As the compound (c), the compound (w) represented by the following general formula (1) and oxyethylene unit having at least 2
A resin obtained from the polyoxyalkylene polyol (x) having 0% by mass, the organic polyisocyanate (y), and if necessary, the low molecular active hydrogen-containing compound (z) is preferable because it can be easily produced. (W) ~
(Z) may be used in combination of two or more kinds. (HO) mR (OX) rm (1) [wherein, R is a residue of an r-valent polyol, X is a group having at least one ethylenically unsaturated bond, r is an integer of 3 or more, m
Is an integer of 2 or more and r-m is 1 or more. ]

In the above general formula (1), R is a residue obtained by removing all OH groups from a polyol having three or more valences.
Examples of the trivalent or higher polyol include aliphatic (including alicyclic) alcohols, phenols and their (poly) oxyalkylene ethers, and these or their (poly) oxyalkylene ethers are alkylene dihalides (having 1 to 4 carbon atoms). The coupling (jump) is used. Specific examples of the aliphatic alcohol include carbon atoms of 3
~ 20 trihydric alcohols (aliphatic triols, for example,
Alkanetriols such as glycerin, trimethylolpropane, trimethylolethane, and hexanetriol; trialkanolamines such as triethanolamine; and alicyclic triols such as cyclohexanetriol); Polyhydric alcohols (aliphatic polyols, for example, alkane polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, and intramolecular or intermolecular dehydrates thereof;
And saccharides such as sucrose, glucose, mannose, lactose and methyl glucoside and derivatives thereof). Examples of phenol include tricyclic or higher monocyclic phenols (pyrogallol, phloroglucin, etc.) and condensates of phenol and formaldehyde (novolak)
Is mentioned.

The above (poly) oxyalkylene ethers can be obtained by adding alkylene oxide to them. The alkylene oxide to be added is preferably an alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO).
, 1,2-, 1,3-, 1,4- and 2,3
-Butylene oxide (hereinafter abbreviated as BO), and a combination of two or more of these (random addition or block addition). Particularly preferably, EO alone or EO and another alkylene oxide [alkylene oxide having 3 or 4 carbon atoms, such as PO, 1,2-BO,
One or more kinds of 1,4-BO and the like]. Among these R, a residue of a trihydric or higher aliphatic alcohol (trivalent or higher hydrocarbon group) is preferable.

In the general formula (1), X is a group having at least one ethylenically unsaturated bond. The number of unsaturated bonds is preferably 1 to 4, more preferably 1. Examples of X include an ethylenically unsaturated hydrocarbon group which may have an ether bond and / or an ester bond, for example, groups represented by the following general formulas (2) and (3). _{- (A 1 O) pQ 1} (2) - _{[CO-A 2 -COO- (A 4} O) sA 3 (OA 4) t-O ] kCO-Q ₂ (3) [wherein, A ₁ and A ₄ is an alkylene group having 1 to ₄ carbon atoms, p, s and t are each an integer of 0 or 1 to 50, and Q ₁ is an alkenyl group, alkadienyl group, alkatrienyl group or alkatetraenyl group having 2 to 24 carbon atoms. A ₂ is an alkenylene group having ₂ to 22 carbon atoms, A ₃ is a divalent hydrocarbon group having 2 to 20 carbon atoms, k is 0 or 1 to 2
An integer of 0, Q ₂ is Q ₁ , A ₂ COOH, or A ₂ CO
O (A ₄ O) s A ₃ (OA ₄ ) tOH. However, when k ≠ 0, Q ₂ may be an alkyl group having 1 to 24 carbon atoms;
When ₂ is Q _1, A ₂ may be an alkylene group having 2 to 22 carbon atoms. As the above-mentioned A ₁ and A _4, a methylene group, an ethylene group, a propylene group, 1,2-, 1,4- and 2,3-butylene group. The A _2, maleic acid, fumaric acid, residues obtained by removing all of the COOH groups from unsaturated dicarboxylic acid having a carbon number 2 to 24, such as itaconic acid and citraconic acid. A ₃
Examples of the low molecular polyols include a residue obtained by removing all OH groups from a dihydric alcohol having 2 to 20 carbon atoms, which will be described later. p, k, s and t are preferably 0. X represents a group X ₁ having no active hydrogen-containing group.
Examples of X ₁ include, among the groups described above, of the group represented by the general formula (3) and the group represented by the general formula (4), wherein Q ₂ is Q ₁ and has 1 to ₁ carbon atoms. 24 alkyl groups.

As a specific example of X, in the general formula (2), p =
For 0, X = Q _1, and the linear 2 to 24 carbon atoms, branched or cyclic alkenyl group such as vinyl group, allyl group, isopropenyl group, oleyl group, cyclohexenyl group: 2 to 24 carbon atoms A straight-chain, branched or cyclic alkadienyl group, for example, a linole group; a straight-chain, branched or cyclic alkatrienyl group having 2 to 24 carbon atoms, for example, a linolenic group; In the case where p is 1 to 50, the alkyl alcohol oxide (having 2 to 4 carbon atoms) adduct of the unsaturated alcohol represented by Q ₁ OH
Residue formed by removing H groups, and _{-CH 2 O (A 1 O)} p -1 Q 1 group (wherein A carbon number of ₁ 2-4) can be mentioned. When k = 0 and Q ₂ = Q _{1 in} the general formula (3), X = COQ ₁ and an unsaturated acyl group having 3 to 25 carbon atoms, for example, an acryloyl group, a methacryloyl group, an oleoyl group and the like can be mentioned. . When k is 1 to 20, the number of carbon atoms is 2 to
One terminal COOH of a (poly) ester of an unsaturated dicarboxylic acid of 24 with the dihydric alcohol having 2 to 20 carbon atoms
And a residue obtained by removing OH from a group.

