JP2003048999A - Water-swellable rubber molded article and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-swelling rubber molding having excellent extrusion moldability and fast vulcanization rate. SOLUTION: This water-swelling rubber molding is obtained by heat-curing a extruded or pressed molding of a kneaded product comprising (A) a water- swelling polyurethane resin having at least one ethylenically unsaturated bond, (B) a polymer elastic body, (C) a vulcanizing agent, (D) a filler and (E) a modified polyolefin resin and characterized by having a water-swelling rate of saturated volume being 1.2-8.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-expandable rubber molded product and a method for producing the same. More specifically, the present invention relates to a water-expandable rubber molded article useful as a waterproofing material in civil engineering, construction and various other fields, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a water-swellable resin molded article in which a water-swellable polyurethane having an ethylenically unsaturated bond is compounded with rubber, one described in JP-A-57-119972 is known.

[0003]

However, in the above, (1) when a water-swelling urethane having an ethylenically unsaturated bond in the polyurethane main chain is used, the vulcanization reaction is slow, and (2) only the polyurethane terminal is used. When it has an ethylenically unsaturated bond, it has a problem that the kneading property is poor because the melt viscosity of polyurethane is low and the surface of the molded product is rough during extrusion molding.

[0004]

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of extensive studies on a water-expandable rubber molded product having good extrusion moldability and high vulcanization rate. That is, the present invention is
The following are (I) to (IV).

(I) Water-swellable polyurethane resin (A) having at least one ethylenically unsaturated bond, elastic polymer (B), vulcanizing agent (C), filler (D), and modified polyolefin A water-expandable rubber molded article, which is obtained by extruding or press-molding a kneaded product of the resin (E), and having a saturated volumetric water expansion ratio of 1.2 to 8 times.

(II) A compound (a1) represented by the following general formula (2), a polyoxyalkylene polyol (b) containing at least 20% by mass of an oxyethylene unit, an organic polyisocyanate (c), and, if necessary, a low content. Water-swellable polyurethane resin (A1) obtained from compound (d) containing molecular active hydrogen, polymer elastic body (B), vulcanizing agent (C), filler (D), and optionally modified polyolefin resin (E The extruded or press-molded product of the kneaded product of 1) is heat-cured, and the saturated volumetric water expansion ratio is 1.
A water-expandable rubber molded product characterized by being 2 to 8 times. (HO) mR (OX ₁ ) rm (2) [wherein, R is a residue of an r-valent polyol, X ₁ is a group having no active hydrogen-containing group and at least one ethylenically unsaturated bond, r Is an integer of 3 or more, m is 2 or more, and r-m is an integer of 1 or more. ]

(III) Water-swellable polyurethane resin (A) having at least one ethylenically unsaturated bond, elastic polymer (B), vulcanizing agent (C), filler (D) and modified polyolefin resin The kneaded product of (E) is extruded or press-molded into a desired shape, and the ethylenically unsaturated bonds of (A) and (B) are reacted with (C) under heating to give a saturated volume expansion ratio of 1 A method for producing a water-expandable rubber molded product, which is characterized in that a molded product of 2 to 8 times is obtained.

(IV) Compound (a1) represented by the following general formula (2), polyoxyalkylene polyol (b) having at least 20% by mass of oxyethylene unit, organic polyisocyanate (c), and optionally low molecular weight Water-swellable polyurethane resin (A1) obtained from active hydrogen-containing compound (d), polymer elastic body (B), vulcanizing agent (C), filler (D), and optionally modified polyolefin resin (E) The kneaded product consisting of is extruded or press-molded into a desired shape, and the ethylenically unsaturated bonds of (A1) and (B) are reacted with (C) under heating to give a saturated volume expansion ratio of 1.2 to A process for producing a water-expandable rubber molded product, which is characterized in that an 8-fold molded product is obtained. (HO) mR (OX ₁ ) rm (2) [wherein, R is a residue of an r-valent polyol, X ₁ is a group having no active hydrogen-containing group and at least one ethylenically unsaturated bond, r Is an integer of 3 or more, m is 2 or more, and r-m is an integer of 1 or more. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The water-expandable rubber molded article of the present invention is
In purified water (distilled water or deionized water) at 23 ° C, it usually has a saturated volumetric water expansion ratio of 1.2 to 8 times. The lower limit is preferably 1.4 times, more preferably 1.5 times,
The upper limit is preferably 7 times, more preferably 6 times.
The volumetric water expansion ratio in this case is obtained by the following method. If the saturated volumetric water expansion ratio is less than 1.2 times, the water-stopping effect after water expansion will not be sufficiently obtained, and if it exceeds 8 times, the resin strength after water expansion will decrease, so that the water-stopping performance can be maintained. Disappear. (Volume of water expansion) From the band of polyurethane molded product 2
A test piece of 0 × 20 × 2 mm was sampled and
The volume when immersed in purified water at ℃ is measured at regular intervals, and the volumetric water expansion ratio is calculated by the following formula. Volumetric water expansion ratio (times) = volume after expansion / volume before expansion Also, the rate of increase in the volumetric water expansion ratio per day is 0.01
The ratio at the time of becoming less than or equal to
The magnification at the time of becoming 1 time or less) is defined as the saturated volumetric water expansion magnification of the test piece.

The water-swellable polyurethane resin (A) in the present inventions (I) and (III) has at least one ethylenically unsaturated bond, and by having an ethylenically unsaturated bond, (A) ), The elastic polymer (B), the vulcanizing agent (C), the filler (D), and the modified polyolefin resin (E) are kneaded, and then extruded or press-molded into a desired shape and heat-cured to obtain water. An expansive rubber molded product (F) can be used. As (A), those having an ethylenically unsaturated bond in the side chain are preferable because the vulcanization reaction becomes faster. The number of ethylenically unsaturated bonds in (A) (average per molecule) is preferably 1 to 1.
It is 00. The lower limit is more preferably 2, and particularly preferably 5, and the upper limit is more preferably 30.
The number is particularly preferably 20. Here, the water-swellable polyurethane resin is 1.2 to 8 in purified water at 23 ° C.
It means that the resin has a double saturated volume expansion coefficient.

As (A), the compound (a) represented by the following general formula (1) and at least 2 units of oxyethylene units are used.
A resin obtained from 0 mass% of the polyoxyalkylene polyol (b), the organic polyisocyanate (c), and optionally the low molecular weight active hydrogen-containing compound (d) is preferable because it can be easily produced. In addition, (a) ~
Two or more kinds of (d) may be used in combination. (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 rm is 1 or more. ]

The water-swellable polyurethane resin (A1) in the present inventions (II) and (IV) is
(A) is a resin obtained by using (a1) in the general formula (2). The number of ethylenically unsaturated bonds in (A1) is also preferably 1 to 100. The lower limit is more preferably 2, and particularly preferably 5, and the upper limit is more preferably 30, and particularly preferably 20. (A1) has at least one ethylenically unsaturated bond in its side chain, and by having an ethylenically unsaturated bond, (A), the polymer elastic body (B), the vulcanizing agent (C ), A filler (D), and optionally a modified polyolefin resin (E), and then extruded or press-molded into a desired shape and heat-cured to obtain a water-expandable rubber molded product (F). .

In the above general formulas (1) and (2),
R is a residue obtained by removing all OH groups from an r-valent (3-8 valent or higher valent) polyol. As the trihydric or higher polyol, aliphatic (including alicyclic) alcohols, phenols and their (poly) oxyalkylene ethers, or these (poly) oxyalkylene ethers are alkylene dihalides (having 1 to 4 carbon atoms). One that has been coupled (jumped) with. Specific examples of the aliphatic alcohol include trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin,
Alkanetriols such as trimethylolpropane, trimethylolethane and hexanetriol; trialkanolamines such as triethanolamine; and cycloaliphatic triols such as cyclohexanetriol), 4 to 8 valences of 5 to 20 carbon atoms or higher. Polyhydric alcohols (aliphatic polyols such as pentaerythritol,
Alkane polyols such as sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and their intramolecular or intermolecular dehydrated products; and saccharides such as sucrose, glucose, mannose, lactose and methylglucoside and their derivatives). Examples of phenols include trivalent or higher monocyclic phenols (pyrogallol, phloroglucin, etc.) and condensates of phenol and formaldehyde (novolak).

The above-mentioned (poly) oxyalkylene ether is obtained by adding alkylene oxide to these. The alkylene oxide to be added is preferably one having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO) and propylene oxide (hereinafter PO).
Abbreviated), 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 and EO and other alkylene oxides [C3 or C4 alkylene oxides such as PO, 1,2-BO,
1,4-BO and the like] or a combination of two or more thereof]. Among these R, a trivalent or higher valent aliphatic alcohol residue (trivalent or higher valent hydrocarbon group) is preferable.

In the general formulas (1) and (2), X is a group having at least one ethylenically unsaturated bond, and X ₁ is X.
Among these, a group having no active hydrogen-containing group. 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 (3) and (4). _{- (A 1 O) pQ 1} (3) - _{[CO-A 2 -COO- (A 4} O) sA 3 (OA 4) t-O ] _kCO-Q 2 (4) [wherein, _{A 1} and A ₄ is an alkylene group having 1 to ₄ carbon atoms, p, s and t are 0 or an integer of 1 to 50, Q
₁ is an alkenyl group having 2 to 24 carbon atoms, an alkadienyl group, an alkatrienyl group or an alkatetraenyl group, A ₂ is an alkenylene group having ₂ to 22 carbon atoms, A _2
3 is a divalent hydrocarbon group having 2 to 20 carbon atoms, k is 0 or an integer of 1 to 20, Q ₂ is Q ₁ , A ₂ COOH, or A ₂ COO (A ₄ O) sA ₃ (OA ₄ ). tOH. However, when k ≠ 0, Q ₂ may be an alkyl group having 1 to 24 carbon atoms, and when Q ₂ is Q ₁ , A ₂ has ₂ carbon atoms.
It may be an alkylene group of ~ 22. ]

The above A ₁ and A ₄ are methylene group, ethylene group, propylene group, 1,2-, 1,4-
And 2,3-butylene group and the like. Examples of A ₂ include a residue obtained by removing all COOH groups from an unsaturated dicarboxylic acid having 4 to 24 carbon atoms such as maleic acid, fumaric acid, itaconic acid and citraconic acid.
Examples of A ₃ include low molecular weight polyols such as a residue obtained by removing all OH groups from a dihydric alcohol having 2 to 20 carbon atoms described below. 0 is preferable for p, k, s and t. As an example of X ₁ , among the groups represented by the general formula (3) and the group represented by the general formula (4), Q ₂ is Q ₁ and an alkyl group having 1 to 24 carbon atoms. The case of a group is mentioned.

As specific examples of X and X ₁ , when p = 0 in the general formula (3), X = Q ₁ and the number of carbon atoms is 2 to 2.
4 linear, branched or cyclic alkenyl groups such as vinyl group, allyl group, isopropenyl group, oleyl group, cyclohexenyl group: linear, branched or cyclic alkadienyl groups having 3 to 24 carbon atoms, such as linole group; A linear, branched or cyclic alkatrienyl group having 4 to 24 carbon atoms, for example, a linolene group; p is 1-5
When it is 0, a residue obtained by removing an OH group from an alkylene oxide (having 2 to 4 carbon atoms) adduct of an unsaturated alcohol represented by Q ₁ OH, and —CH ₂ O
(A ₁ O) p ₋₁ Q ₁ group (however, the carbon number of A ₁ is 2 to
4) is mentioned. In the general formula (4), k = 0, Q ₂ = Q ₁
In the case of, X = COQ ₁ and an unsaturated acyl group having 3 to 25 carbon atoms, such as an acryloyl group, a methacryloyl group, or an oleoyl group, can be mentioned. When k is 1 to 20, OH is removed from one terminal COOH group of the (poly) ester of the unsaturated dicarboxylic acid having 4 to 24 carbon atoms and the dihydric alcohol having 2 to 20 carbon atoms. Examples include residues.