The number m of the hydroxyl groups in the formula (1) is determined from the viewpoint of the reactivity with the isocyanate group and the water swellability of the obtained resin.
Usually, it is 2 or more, preferably 2-3, and more preferably 2. In order to introduce an ethylenically unsaturated bond into (c), rm must be 1 or more, preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

Preferred examples of (w) include:
The trihydric or higher aliphatic alcohol and an unsaturated alcohol having 2 to 24 carbon atoms (such as vinyl alcohol, allyl alcohol, isopropenyl alcohol, and oleyl alcohol) or an alkylene oxide thereof (having 2 to 2 carbon atoms)
4) a partial ether with an adduct (e.g., obtained by jumping with an alkylene dihalide having 1 to 4 carbon atoms), and the above trihydric or higher aliphatic alcohol and an unsaturated carboxylic acid having 3 to 25 carbon atoms (acrylic) Acid, methacrylic acid, oleic acid, etc.). Among these, more preferred are mono- or polyallyl ethers of trihydric or higher aliphatic alcohols, such as glycerin monoallyl ether, trimethylolpropane monoallyl ether, and pentaerythritol diallyl ether; Mono- or polyacrylates, such as glycerin monoacrylate, trimethylolpropane monoacrylate, pentaerythritol diacrylate; mono- or polymethacrylates of trihydric or higher aliphatic alcohols, such as glycerin monomethacrylate;
Trimethylolpropane monomethacrylate and pentaerythritol dimethacrylate. Among these, glycerin monoallyl ether is particularly preferred.

The number average molecular weight of (w) (determined by a terminal group quantification method) is preferably 2,000 or less, more preferably 1 or less.
000 or less. When the molecular weight is 2,000 or less, the compatibility with the polyoxyalkylene polyol (x) is improved, and the physical properties of the water-swellable polyurethane resin (c) are stabilized.

As (x), a low-molecular-weight active hydrogen-containing compound having a molecular weight of 400 or less such as the following (i) to (iii):
EO adduct and / or EO and another alkylene oxide [one or two of alkylene oxides having 3 or 4 carbon atoms, such as PO, 1,2-BO, 1,4-BO, etc.]
Species or more) (random or block). The amount of EO used in the above adduct is such that the content of oxyethylene units in (x) is 20% by mass or more, particularly 30%, since the obtained (c) has good water swellability.
The amount of EO in the alkylene oxide used for the addition is preferably 25% by mass or more, more preferably 40% by mass or more, and particularly preferably 50 to 95% by mass. In addition, two or more (x)
In the case where is used, the weighted average EO content is preferably within the above range.

Examples of low molecular weight active hydrogen-containing compounds: (i) low molecular weight polyols: dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4 Alkylene glycols such as -butanediol, 1,6-hexanediol and neopentyl glycol; and alicyclic diols such as cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol), trihydric alcohols having 3 to 20 carbon atoms [ Those exemplified in the description of the general formula (1)];
Octahydric or higher polyhydric alcohol [the general formula (1)
As exemplified in the above description). (Ii) Polyhydric phenols: monocyclic phenols such as hydroquinone, resorcin, catechol, pyrogallol and phloroglucin; bisphenols such as bisphenol A, bisphenol B, bisphenol F and bisphenol S; and condensates of phenol and formaldehyde (novolak) ); For example, US Pat.
Polyphenols described in JP-A-5641.

(Iii) Low molecular amines: ammonia; alkanolamines having 2 to 20 carbon atoms (eg, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine) as aliphatic amines, 1 to 20 carbon atoms Alkylamines (e.g., n-butylamine and octylamine), alkylene diamines having 2 to 6 carbon atoms (e.g., ethylene diamine, propylene diamine and hexamethylene diamine), and polyalkylene polyamines having 4 to 20 carbon atoms (e.g., Dialkylenetriamine having 2 to 6 carbon atoms to hexaalkyleneheptamine, for example, diethylenetriamine and triethylenetetramine; aromatic mono- or polyamines having 6 to 20 carbon atoms (for example,
Aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine), alicyclic amines having 4 to 20 carbon atoms (isophoronediamine,
Cyclohexylenediamine and dicyclohexylmethanediamine), heterocyclic amines having 4 to 20 carbon atoms (eg, piperazine and aminoethylpiperazine) and the like.

Preferred as (x) are EO adducts of low molecular weight polyols or polyhydric phenols and EO adducts.
It is a co-adduct of O and another alkylene oxide. More preferably, urethane resins derived from aromatic ring-containing polyols have good physical properties after water expansion. Therefore, EO and PO coadducts (random or block) of polyhydric phenols (particularly bisphenols) and these are preferred. Is a combination of
The number average molecular weight of (x) (based on gel permeation chromatography, hereinafter abbreviated as GPC) is preferably 60
It is 0-8000, more preferably 1000-6000. Further, the number of functional groups of (x) is preferably 2 to 3,
More preferably, it is 2.

As the organic polyisocyanate (y),
For example, aliphatic polyisocyanates having 2 to 18 carbon atoms (excluding carbon in the isocyanate group, the same applies hereinafter) [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethyl Hexane diisocyanate, lysine diisocyanate,
2,6-diisocyanatomethylcaproate, bis (2
-Isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, etc.], an alicyclic polyisocyanate having 8 to 15 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, Methylcyclohexylene diisocyanate (hydrogenated T
DI), bis (2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate, etc.], araliphatic polyisocyanates having 8 to 15 carbon atoms [xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI) And the like, and modified products of these polyisocyanates (modified products containing a carbodiimide group, a uretdione group, a uretoimine group, a urea group, a buret group, an isocyanurate group, and the like). In consideration of chemical resistance, weather resistance, and the like, preferred of these are aliphatic or alicyclic polyisocyanates (particularly, diisocyanates), and more preferred are HDI, IPDI, and hydrogenated MDI.

Examples of the low-molecular-weight active hydrogen-containing compound (z) include low-molecular-weight polyols, low-molecular-weight amines, and adducts of alkylene oxides having 2 to 4 carbon atoms. Among the low-molecular-weight active hydrogen-containing compounds exemplified as the starting material of x), low-molecular-weight polyols (i), low-molecular-weight amines (iii), and (i), polyhydric phenols (ii) or (iii) An alkylene oxide having 2 to 4 carbon atoms (EO alone or a combination of EO and the alkylene oxide having 3 or 4 carbon atoms) adduct may be used. The number average molecular weight (by GPC) of (z) is usually less than 600, preferably 500 or less.
When (i) is used as (z), or when an alkylene oxide adduct of (i), (ii) or (iii) is used, a urethane bond is formed in (c), and when (iii) is used, urea is used. A bond is created.

The amount of (w) used to obtain (c) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on (x). The amount of (z) used is preferably 3 with respect to (x).
0 mass% or less, more preferably 1 to 20 mass%.

The water-swellable polyurethane resin (c) can be produced, for example, using (w), (x), (y) and, if necessary, (z), by either the one-shot method or the prepolymer method. Preferably, the prepolymer method has little production variation. As an example of a method for producing a prepolymer having a terminal isocyanate group, which is an intermediate in the case of production by the prepolymer method, at least a part of the above (x) and an excess equivalent [based on 1 equivalent of the active hydrogen-containing group in (x)] The equivalent weight of the isocyanate group in y) is preferably obtained by reacting (y) with preferably 1.2 to 10] at 70 to 130 ° C in a conventional manner. The isocyanate group content in the obtained prepolymer is preferably 2 to 15% by mass, more preferably 3 to 10% by mass.

As an example of the production method when (c) is produced by the prepolymer method, at least a part of (x) and a prepolymer containing a terminal isocyanate group from (y) are used as main components, and (w) is optionally used. A curing agent component consisting of the balance of (x) and / or the mixture of (z),
An additive such as an antioxidant is preliminarily mixed, and both components are cast into a mold, preferably at 70 to 140 ° C, more preferably at 9 to 140 ° C.
By reacting at 0 to 120 ° C for 0.5 to 8 hours, (c) is obtained. The equivalent ratio of the active hydrogen group in the curing agent component to the isocyanate group in the main component is preferably 0.8 to 1.0, and more preferably 0.93 to 0.9.
9 When the equivalent ratio between the isocyanate group and the active hydrogen group is 0.8 or more, the urethane bond concentration is ensured, and the amount of eluate in water during water expansion is reduced. When it is 1.0 or less, the plasticity of (c) is secured, and the subsequent kneading and extrusion molding become easy.

In the production of the water-swellable polyurethane resin (c), a catalyst usually used for polyurethane can be used if necessary. Examples of the catalyst include tertiary amines [triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, N-methylmorpholine, dimethylaminomethylphenol, N-methyl-
N-dimethylaminoethylpiperazine, pyridine, etc.]
And acid blocking compounds thereof, metal salts of carboxylic acids (such as sodium acetate, lead octylate, zinc octylate, cobalt naphthenate, stannas octoate, dibutyltin dilaurate), alkoxides or phenoxides of alkali metals or alkaline earth metals. (Sodium methoxide, sodium phenoxide, etc.), quaternary ammonium salts (tetraethylhydroxylammonium, etc.), imidazoles (imidazole, 2-ethyl-4
-Methylimidazole and the like, and organometallic compounds containing metals such as tin and antimony (such as tetraphenyltin and tributylantimony oxide). These catalysts can be used alone or in combination. The amount of the catalyst used is based on the total mass of all components for obtaining the water-swellable polyurethane resin (c).
It is usually 5% or less, preferably 0.001 to 4%.

Water-swellable polyurethane resin (c) 1000
The total equivalent (calculated from the reaction equivalent ratio) of the urethane bonds and the urea bonds per g is preferably 0.5 to 2.5 equivalents, particularly preferably 0.6 to 2.2 equivalents. If it is 0.5 equivalent or more, the strength after water expansion is secured, and it does not dissolve after water expansion. 2.
In the case of 5 equivalents or less, depending on the content of oxyethylene units,
A corresponding water expansion ratio is obtained.

(A) Total equivalent of urethane bonds and urea bonds per 1000 g (calculated from reaction equivalent ratio)
Is preferably 0.5 to 2.5 equivalents, particularly preferably 0.6 to 2.2 equivalents. If it is 0.5 equivalent or more, the strength after water expansion is secured, and it does not dissolve after water expansion. When it is 2.5 equivalents or less, a corresponding water expansion ratio can be obtained depending on the content of oxyethylene units.

(C) The equivalent of ethylenically unsaturated bond per 1000 g (calculated from the reaction equivalent ratio) is 0.00
1-3 equivalents, especially 0.01-2 equivalents, are preferred. When it is 3 equivalents or less, a corresponding water expansion ratio is obtained according to the content of the oxyethylene unit, and when it is 0.001 equivalents or more, the eluate in water after the water expansion can be suppressed.