The number m of hydroxyl groups in the formula (1) means that the reactivity with an isocyanate group and the water swelling property of the resulting resin are:
It is usually 2 to 7 or more, preferably 2 to 3, and more preferably 2. It is also preferable that it is 2 or more from the viewpoint that (A) has an ethylenically unsaturated bond in its side chain. In order to introduce an ethylenically unsaturated bond into (A), r-m needs to be 1 or more, preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

As a preferable example of (a),
The trihydric or higher aliphatic alcohol and an unsaturated alcohol having 2 to 24 carbon atoms (vinyl alcohol, allyl alcohol, isopropenyl alcohol, oleyl alcohol, etc.) or its alkylene oxide (having 2 carbon atoms).
4) Partial ether with an adduct (for example, obtained by jumping with an alkylene dihalide having 1 to 4 carbon atoms), the above-mentioned trihydric or higher aliphatic alcohol and an unsaturated carboxylic acid having 3 to 25 carbon atoms (acryl) Acid, methacrylic acid, oleic acid, etc.) and partially acylated products by a partial esterification reaction. Among these, more preferable are mono- or polyallyl ethers of trihydric or higher aliphatic alcohols such as glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol diallyl ether; trihydric or higher aliphatic alcohols. 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, pentaerythritol dimethacrylate; Of these, glycerin monoallyl ether is particularly preferable.

The number average molecular weight of (a) (determined by the end group quantification method) is preferably 2000 or less, more preferably 1
It is 000 or less. When the molecular weight is 2000 or less, the compatibility with the polyoxyalkylene polyol (b) is improved and the physical properties of the polyurethane resin (A) are stabilized.

Examples of (b) include low molecular weight active hydrogen-containing compounds having a molecular weight of 400 or less, such as the following (i) to (iii):
EO adduct and / or EO and other alkylene oxides [C1 or C3 alkylene oxides such as PO, 1,2-BO, 1,4-BO, etc.
Or more] co-adducts (random or block) and the like. The amount of EO used in the above-mentioned adduct is such that the content of oxyethylene units in (b) is 20% by mass or more, especially 30 because the water-swelling property of (A) obtained is good.
The amount of EO in the alkylene oxide used for addition is preferably 25% by mass or more, more preferably 40% by mass or more, and particularly preferably 50 to 95% by mass. Two or more types of (b)
When using, 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: C2-C20 dihydric alcohols (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4 -Butane diol, 1,6-hexane diol, alkylene glycol such as neopentyl glycol; and alicyclic diol (for example, cyclohexane glycol such as cyclohexane diol and cyclohexane dimethanol), trihydric alcohol having 3 to 20 carbon atoms [ Those exemplified in the description of the general formula (1)], 4 to 5 having 20 to 20 carbon atoms
Octahydric or higher polyhydric alcohol [the above general formula (1)
What was illustrated in the explanation of]] etc. (Ii) Polyphenols: monocyclic phenols such as hydroquinone, resorcin, catechol, pyrogallol and phloroglucin; bisphenols such as bisphenol A, bisphenol B, bisphenol F, bisphenol S; and a condensate of phenol and formaldehyde (novolak ); U.S. Pat. No. 326
Polyphenols and the like described in Japanese Patent No. 5641.

(Iii) Low molecular weight amines: ammonia; as aliphatic amines, alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine), 1 to 20 carbon atoms. Alkylamines (for example, n-butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine, and hexamethylenediamine), polyalkylenepolyamines having 4 to 20 carbon atoms (of alkylene groups) Dialkylenetriamine to hexaalkyleneheptamine having 2 to 6 carbon atoms, such as 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 (for example, piperazine and aminoethylpiperazine), and the like.

Preferred as (b) are EO adducts of low molecular weight polyols or polyhydric phenols and co-adducts of EO with other alkylene oxides. More preferably, since the urethane resin from the aromatic ring-containing polyol has good physical properties after water expansion, a co-addition product (random or block) of EO and PO of polyhydric phenols (particularly bisphenols) and these It is a combination of. The number average molecular weight of (b) (by gel permeation chromatograph, hereinafter abbreviated as GPC) is preferably 600 to 8000, more preferably 1000 to 600.
It is 0. The number of functional groups in (b) is preferably 2 to
3 and more preferably 2.

As the organic polyisocyanate (c),
For example, an aliphatic polyisocyanate having 2 to 18 carbon atoms (excluding carbon in an 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.], 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, etc.) and the like. In view of chemical resistance, weather resistance and the like, preferred among these are aliphatic or alicyclic polyisocyanates (particularly diisocyanates), and particularly preferred are HDI, IPDI and hydrogenated MDI.

Examples of the low molecular weight active hydrogen-containing compound (d) include low molecular weight polyols, low molecular weight amines, and alkylene oxide adducts thereof having 2 to 4 carbon atoms, and specific examples thereof include the above ( Among the low molecular weight active hydrogen-containing compounds exemplified as the starting material of b), 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 above alkylene oxide having 3 or 4 carbon atoms) is included. The number average molecular weight (according to GPC) of (d) is usually less than 600, preferably 500 or less.
When (i) is used as (d) or an alkylene oxide adduct of (i), (ii) or (iii) is used, a urethane bond is formed in (A), and when (iii) is used, a urea bond is formed. A bond is created.

The amount of (a) used to obtain (A) is preferably 0.1 to 20% by mass, more preferably the lower limit is 0.5% by mass and the upper limit is based on (b). Is 1
It is 0 mass%. The amount of (d) used is preferably 30% by mass or less, and more preferably 1% with respect to (b).
Is about 20% by mass.

The polyurethane resin (A) is, for example,
Using (a), (b), (c) and optionally (d), it can be produced by either the one-shot method or the prepolymer method. Preferred is a prepolymer method with less manufacturing variation. As an example of the production method of the terminal isocyanate group-containing prepolymer which is an intermediate in the case of producing by the prepolymer method, at least a part of the above (b) and an excess equivalent [(1 equivalent of active hydrogen-containing group in (b) ( The equivalent amount of the isocyanate group in c) is preferably obtained by reacting with (c) of 1.2 to 10] at 70 to 130 ° C. by a conventional method. 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 method for producing (A) by the prepolymer method, at least a part of (b) and the terminal isocyanate group-containing prepolymer from (c) are used as the main component, and (a) and, if necessary, The curing agent component comprising the balance of (b) and / or the mixture of (d), a catalyst,
An additive such as an antioxidant is mixed in advance, both components are cast into a mold, and usually 70 to 120 ° C, preferably 90 to 120 ° C.
(A) is obtained by reacting for 0.5 to 5 hours. The equivalent ratio of the isocyanate group in the main component to the active hydrogen-containing group in the curing agent component is preferably 0.8 to
1.0, and more preferably 0.93 to 0.99.
When the equivalent ratio of the isocyanate group to the active hydrogen-containing group is 0.8 or more, the urethane bond concentration is secured and the amount of eluate in water during water expansion is reduced. When it is 1.0 or less, the plasticity of (A) is secured, and the subsequent kneading and extrusion molding become easy.

In producing the water-swellable polyurethane resin (A), 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 these acid block compounds, metal salts of carboxylic acids (sodium acetate, lead octylate, zinc octylate, cobalt naphthenate, stannas octoate, dibutyltin dilaurate, etc.), alkali metal or alkaline earth metal alkoxides or phenoxides (Sodium methoxide, sodium phenoxide, etc.), quaternary ammonium salt (tetraethylhydroxylammonium, etc.), imidazoles (imidazole, 2-ethyl-4)
-Methylimidazole) and organometallic compounds containing metals such as tin and antimony (tetraphenyl tin, tributyl antimony oxide, etc.) and the like. These catalysts can be used alone or as a mixture. The amount of the catalyst used is preferably 5% with respect to the total mass of all components for obtaining the polyurethane resin.
Below, it is 0.001 to 4% more preferably.

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

(A) The equivalent of ethylenically unsaturated bond per 1000 g (calculated from the reaction equivalent ratio) is 0.00
1 to 3 equivalents are preferred. More preferably, the lower limit is 0.
01 equivalent, the upper limit is 2 equivalents. When the amount is 3 equivalents or less, a corresponding water expansion ratio is obtained according to the content of oxyethylene units, and when the amount is 0.001 equivalents or more, elution into water after water expansion can be suppressed.

Examples of the polymer elastic body (B) blended with the water-swelling polyurethane resin (A) include natural rubber and synthetic rubber (styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile-butadiene rubber). , Ethylene-propylene-diene rubber, butyl rubber, etc.) and recycled rubber thereof, and non-water-expandable (saturation volume water expansion ratio is less than 1.2 times) polyurethane resin having an ethylenically unsaturated bond. It is selected according to the purpose. Of these, preferred are ethylene-propylene-diene rubber, chloroprene rubber and acrylonitrile-butadiene rubber. The compounding amount of (B) is preferably 10 to 800 parts by mass, more preferably the lower limit is 20 parts by mass and the upper limit is 500 parts by mass, relative to 100 parts by mass of (A). When the blending amount of (B) is 10 parts by mass or more, the extruded skin is improved, and when it is 800 parts by mass or less, a corresponding water expansion ratio is obtained according to the content of (B).

The vulcanizing agent (C) blended with the water-swellable polyurethane resin (A) and the elastic polymer (B) is
It may be one usually used for vulcanization of rubber, and examples thereof include 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 (p-quinone dioxime, p,
p'-dibenzoylquinone dioxime, etc.), metal oxides (magnesia, litharge, etc.), alkylphenol resins, polythiol compounds [trimethylolpropane trithioglycolate, trimethylolpropane tri (3
-Mercaptopropionate), glycol dimercaptopropionate, glycol dimercaptoacetate, pentaerythritol tetrathioglycolate, dipentaerythritol hexa (3-mercaptopropionate), etc.], polyamine compound (aldehyde-amine condensate, Guanidines), azo compounds (azobisisobutyronitrile, 2-t-butylazo-2-cyano-4-methylpentane, 4-t-butylazo-4-cyano-valeric acid, etc.), and the like. These vulcanizing agents can be used alone or in combination of two or more kinds. Among these, preferred is sulfur and a combination of sulfur and other vulcanizing agents, particularly sulfur, from the viewpoint of easy handling. Further, the blending amount of (C) is preferably 0.2 with respect to the total 100 parts by mass of (A) and (B).
-10 parts by mass, more preferably, the lower limit is 0.5 parts by mass and the upper limit is 8 parts by mass. When the compounding amount of (C) is 0.2 parts by mass or more, the amount of elution into water during water expansion is small, and 10
When the amount is less than or equal to parts by mass, the vulcanizing agent will not be deposited on the surface after vulcanization.

The filler (D) used in the present invention 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. Can be mentioned.
Of these, carbon black and / or talc is preferable, and FEF black is more preferable among carbon black, and mistron vapor is also preferable among talc. As (D), it is preferable to select one that can suppress the increase in Mooney viscosity even if the relative amount of addition is large, and that can form a stable molded product without causing expansion during molding. The compounding amount of (D) is preferably 10 to 150 parts by mass, more preferably the lower limit is 15 parts by mass and the upper limit is 100 parts by mass, relative to 100 parts by mass of the total of (A) and (B). If it is 10 parts by mass or more, expansion during extrusion molding will be reduced, and the tackiness of the compound will be strong and the processability will be improved. When the amount is 100 parts by mass or less, the extruded skin is improved. Two or more kinds of (D) may be used depending on the Mooney viscosity and tackiness of the kneaded product.