The vulcanizing agent (d) used for the water-swellable rubber (A) may be any of those usually used for vulcanizing rubber, for example, sulfur, sulfur chloride, organic peroxides (benzoyl peroxide). , Dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, t-butylbenzene peroxide, cumene hydroperoxide, t-butyl peroctoate, etc. ), Oximes (such as p-quinone dioxime, p, p'-dibenzoylquinone dioxime), metal oxides (such as magnesia and litharge), alkylphenol resins, polythiol compounds [trimethylolpropane trithioglycolate, Methylol propane tri (3-mel Captopropionate), glycol dimercaptopropionate, glycol dimercaptoacetate, pentaerythritol tetrathioglycolate, dipentaerythritol hexa (3-mercaptopropionate), etc.], polyamine compounds (aldehyde-amine condensates, guanidine And azo compounds (azobisisobutyronitrile, 2-tert-butylazo-2-cyano-4-methylpentane, 4-tert-butylazo-4-cyano-valeric acid and the like), and the like.
The above vulcanizing agents can be used alone or in appropriate combination of two or more kinds. Among these, sulfur and sulfur in combination with other vulcanizing agents, particularly sulfur, are preferred from the viewpoint of easy handling.

The compounding amount of (d) is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass in total of (c) and the elastic polymer (f) described later. ~
8 parts by mass. If the blending amount of (d) is 0.2 parts by mass or more, the amount of eluted substances into water during water expansion is small, and if it is 10 parts by mass or less, there is no possibility that the vulcanizing agent will precipitate on the surface after vulcanization.

The filler (e) may be one generally used as a filler for rubber, and examples thereof include carbon black, talc, calcium carbonate, silicic anhydride, hydrous silicic acid and clay. Of these, carbon black and / or talc are preferable, and FE is more preferable among carbon blacks.
Among F black and talc, it is Mistron Vapor. As (e), it is preferable to select a material capable of suppressing an increase in Mooney viscosity even if the relative addition amount is large and capable of forming a stable molded product without causing expansion during molding.

The compounding amount of (e) is (c) and (f) described later.
To 100 parts by mass of
Parts by mass, more preferably 15 to 100 parts by mass.
When the amount is 10 parts by mass or more, the expansion at the time of extrusion molding is reduced, the adhesiveness of the composition is high, and the workability is improved. Two or more kinds of (e) may be used in accordance with the Mooney viscosity and tackiness of the kneaded material.

Examples of the polymer elastic body (f) optionally used in (A) include natural rubber and synthetic rubber [styrene butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, ethylene- Propylene-diene rubber (EPD
M), butyl rubber, etc.] and their reclaimed rubbers, and non-water-swellable polyurethane resins having an ethylenically unsaturated bond, and the like, which are selected according to the application and purpose. Preferred among these are ethylene-propylene-diene rubber, chloroprene rubber and acrylonitrile-butadiene rubber. The compounding amount of (f) is
(C) The amount is preferably 800 parts by mass or less, more preferably 10 to 500 parts by mass, per 100 parts by mass.
When the compounding amount of (f) is 800 parts by mass or less, a corresponding water expansion ratio is obtained according to the content of (c), and when it is 10 parts by mass or more, the extruded skin is improved.

When the polymer elastic material (f) is blended with the water-swellable rubber (A), (f) is a non-polar rubber (for example,
In the case of EPDM, etc., a modified polyolefin resin (g) may be blended if necessary. (G)
Is compatible with both (c) and (f), or (c)
Those having reactivity with are preferred. Examples of compatible ones include a molecule having a portion having a difference in SP (solubility parameter by the Fedors method) from (c) within 2 and a portion having a difference in SP from (f) being within 2 in one molecule. No. Specific examples of (g) include one or more functional groups selected from the group consisting of carboxylic acid groups, carboxylic acid groups, carboxylic acid anhydride groups, amide groups, hydroxyl groups, and epoxy groups on the main chain or side chains of the polyolefin. And a modified polyolefin resin containing a group. Among the functional groups (g), a carboxylic acid anhydride group and an epoxy group having reactivity with the water-swellable urethane resin (c) are preferable, and a carboxylic acid anhydride group is more preferable.

Examples of the polyolefin forming the skeleton of (g) include one or more (co) olefins of olefins having 2 to 10 carbon atoms (ethylene, propylene, 1-butene, etc.).
Polymers. Preferred are polyethylene and polypropylene. The functional group concentration of (g) is usually 0.1.
It is 1 to 10% by mass, preferably 1 to 8% by mass. When the functional group concentration is 0.1% by mass or more, the surface of the extruded product is good, and when it is 10% by mass or less, the compatibility with (f) is good. The number average molecular weight (by GPC method) of (g) is preferably 800 to 20,000, more preferably 1,000.
１８18000. If the number average molecular weight is 20,000 or less, the surface of the extruded product becomes good, and if it is 800 or more, it does not precipitate on the surface after extrusion. The amounts of (g) are (c) and (f)
Is usually 30 parts by mass or less, preferably 1 to 28 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass in total. When the blending amount of (g) is 30 parts by mass or less, a corresponding water expansion ratio is obtained, and when the amount is 1 part by mass or more, the surface of the extruded product is particularly excellent.

The water-swellable rubber (A) may contain, if necessary, pigments (inorganic pigments (titanium oxide, red iron oxide, graphite, cadmium sulfide, ultramarine blue, etc.) and organic pigments (azo, phthalocyanine, quinacridone, dioxazine). And the like). The amount of these pigments is usually 150 parts by mass or less, preferably 100 parts by mass or less, based on 100 parts by mass of the total of (c) and (f).