As the modified polyolefin resin (E),
Compatible with both (A) and (B), or (A)
Those having reactivity with are preferable. Examples of compatible compounds include those having a portion in which the difference in SP (solubility parameter by the Fedors method) from (A) is within 2 and a portion in which the difference in SP from (B) is within 2 in one molecule. Can be mentioned. The SP is represented by the square root of the ratio of cohesive energy density and molecular volume, as shown below. [SP] = (ΔE / V) ^1/2 Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Calculated by Fedors et al., For example, Polymerengin
earning and science Volume 14, 1
47-154.

As a specific example of (E), one selected from the group consisting of a carboxylic acid group, a carboxylic acid group, a carboxylic acid anhydride group, an amide group, a hydroxyl group and an epoxy group in the main chain or side chain of polyolefin. The modified polyolefin resin containing the above functional groups is mentioned. Among the functional groups of (E), a carboxylic acid anhydride group and an epoxy group having reactivity with the water-swellable urethane resin (A) are preferable,
More preferably, it is a carboxylic acid anhydride group. Examples of the polyolefin forming the skeleton of (E) include olefins having 2 to 10 carbon atoms (ethylene, propylene, 1-
One or more (co) polymers (such as butene).
Preferred are polyethylene and polypropylene.
The functional group concentration of (E) is usually 0.1 to 10% by mass, preferably the lower limit is 1% by mass and the upper limit is 8% by mass. When the functional group concentration is 0.1% by mass or more, the surface of the extrusion molded article is good, and when it is 10% by mass or less, the compatibility with (B) is good. The number average molecular weight of (E) (by GPC method) is usually 800 to 20,000, preferably 1,000 to 18,000.
Is. When the number average molecular weight is 20000 or less, the surface of the extrusion-molded product is good, and when it is 800 or more, it does not deposit on the surface after extrusion. The compounding amount of (E) is 100 in total of (A) and (B).
It is preferably 30 parts by mass or less with respect to parts by mass. The lower limit is more preferably 1 part by mass, particularly preferably 3 parts by mass, and the upper limit is more preferably 28 parts by mass, particularly preferably 20 parts by mass. (E) content of 30
When the amount is less than or equal to parts by mass, the corresponding water expansion ratio is obtained, and when the amount is greater than or equal to 1 part by mass, the surface of the extrusion molded article becomes particularly good.

In the present invention (I) and (III),
Although it is necessary to use (E) as an essential component, in the present inventions (II) and (IV), the compatibility between the water-swellable polyurethane resin (A1) and the polymeric elastomer (B) is relatively good. Therefore, it is preferable to use (E), but it is not always necessary.

In the water-swellable rubber molded article of the present invention, if necessary, a pigment [inorganic pigment (titanium oxide, red iron oxide, yellow lead,
Cadmium sulfide, ultramarine, etc.), and organic pigments (azo, phthalocyanine, quinacridone, dioxazine, etc.)] can also be contained. The amount of these pigments to be added 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 (A) and (B).

Further, if necessary, a vulcanization accelerator [eg, guanidines (diphenylguanidine, diorsotolylguanidine, etc.), thiazoles (2-mercaptobenzothiazole, dibenzothiazyl disulfide, etc.), thiurams (tetramethylthiuram disulfide, Tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram tetrasulfide, etc.) and sulfenamides (N-cyclohexyl-2-benzothiazole sulfenamide, N-
t-butyl-2-benzothiazolesulfenamide, etc.), vulcanization accelerator [fatty acids having 8 to 24 carbon atoms and their derivatives (stearic acid, oleic acid, lauric acid, zinc stearate, etc.) and metal oxidation] And metal salts (zinc oxide, zinc carbonate, etc.), foaming agents [nitroso compounds (N, N′-dinitrosopentamethylenetetramine, etc.), and azo compounds (azobisisobutyronitrile, azodicarbonamide, etc.) Etc.], softener [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, etc. , 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, sub (white sub, black sub, amesub), polyester-based, epoxy-based, etc.],
And an antioxidant [amines (N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-
Phenyl-N'-isopropyl-p-phenylenediamine, etc., amine ketones (2,2,4-trimethyl-)
1,2-dihydroquinoline polymer), hindered phenols [2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis (3-methyl-6-t-butylphenol), 4 , 4'-butylidene bis (3-methyl-6-t-butylphenol) and the like], and dithiocarbamate salts (nickel dibutyldithiocarbamate and the like)] and the like] can be added. If necessary, a trifunctional or higher functional ethylenically unsaturated bond-containing compound (for example, triallyl isocyanurate) may be blended with (C) as a urethane crosslinking agent during vulcanization.

The addition amount (mass basis) of these additives is
The vulcanization accelerator, the vulcanization acceleration aid and the foaming agent are each usually 10% or less, preferably 0.001 to 5%, and the softening agent is usually 20% or less with respect to the total mass of the molded article of the present invention. , Preferably 0.1 to 15%, and the antiaging agent is usually 10% or less, preferably 0.001 to 5%. The total addition amount of these additives is preferably 20% or less,
More preferably, it is 0.1 to 15%.

Kneaded product of water-swellable polyurethane resin (A), polymer elastic body (B), vulcanizing agent (C), filler (D) and modified polyolefin resin (E), and water-swellable polyurethane resin ( A1), (B), (C) and (D)
The kneaded product of No. 1 has a Mooney viscosity of 100 ° C. according to JIS K6300 “Unvulcanized Rubber Physical Test Method” (1994 version).
After preheating for 1 minute at, the value after rotating the L-shaped rotor for an additional 4 minutes, preferably [15ML (1 + 4) 100
° C] or higher, more preferably [20 ML (1 + 4) 10
0 ° C.] or higher. Mooney viscosity [15ML (1+
4) When the temperature is 100 ° C. or higher, shape retention after extrusion becomes easy.