In (A), if necessary, vulcanization accelerators (eg, guanidines (eg, diphenylguanidine, diorthotolylguanidine), thiazoles (eg, 2-mercaptobenzothiazole, dibenzothiazyldisulfide), thiuram (Tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, etc.), and sulfenamides (N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl- 2-benzothiazolesulfenamide and the like), a vulcanization accelerating aid [C 8 -C 2
4 fatty acids and their derivatives (stearic acid, oleic acid,
Lauric acid, zinc stearate, etc.) and metal oxides and metal salts (zinc oxide, zinc carbonate, etc.), blowing agents [nitroso compounds (N, N'-dinitrosopentamethylenetetramine, etc.), and azo compounds (azo Bisisobutyronitrile, azodicarbonamide, etc.), softeners (lubricating oil, process oil, paraffin oil, aromatic process oil, petroleum asphalt, fatty acid oil, phthalic acid derivative oil, adipic acid derivative oil, sebacic acid derivative) Oil, maleic acid derivative oil, fumaric acid derivative oil, trimellitic acid derivative oil, citric acid derivative oil, oleic acid derivative oil, ricinoleic acid derivative oil, stearic acid derivative oil, phosphoric acid derivative oil, glycolic acid derivative oil, polyester type , And epoxy type And an antioxidant [amines (N-phenyl-α-naphthylamine, N-phenyl-
β-naphthylamine, N-phenyl-N′-isopropyl-p-phenylenediamine, etc.), amine ketones (eg, 2,2,4-trimethyl-1,2-dihydroquinoline polymer), hindered phenols [2,6 -Ji-
t-butyl-4-methylphenol, 4,4′-thiobis (3-methyl-6-t-butylphenol), 4,
Known additives such as 4′-butylidenebis (3-methyl-6-t-butylphenol)] and dithiocarbamic acid salts (eg, nickel dibutyldithiocarbamate). If necessary, a trifunctional or higher functional ethylenically unsaturated bond-containing compound (for example, triallyl isocyanurate) may be used as a urethane crosslinking agent during vulcanization.
May be blended together with (d).

The vulcanization accelerator, vulcanization acceleration aid and foaming agent are each usually 10% by mass or less, preferably 0.0% by mass, based on the total mass of the water-swellable rubber (A).
0.01 to 5% by mass, and the softener is usually 20% by mass or less,
It is preferably 0.1 to 15% by mass, and the antioxidant is usually 10% by mass or less, preferably 0.001 to 5% by mass. The total amount of these additives in (A) is preferably 20% by mass or less, more preferably 0.1 to 18%.
% By mass.

The non-water-swellable rubber (B) used in the first invention and the second invention is not particularly limited, but the saturated volume water expansion ratio by the above method is usually less than 1.5 times, preferably 1 time. .2 times or less. As (B), a vulcanized rubber which does not substantially change in volume even when it comes into contact with water is preferable. As the vulcanized rubber, a polymer elastic body (f),
Forming a kneaded product of the vulcanizing agent (d) and the filler (e),
Those cured by heating can be used.

As the above-mentioned elastic polymer (f), those similar to those used in the above (A) can be mentioned, and preferred ones are also the same. As the vulcanizing agent (d) and the filler (e), the same ones as those used in the above (A) can be mentioned, and the preferable ones are also the same. Further, the compounding amount of (d) is preferably 0.2 to 1 with respect to 100 parts by mass of (f).
0 parts by mass, more preferably 0.5 to 8 parts by mass.
If the blending amount of (d) is 0.2 parts by mass or more, the amount of eluted substances into water during water expansion is small, and if it is 10 parts by mass or less, there is no possibility that the vulcanizing agent will precipitate on the surface after vulcanization. The amount of (e) is
(F) preferably 10 to 150 parts by mass with respect to 100 parts by mass.
Parts by mass, more preferably 15 to 100 parts by mass.
When the amount is 10 parts by mass or more, the expansion at the time of extrusion molding is reduced, the adhesiveness of the composition is high, and the workability is improved. When the amount is 100 parts by mass or less, the extruded skin is improved. Two or more kinds of (e) may be used in accordance with the Mooney viscosity and tackiness of the kneaded material.

In the non-water-swellable rubber (B), if necessary,
Pigments and organic pigments can also be used. These specific examples are the same as in the case of (A). These blending amounts are based on 100 parts by mass of the elastic polymer (f).
It is usually at most 150 parts by mass, preferably at most 100 parts by mass.

In (B), if necessary, known additives such as the aforementioned vulcanization accelerator, vulcanization accelerator, foaming agent, softener and antioxidant can be blended. As for these additives, the vulcanization accelerator, the vulcanization acceleration aid and the foaming agent are each usually 10% by mass or less, preferably 0.001 to 5% by mass, based on the total mass of (B). Is usually 20
%, Preferably 0.1 to 15% by mass, and the antioxidant is usually 10% by mass or less, preferably 0.001% by mass.
~ 5% by mass. The total amount of these additives in (B) is preferably 20% by mass or less, more preferably 0.1 to 18% by mass.

As a method for producing the segment sealing material of the first and second inventions, for example, after kneading the components other than the vulcanizing agent (d) and the vulcanization accelerator with a Banbury mixer or a kneader, d) and if necessary, a vulcanization accelerator is kneaded on a roll, and the molding method usually used in the rubber industry (press molding, continuous extrusion crosslinking / molding method, etc.)
And heat molding. A strip-shaped molded product is obtained by a continuous extrusion crosslinking / molding method such as a UHF vulcanization equipment (ultra high frequency vulcanization equipment), and both ends are connected by a method such as adhesion, fusion or vulcanization adhesion,
The whole may be annular. The heat curing temperature is set according to the type of the vulcanizing agent, but is preferably 150 to 200 ° C.
It is.

The segment sealing material of the first invention (1)
As shown in FIG. 25, the lower half of the (partial) circular portion (2a) of the main portion (2) is connected to the joint (1) of the segment (6).
The groove (9) formed in the groove (9) is fitted so that the attachment portion (3) is in contact with the joint (10) of the groove (9). Further, as shown in FIG. 26, the segment sealing material (1 ′) of the second aspect of the present invention, as shown in FIG. )) And fitted so that the quadrilateral part (3 ′) is in contact with the joint part (10) of the concave groove (9). At this time, an adhesive or the like may be used to fix the segment seal material (1) or (1 ′) to the concave groove (9). As an adhesive,
An adhesive generally used for fixing a sealing material can be used, and examples thereof include a synthetic rubber-based adhesive.

When the segments (6) are connected and joined, in the first invention, as shown in FIG.
Since the attachment portion (3) of the segment sealing material (1) is located at (0), the segment sealing material (1) is compressed to have a desired opening width. In the second invention, as shown in FIG. 26, the quadrangular portion (3 ′) of the segment sealing material (1 ′) is located at the joint portion (10), so that the segment sealing material (1 ′) is formed. It is compressed to a desired aperture width.

The segment sealing material of the present invention and the segment sealing structure using the same are suitably used for NM segments.

[0060]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. In addition, the part in an Example means a mass part.

[Performance Test Examples] Table 1 shows the results of the volume water expansion ratio test, the mass reduction rate test, the water stop performance test and the appearance of Examples 1-4 and Comparative Examples 1-2. Comparative Examples 3-4 volume water expansion magnification test, mass reduction rate test,
Table 2 shows the results of the water stopping performance test and the appearance.

(Volume water expansion ratio) 20 × 20
A test piece of × 2 mm was collected, immersed in purified water at 23 ° C., and the volume expansion ratio after 6 months was calculated by the following equation. Volumetric water expansion ratio (times) = volume at the time of expansion / volume before expansion (mass reduction ratio) The test piece after measuring the volumetric water expansion ratio for 6 months is dried in an oven at 60 ° C., and the decrease in mass is 0.1 g.
The mass at the time of the following became the mass after drying, and it was calculated by the following equation. Mass reduction rate (%) = 100 × (mass before expansion−mass after drying) / mass before expansion

(Water stop performance test) A test piece of the segment sealing material of each of the following Examples 1 to 4 was applied to the lower surface (upper (12) and lower (13)) of a pair of steel flanges as shown in FIG. Attached portion (3) is directed outward (partial) circular portion (2a) into concave groove (19) (cross-sectional shape: semicircle with a radius of 4 mm) of 13)
The lower half is fitted and fixed with an adhesive. Similarly, the test pieces of the segment sealing materials of Comparative Examples 1 and 2 were used as the concave grooves (19) in the lower surface (13) of the pair of steel flanges as shown in FIG.
And fixed with adhesive. Using a spacer (14) and fastening with bolts and nuts (15) to a thickness of 2 mm, a test device is used. Thereafter, the inside of the test apparatus is filled with water, and after a water absorption curing is performed for one week, water pressure is applied by a water pressure pump (18), and the water pressure immediately before the water leakage occurs is measured with a pressure gauge (1).
It measured in 7) and set it as the still water pressure. The pressure was set at a pitch of 0.1 MPa, and the pressure was increased up to 1.0 MPa. (16) is an air vent valve. Examples 1-4 and Comparative Examples 1-2
Of the cross-sectional shape of the segment seal material (see FIG. 29)
Is shown in Table 1. In addition, the test pieces of the segment sealing materials of Examples 5 to 8 described below were used for the lower surface (1) of the pair of steel flanges (upper (12) and lower (13)) as shown in FIG.
The lower half part (2d) of the circular part (2 ') is fitted with the quadrilateral part (3') facing outward in the concave groove (19) (cross-sectional shape: semicircle with a radius of 4 mm) of 3). , Fix with adhesive. Similarly,
The test pieces of the segment sealing materials of Comparative Examples 3 and 4 are fitted into the concave grooves (19) of the lower surface (13) of the pair of steel flanges as shown in FIG. 28, and fixed with an adhesive. The water stop pressure was determined in the same manner as in Examples 1 to 4. Table 2 shows the dimensions of the sectional shapes of the segment sealing materials of Examples 5 to 8 and Comparative Examples 3 and 4.

(Appearance) After the water stopping performance test, the position of the end of the flange of the segment sealing material on the open side of the flange was the same as that at the start of the test. , And.

Production Example 1 A mixture of bisphenol A and EO and PO (mass ratio 80 /
By reacting 1000 parts of polyether glycol having a number average molecular weight of 4000 obtained by adding 20) with 383 parts of dicyclohexylmethane diisocyanate at 120 ° C. for 3 hours, a prepolymer having an isocyanate group content of 8% was obtained. Next, 39.5 parts of glycerin monoallyl ether, 1567 parts of polyethylene glycol (number average molecular weight 1500) and 2.83 parts of triethylenediamine were added as curing agent components, and reacted at 110 ° C. for 5 hours to obtain a polyoxyethylene urethane resin. (C1) was obtained.

Production Example 2 FEF black [Asahi # 60; Asahi Carbon Co., Ltd.] based on 100 parts of polyoxyethylene urethane resin (c1)
50%, stearic acid 0.5 part, and zinc oxide 1 part were kneaded with a Banbury mixer, and sulfur 2 parts,
4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole were blended with two rolls to obtain blended product 1.