The water-swellable rubber molded article of the present invention is, for example, a Banbury mixer or a kneader, and is used as a water-swellable polyurethane resin (A), polymer elastic body (B), filler (D), modified polyolefin (E) and After kneading the other compounding agent as necessary, the vulcanizing agent (C) and, if necessary, the vulcanization accelerator are kneaded on a roll and subjected to extrusion molding, press molding or the like to obtain a desired shape (for example, prismatic shape, cylindrical shape, Sheet)
It is obtained by molding into a vulcanized product and vulcanization under heating. In addition, after kneading the water-swellable polyurethane resins (A1), (B), (D) and, if necessary, other compounding agents, kneading (C) and, if necessary, a vulcanization accelerator on a roll, and similarly kneading. Obtained by sulfurization. The heat curing temperature is set according to the type of vulcanizing agent, but is preferably 150 to 200 ° C. In addition, a composite water-stop having an expanding portion and a non-expanding portion can be obtained by co-extruding with a normal non-expanding rubber [for example, one obtained by kneading (B), (C), (D) and optionally (E)] Materials can also be created.

The water-expandable rubber molded product of the present invention is (1) extruded or co-extruded with a non-expandable rubber to obtain a seal material for segments having various cross-sectional shapes; (2)
By forming it into a hollow or plate shape, it can be used for building gaskets, etc .; (3) It can be used for water-expandable packing such as grout holes by forming it into a ring shape with a circular cross section by press molding, especially for shield tunnels. It is suitable for segment sealing materials and water stop plates for concrete joints.

[0045]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following,% means% by mass and part means part by mass.

Example 1 A mixture of EO and PO in bisphenol A (mass ratio 80 /
20) was added to 1000 parts of a polyether glycol having a number average molecular weight of 4000 and 383 parts of dicyclohexylmethane diisocyanate were reacted at 120 ° C. for 3 hours to obtain a prepolymer having an isocyanate group content of 8%. Then, as a curing agent component, 39.5 parts of glycerin monoallyl ether (the obtained urethane resin 1000
0.1 equivalent to g of ethylenically unsaturated bond) and polyethylene glycol (number average molecular weight 1500) 15
67 parts (amount in which the equivalent ratio of the isocyanate groups of the prepolymer to the total of the hydroxyl groups of the curing agent component is 0.98)
And 2.83 parts of triethylenediamine were added and reacted at 110 ° C. for 5 hours to obtain a polyoxyethylene-based urethane resin (urethane bond concentration 1.05 equivalent / 1000 g). To 100 parts of this resin, ethylene-propylene-diene rubber [Mitsui EPT4070, Mitsui Chemicals, Inc.
100 parts, FEF black [Asahi # 60, manufactured by Asahi Carbon Co., Ltd.] 50 parts, stearic acid 0.5 parts, zinc oxide 1
Parts, maleic anhydride modified polyethylene [UMEX 2
000, Sanyo Chemical Industry Co., Ltd.] 10 parts, process oil [Dyna Process Oil PW-380, Idemitsu Kosan Co., Ltd.] 20 parts, after kneading with a Banbury mixer,
After compounding 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole with a two-roll mill (the Mooney viscosity [42 ML (1 + 4) 100 of the compound)
℃]), molded with an extruder using a Garve die, 180 ℃
Heated in an oven for 10 minutes.

Example 2 To 100 parts of the polyoxyethylene-based urethane resin of Example 1, ethylene-propylene-diene rubber [Mitsui E
PT4070, manufactured by Mitsui Chemicals, Inc.] 100 parts, FEF black [Asahi # 60, manufactured by Asahi Carbon Co., Ltd.] 25 parts, talc [Misstron vapor, manufactured by Japan Mistron Co., Ltd.] 2
5 parts, stearic acid 0.5 part, zinc oxide 1 part, maleic anhydride-modified polyethylene [UMEX 2000, Sanyo Kasei Co., Ltd.] 10 parts, process oil [Dyna Process Oil PW-380, Idemitsu Kosan Co., Ltd.] 20 parts by mass was kneaded with a Banbury mixer, and then 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole were compounded with a two-roll mill (the Mooney viscosity [40 ML (1 + 4) 100 of the compound). ℃]), was molded by an extruder using a Garve die, and heated in an oven at 180 ° C. for 10 minutes.

Example 3 To 100 parts of the polyoxyethylene-based urethane resin of Example 1, ethylene-propylene-diene rubber [Mitsui E
PT4070, manufactured by Mitsui Chemicals, Inc.] 180 parts, FEF black [Asahi # 60, manufactured by Asahi Carbon Co., Ltd.] 50 parts, stearic acid 0.5 part, zinc oxide 1 part, process oil [Dyna Process Oil PW-380]. Manufactured by Idemitsu Kosan Co., Ltd.]
After kneading 20 parts with a Banbury mixer, 2 parts of sulfur,
After blending 4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole with a two-roll roll (Moonie viscosity of the blend [37 ML (1 + 4) 100 ° C.]), the mixture was molded by an extruder using a garve die, and 180 ° C. Heated in an oven for 10 minutes.

Example 4 A mixture of EO and PO in bisphenol A (mass ratio 50 /
50) and a mixture of 350 parts of polyether glycol having a number average molecular weight of 5300 and 650 parts of an EO adduct of bisphenol A (number average molecular weight of 670) and 376 parts of isophorone diisocyanate are reacted at 120 ° C. for 3 hours. Then, a prepolymer having an isocyanate group content of 4% was obtained. Next, as a curing agent component, 38.7 parts of trimethylolpropane monomethacrylate (corresponding to 0.1 equivalent of ethylenic unsaturated bond to 1000 g of the obtained urethane resin) and polyethylene glycol (number average molecular weight 1500) 687 parts (prepolymer) (Equivalent ratio of the isocyanate groups to the total number of hydroxyl groups of the curing agent component is 0.98) and 2.84 parts of triethylenediamine are added and reacted at 110 ° C. for 5 hours to give a polyoxyethylene-based urethane resin (urethane). Binding concentration 1.61 equivalent /
1000 g) was obtained. To 100 parts of this resin, ethylene-propylene-diene rubber [Mitsui EPT4070,
Mitsui Chemicals, Inc.] 100 parts, FEF black [Asahi # 6
0, manufactured by Asahi Carbon Co., Ltd.] 50 parts, stearic acid 0.5
Parts, zinc oxide 1 part, maleic anhydride-modified polyethylene [UMEX 2000, Sanyo Chemical Industry Co., Ltd.] 10
Parts, process oil [DYNA process oil PW-38
0, manufactured by Idemitsu Kosan Co., Ltd.] 20 parts by kneading with a Banbury mixer, and then 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide and 2 parts of 2-mercaptobenzothiazole were blended with two rolls (Moonie of the compound) Viscosity [42ML (1
+4) 100 ° C.]), the mixture was molded by an extruder using a Garve die, and heated in an oven at 180 ° C. for 10 minutes.