Production Example 3 30 parts of EPDM [Mitsui EPT4070; manufactured by Mitsui Chemicals, Inc., the same applies hereinafter], 100 parts of polyoxyethylene urethane resin (c1), 50 parts of FEF black,
After kneading 0.5 part of stearic acid and 1 part of zinc oxide with a Banbury mixer, 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole are mixed with 2 parts.
The mixture was blended with this roll to obtain a blended product 2.

Production Example 4 Chloroprene rubber [Skyprene B-10; 100 parts of polyoxyethylene urethane resin (c1)
Tosoh Corporation, same hereafter) 30 parts, FEF Black 5
After kneading 0 part, 0.5 part of stearic acid and 1 part of zinc oxide with a Banbury mixer, 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide, and 2-mercaptobenzothiazole 2
Parts were blended with two rolls to obtain a blended product 3.

Production Example 5 100 parts of EPDM, 50 parts of FEF black and process oil [Dyna Process Oil PW-380;
20 parts, 0.5 part of stearic acid and 1 part of zinc oxide are kneaded with a Banbury mixer, and then 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide,
2-mercaptobenzothiazole (2 parts) was blended with two rolls to obtain blended product 4.

Production Example 6 FEF black 5 was added to 100 parts of chloroprene rubber.
0 parts, process oil 20 parts, stearic acid 0.5 part,
After kneading 1 part of zinc oxide with a Banbury mixer, 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole were compounded with two rolls to obtain compounded product 5.

Production Example 7 100 parts of chloroprene rubber was mixed with FEF black 5
0 parts, process oil 20 parts, stearic acid 0.5 part,
After kneading 1 part of zinc oxide with a Banbury mixer, 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide, 2 parts of 2-mercaptobenzothiazole, and 0.5 part of azobisisobutyronitrile are compounded with two rolls and mixed. Product 6 was obtained.

Example 1 In the cross-sectional shape of the segment sealing material (1) shown in FIG. 1, a water-swellable rubber (4) was extruded into a band with compound 1 and a non-water-swellable rubber (5) was compounded with band 4. Then, the mixture was heated in an oven at 180 ° C. for 10 minutes to obtain a molded product.

Example 2 In the sectional shape of the segment sealing material (1) in FIG. 1, a water-swellable rubber (4) was extruded into a compound 2 and a non-water-swellable rubber (5) was extruded into a band with compound 4. Then, the mixture was heated in an oven at 180 ° C. for 10 minutes to obtain a molded product.

Example 3 In the sectional shape of the segment sealing material (1) in FIG. 1, a water-swellable rubber (4) was extruded into a band with compound 3 and a non-water-swellable rubber (5) was compounded with band 5. Then, the mixture was heated in an oven at 180 ° C. for 10 minutes to obtain a molded product.

Example 4 In the cross-sectional shape of the segment sealing material (1) in FIG. 8, a water-swellable rubber (4) was extruded into a band with compound 1 and a non-water-swellable rubber (5) was compounded with band 5. Then, the mixture was heated in an oven at 180 ° C. for 10 minutes to obtain a molded product.

Comparative Example 1 A sectional shape similar to that of the segment sealing material (1) in FIG.
Everything was extruded in a strip shape with Compound 1, and heated in an oven at 180 ° C. for 10 minutes to obtain a molded product.

Comparative Example 2 A sectional shape similar to the segment sealing material (1) in FIG.
Everything was extruded in a strip shape with Compound 1, and heated in an oven at 180 ° C. for 10 minutes to obtain a molded product.

Example 5 In the sectional shape of the segment sealing material (1 ') shown in FIG. 12, a water-swellable rubber (4) was used in the compound 1 and a solid non-water-swellable rubber (5) was used in the compound 4. Extruded into strips, 180 ° C at 10
Heated in an oven for minutes to obtain a molded article.

Example 6 In the sectional shape of the segment sealing material (1 ') shown in FIG. 12, the water-swellable rubber (4) was used in the compound 2 and the solid non-water-swellable rubber (5) was used in the compound 4. Extruded into strips, 180 ° C at 10
Heated in an oven for minutes to obtain a molded article.

Example 7 In the sectional shape of the segment sealing material (1 ') shown in FIG. 12, a water-swellable rubber (4) was used in compound 3 and a solid non-water-swellable rubber (5) was used in compound 5. Extruded into strips, 180 ° C at 10
Heated in an oven for minutes to obtain a molded article.

Example 8 In the sectional shape of the segment sealing material (1 ') shown in FIG. 22, the water-swellable rubber (4) was used in the compound 1 and the solid non-water-swellable rubber (5) was used in the compound 5. Extruded into strips, 180 ° C at 10
Heated in an oven for minutes to obtain a molded article.

Comparative Example 3 As shown in FIG. 30, a central portion made of non-water-swellable rubber (5) having a circular hollow portion, an outer peripheral portion made of water-swellable rubber (4), and a quadrilateral portion were provided. Compound 1 having a water-swellable rubber (4) in cross section and compound 4 having a non-water-swellable rubber (5)
After extrusion molding into a belt shape by heating at 180 ° C. for 10 minutes in an oven, a molded product was obtained.

Comparative Example 4 As shown in FIG. 31, a cross-sectional shape having a central portion made of a circular non-water-swellable rubber foam (5 '), an outer peripheral portion made of a water-swellable rubber (4), and a quadrilateral portion Then, after extruding the water-swellable rubber (4) with the compound 3 and the non-water-swellable foamed rubber (5 ′) with the compound 6 in a belt shape, the mixture is heated in an oven at 180 ° C. for 10 minutes to form a molded product. Obtained.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

As described above, the segment sealing material of the present invention has the following effects. (1) The adhesion between the NM segment and the sealing material at the time of joining the NM segment is improved, and high water stopping performance can be maintained. (2) The dimensional change in the strip direction and joints is small, the shape stability is excellent, the appearance after the segment is performed is good, and high water stopping property can be maintained. (3) Further, when a sealing material having a hollow portion is used, the pressure at the time of water expansion becomes uniform, and higher water stopping properties can be obtained. Therefore, it is extremely useful as a sealing material for NM segments.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a segment sealing material of the first invention.

FIG. 2 is a perspective view showing one embodiment of an NM segment.

FIG. 3 is an exploded perspective view of a water blocking structure using the segment sealing material according to the first invention.

FIG. 4 is a sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 5 is a cross-sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 6 is a sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 7 is a cross-sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 8 is a sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 9 is a cross-sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 10 is a sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 11 is a sectional view showing another embodiment of the segment sealing material according to the first invention.

FIG. 12 is a cross-sectional view showing one embodiment of the segment sealing material of the second invention.

FIG. 13 is an exploded perspective view of a water blocking structure using the segment sealing material according to the second invention.

FIG. 14 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 15 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 16 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 17 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 18 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 19 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 20 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 21 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 22 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 23 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 24 is a sectional view showing another embodiment of the segment sealing material according to the second invention.

FIG. 25 is a perspective view of a water stopping structure using the segment sealing material according to the first invention.

FIG. 26 is a perspective view of a water blocking structure using a segment sealing material according to the second invention.

FIG. 27 is a cross-sectional view showing an embodiment of a water stoppage test.

FIG. 28 is a cross-sectional view showing an embodiment of a water stoppage test.

FIG. 29 is a cross-sectional view (for explaining dimensions in Examples) showing an embodiment of the segment seal material according to the first invention;

FIG. 30 is a sectional view showing a comparative segment sealing material.

FIG. 31 is a cross-sectional view showing a comparative segment sealing material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Segment seal material (1st invention) 2 Main part 2a (partial) circular part 2b Quadrilateral part 3 Attached part 3a Open surface at the time of segment association 4 Water-expandable rubber 5 Non-water-expandable rubber 6 Segment 7 Step 8 Board Part 9 Groove 10 Joint part 11 Hollow part 1 'Segment seal material (second invention) 2' (Partial) circular part 2c (Partial) Upper half part of circular part 2d (Partial) Lower half part of circular part 3 'Four sides Form part 3b Upper surface of quadrilateral part 3c Lower surface of quadrilateral part 11 'hollow part 12 Upper steel flange 13 Lower steel flange 14 Spacer 15 Bolt / nut 16 Air release valve 17 Pressure gauge 18 Water pressure pump 19 Concave groove 20 (part) Circle part diameter 21 Main part thickness 22 Quadrilateral part thickness 23 Quadrilateral part length 24 Attached part thickness 25 Attached part length 26 Hollow part diameter 5 'Non-water-expandable foam rubber 27 Outer part diameter 28 Medium Part diameter 29 quadrilateral director of 30 trapezium section thickness 31 hollow portion diameter

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 75/14 C08L 75/14 F term (Reference) 2D055 GC09 KB09 KB10 KB14 LA02 4J002 AC013 AC033 AC063 AC083 AC093 BB153 BB173 BB204 BB214 CC052 CC152 CK021 CK041 CK051 DA037 DA046 DE076 DE156 DE237 DG016 DJ007 DJ037 DJ047 EK036 EK046 EK066 EV066 FD017 FD142 FD146

Claims (8)

[Claims] 1. A band-shaped segment sealing material comprising a water-expandable rubber (A), a main part (I) fitted into a groove of a segment, and a non-water-expandable rubber (B),
A segment sealing material consisting of an attached part (II) that is connected to the main part substantially radially and becomes an open surface side during segment association. 2. A sectional shape of a main part is a (partial) circle or a shape in which a (partial) circle is connected to one side of a quadrilateral, and at least one pair of opposing sides is parallel to each other. 2. The segment sealing material according to claim 1, wherein the segment sealing material has a rectangular shape. 3. The segment sealing material according to claim 1, wherein (I) has a void. 4. A band-shaped segment sealing material having a (partial) circular portion and a quadrilateral portion in cross section, and a solid portion extending from substantially the center of the (partial) circular portion to an end of the quadrilateral portion. A segment sealing material comprising a non-water-swellable rubber (B) and a water-swellable rubber (A) extending from the periphery of the (partial) circular portion (B) to the end of the quadrilateral portion. 5. The segment sealing material according to claim 4, further comprising a gap between (A) and (B) substantially at the center of the (partial) circular portion. 6. A water-swellable polyurethane resin (A) wherein (A) has at least one ethylenically unsaturated bond, a vulcanizing agent (d), a filler (e), and if necessary, a polymer elastic material ( The segment sealing material according to any one of claims 1 to 5, wherein a kneaded product of f) or (f) and the modified polyolefin resin (g) is formed and heat-cured. 7. The method according to claim 1, wherein (B) is a kneaded product of a polymer elastic body (f), a vulcanizing agent (d), and a filler (e), which is molded and heat-cured. The segment sealing material according to 1. 8. A segment water stopping structure for mounting the segment sealing material according to claim 1 in a segment concave groove having a semicircular or semielliptical cross section.