Example 5 To 100 parts of the polyoxyethylene-based urethane resin of Example 1, ethylene-propylene-diene rubber [Mitsui E
PT4070, manufactured by Mitsui Chemicals, Inc.] 100 parts, FEF black [Asahi # 60, manufactured by Asahi Carbon Co., Ltd.] 50 parts, stearic acid 0.5 part, zinc oxide 1 part, maleic anhydride modified polyethylene [Umex 2000, Sanyo Kasei Kogyo Co., Ltd.] 10 parts, process oil [Dyna Process Oil PW-380, Idemitsu Kosan Co., Ltd.] 40 parts were kneaded with a Banbury mixer, then 2 parts of sulfur, 4 parts of dibenzothiazyl disulfide, 2 -After blending 2 parts of mercaptobenzothiazole in two rolls (Moonie viscosity of the blend [33 ML (1 + 4) 100 ° C]), it was molded in an extruder using a garve die and heated in an oven at 180 ° C for 10 minutes. .

Comparative Example 1 A mixture of EO and PO in propylene glycol (mass ratio 7
8/22) was added to obtain 423 parts of a polyether glycol having a number average molecular weight of 7050, 4.1 parts of allyl alcohol, and 16.5 parts of toluylene diisocyanate, and the mixture was stirred and reacted at 110 ° C. for 5 hours. Polyoxyethylene-based urethane resin (urethane bond concentration 0.43
Equivalent / 1000 g) was obtained. With respect to 100 parts of this resin, 182 parts of natural rubber, 55 parts of HAF carbon black [SEAST 3 HAF, manufactured by Tokai Carbon Co., Ltd.], 91 parts of calcium carbonate, 1.8 parts of stearic acid, 9.0 parts of zinc oxide, After blending 5.5 parts of sulfur and 2.7 parts of N-cyclohexyl-2-benzothiazole sulfenamide with a two-roll mill (the Mooney viscosity [58 ML (1+
4) 100 ° C.]), was molded by an extruder using a Garve die, and heated in an oven at 145 ° C. for 30 minutes.

Comparative Example 2 Mixture of EO and PO in glycerin (mass ratio 45/55)
420 parts of polyether glycol having a number average molecular weight of 4,200 and toluylene diisocyanate 5
2.2 parts were reacted at 120 ° C. for 3 hours to obtain a prepolymer having an isocyanate group content of 2.7%. Next, as a curing agent component, 9.7 parts of butenediol was added at 110 ° C.
At room temperature for 5 hours to obtain a polyoxyethylene-based urethane resin (urethane bond concentration: 1.25 equivalent / 1000 g). 182 parts of natural rubber, H of 100 parts of this resin
AF carbon black [SEAST 3 HAF, manufactured by Tokai Carbon Co., Ltd.] 55 parts, calcium carbonate 91 parts, stearic acid 1.8 parts, zinc oxide 9.0 parts, sulfur 5.5 parts, N
-Cyclohexyl-2-benzothiazole sulfenamide (2.7 parts) was compounded with a two-roll mill (Moonie viscosity of the compound [60 ML (1 + 4) 100 ° C]), and then molded with an extruder using a garve die and 145 ° C. Heated in oven for 30 minutes.

[Performance Test Example] The hardness, tensile property value and extrusion moldability of each molded product of Examples 1 to 5 and Comparative Examples 1 to 2 are shown in Table 1, and the volume water expansion ratio test and the mass reduction rate test are performed. The results are shown in Table 2. The test method is as follows. (Moonie viscosity) According to "Unvulcanized rubber physical test method" described in JISK6300 (1994 version), an L-shaped rotor was used, preheated at 100 ° C for 1 minute, and then rotated.
The value after 4 minutes was measured. (Hardness) According to "Hardness test method of vulcanized rubber and thermoplastic rubber" described in JISK6253 (1997 edition), 2
Type A by stacking 4 sheets that are press-formed to a thickness of mm
It was measured with a durometer. (Tensile strength, elongation) JISK6251 (1993 version)
According to the “Tensile test method for vulcanized rubber” described, a No. 3 dumbbell test piece was punched out from a sheet press-molded to a thickness of 2 mm and measured. The tensile strength after expansion was measured after the No. 3 dumbbell test piece prepared in the same manner was immersed in tap water at 23 ° C. for 1 month.

(Extrusion Moldability) The extrusion moldability of the rubber was evaluated by ASTM D2230 (B evaluation) of the Garve die extrusion molded product. (Volume of water expansion) A 20 × 20 × 2 mm test piece was sampled from the strip, and the volume when the test piece was immersed in purified water at 23 ° C. was measured at regular intervals. The expansion ratio was calculated. Volumetric water expansion ratio (times) = Volume when expanded / Volume before expansion Also, the rate of increase in the volumetric water expansion ratio per day is 0.01
The ratio at the time of becoming less than or equal to
The magnification at the time of becoming 1 time or less) was taken as the saturated volumetric water expansion magnification of the test piece. (Mass reduction rate) Volumetric water expansion ratio 6 months After the measurement, the test piece is dried in an oven at 60 ° C.
The mass when the following became the mass after drying and was calculated by the following formula. Mass reduction rate (%) = 100 × (mass before expansion−mass after drying) / mass before expansion

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

The water-expandable rubber molded product of the present invention has the following effects. (1) It is stable with no reactivity during compounding and kneading, and can be easily processed on a Banbury mixer and rolls like ordinary rubber. (2) A rubber can be molded by a commonly used molding method (extrusion molding, press molding, etc.) to obtain molded articles of various shapes. (3) By performing the three-dimensional reaction at the vulcanization temperature,
The elution of water-absorbing components after water expansion is significantly reduced, and stable expansion performance is exhibited over a long period of time. (4) The water swellability can be adjusted by adjusting the oxyethylene unit content and the ethylenically unsaturated bond content of the water swellable polyurethane resin. From the above effects, the water-expandable rubber molded product of the present invention can be used as a sealing material for various industrial applications, and in particular, a segment sealing material for shield tunnels, a water stop plate for concrete joints and a building gasket. Is useful as

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C08L 23/26 C08L 23/26 75/14 75/14 75/14 (72) Inventor Kimio Miura Hitotsubashi-honcho, Higashiyama-ku, Kyoto-shi, Kyoto Prefecture 1 at 11 Sanyo Kasei Co., Ltd. (72) Inventor Jiro Nagago Ichihashi Honcho, Higashiyama-ku, Kyoto City, Kyoto Prefecture 1 at 11 Sanyo Kasei Co., Ltd. (72) Inventor Tatsuro Toyota Misono-cho, Nishi-ku, Hiroshima-shi, Hiroshima 2-2-8 Nishikawa Rubber Industry Co., Ltd. (72) Inventor Hiroshi Matsuoka 2-2-8, Misonomachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Nishikawa Rubber Industry Co., Ltd. F-term (reference) 4F071 AA15X AA20X AA53 AA76 AB03 AB04 AC08 AC13 AE02 AF04 BA09 BB03 BB06 BC03 4J002 AC01X AC03X AC06X AC07X AC08X BB15X BB18X BB213 CC104 CK02X CK04W DA037 DA046 DE076 DE156 DE237 DG016 DJ017 DJ037 FD017 EV046 DJFD47 EV036 EK046 EN046 EQ016 ES016 EN046 EQ016 ES016

Claims (12)

[Claims] 1. A water-swellable polyurethane resin (A) having at least one ethylenically unsaturated bond, a polymeric elastomer (B), a vulcanizing agent (C), a filler (D), and a modified polyolefin resin. An extruded or press-molded product of the kneaded product of (E) is heat-cured, and has a saturated volumetric water expansion ratio of 1.2 to 8 times, which is a water-expandable rubber molded product. 2. (A) is a compound (a) represented by the following general formula (1), a polyoxyalkylene polyol (b) containing at least 20% by mass of an oxyethylene unit,
The molded article according to claim 1, which is a resin obtained from the organic polyisocyanate (c) and, if necessary, the low molecular weight active hydrogen-containing compound (d). (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 rm is 1 or more. ] 3. A compound (a) represented by the following general formula (2):
1), a polyoxyalkylene polyol (b) containing at least 20 mass% of oxyethylene units, an organic polyisocyanate (c), and optionally a low-molecular active hydrogen-containing compound (d), a water-swellable polyurethane resin ( An extruded or press-molded product of a kneaded product comprising A1), a polymeric elastic body (B), a vulcanizing agent (C), a filler (D), and optionally a modified polyolefin resin (E) is heat-cured, A water-expandable rubber molded article having a saturated volume expansion ratio of 1.2 to 8 times. (HO) mR (OX ₁ ) rm (2) [wherein, R is a residue of an r-valent polyol, X ₁ is a group having no active hydrogen-containing group and at least one ethylenically unsaturated bond, r Is an integer of 3 or more, m is 2 or more, and r-m is an integer of 1 or more. ] 4. The total equivalent of urethane bonds and urea bonds per 1000 g of (A) is 0.5 to 2.5 equivalents, and the equivalent of ethylenically unsaturated bonds is 0.001 to 3 equivalents. The molded article according to any one of 3 to 3. 5. The molded article according to claim 2, wherein (c) is an aliphatic and / or alicyclic polyisocyanate. 6. The method according to claim 1, wherein (B) is at least one selected from natural rubber, synthetic rubber, recycled rubber thereof, and non-water-swelling polyurethane resin having an ethylenically unsaturated bond. The molded product described in. 7. The molded product according to claim 1, wherein (C) is sulfur. 8. The molded article according to claim 1, wherein (D) is carbon black and / or talc. 9. The molded product according to claim 1, which is used for a water blocking material. 10. The molded product according to any one of claims 1 to 9, which is a segment sealing material for a shield tunnel or a water blocking plate for a concrete splicing part. 11. A water-swellable polyurethane resin (A) having at least one ethylenically unsaturated bond, a polymeric elastomer (B), a vulcanizing agent (C), a filler (D) and a modified polyolefin resin ( The kneaded product consisting of E) is extruded or press-formed into a desired shape, and the ethylenically unsaturated bonds of (A) and (B) are reacted with (C) under heating to give a saturated volume expansion ratio of 1. A method for producing a water-expandable rubber molded product, which is characterized in that a molded product of 2 to 8 times is obtained. 12. A compound (a1) represented by the following general formula (2) and at least 20% by mass of oxyethylene units.
A water-swellable polyurethane resin (A1), a polymer elastic body (B), and a polyoxyalkylene polyol (b), an organic polyisocyanate (c), and optionally a low-molecular active hydrogen-containing compound (d) Sulfurizing agent (C),
A kneaded material comprising a filler (D) and optionally a modified polyolefin resin (E) is extruded or press-molded into a desired shape, and the ethylenically unsaturated bond of (A1) and (B) and (C) are heated. ) Is reacted to obtain a molded product having a saturated volume expansion ratio by water of 1.2 to 8 times, which is a method for producing a water-expandable rubber molded product. (HO) mR (OX ₁ ) rm (2) [wherein, R is a residue of an r-valent polyol, X ₁ is a group having no active hydrogen-containing group and at least one ethylenically unsaturated bond, r Is an integer of 3 or more, m is 2 or more, and r-m is an integer of 1 or more. ]