JPH0139472B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-swellable waterproof material. Regarding the use of compositions made of rubber and water-swellable polymer substances as water-stopping materials or caulking materials, see Japanese Patent Application Laid-open Nos. 53-143653 and 54-7461.
No. 54-7463, No. 54-20066, etc., and are publicly known. However, conventionally, when manufacturing such a rubber and water-swellable polymer composition, the manufacturing method simply kneads the rubber and water-swellable polymer material and vulcanizes only the rubber component, resulting in poor compatibility and blooming. There have been major practical difficulties, such as easily causing water damage, lacking mechanical strength, and when used as a waterproofing material, water-swellable polymer substances elute into water and contaminate the water. The present inventors continued their studies with the aim of improving the above problems and obtaining high-quality water-swellable polymeric substances for use in water-stopping materials, waterproofing materials, etc. The present invention was completed by discovering that by crosslinking the material with a crosslinking agent, the material has good long-term storage stability, high strength, and no water-swellable material is eluted when immersed in water. That is, in the water-swellable water-stopping material of the present invention, a water-swellable substance () having a hydrophilic polyether bond and an ethylenically unsaturated bond in the molecule and a rubber () form a bridge between the molecules. It is characterized by containing a substance crosslinked by substance (). Such a substance can be produced, for example, by crosslinking a composition consisting of the above-mentioned water-swellable substance () and rubber () with a substance () that creates cross-linking between molecules, but the method is not limited to this method. It's not a thing. This manufacturing method will be explained below. In order to fully exhibit its water-swelling effect, the water-swellable substance used in the present invention has a hydrophilic polyether bond of 20% by weight or more in the molecule, and an average of 1 or more in the molecule. It has ethylenically unsaturated bonds, and more preferably polyethylene oxide bonds are introduced as hydrophilic polyether bonds. In addition, the water-swellable substance () can have a molecular weight of 200 or more, preferably 1,000 or more, and can be used in the hundreds of thousands. Just choose something. Examples of such water-swellable substances include esterified compounds, ether compounds, urethanized compounds, and other compounds as shown below. First, as esterified products or ether compounds, there are the following compounds. A polyether preferably having an average molecular weight of 200 or more obtained by adding an alkylene oxide (2) to an active hydrogen-containing compound (1) having no ethylenically unsaturated bond, or a compound with the polyether
Esterified product obtained by condensing a mixture of (1) with an acid having an ethylenically unsaturated bond or its acid anhydride (3) An active hydrogen-containing compound (1) having no ethylenically unsaturated bond An alkylene oxide (2) is added to a condensate preferably having an average molecular weight of 200 or more obtained by condensing an acid having an ethylenically unsaturated bond or its acid anhydride (3), or a mixture of the condensate and compound (1). ) An esterified product obtained by further condensing the above esterified product with the above acid or its acid anhydride (3), or an esterified product obtained by adding the above compound (1) with an acid or acid having no ethylenically unsaturated bond. Its acid anhydride (4)
and an esterified product obtained by adding alkylene oxide (2) to a condensate, preferably having an average molecular weight of 200 or more, or a mixture of the condensate and compound (1), which has an ethylenically unsaturated bond. An esterified product obtained by further condensing an acid or its acid anhydride (3) A polyether compound obtained by adding an alkylene oxide (2) to an active hydrogen-containing compound (5) having an ethylenically unsaturated bond The above-mentioned polyether compound or this and compound
An acid or its acid anhydride (3) and/or an acid or its acid anhydride (4) in a mixture with (1) or (5)
An esterified product obtained by condensing the above compound (5) and an acid or its acid anhydride (3) and/or an acid or its acid anhydride (4), or a condensate and a compound ( An esterified product obtained by adding an alkylene oxide (2) to a mixture of 1) or (5). An acid or an acid anhydride (3) to the above esterified product or a mixture of this and compound (1) or (5). and/or an esterified product obtained by condensing an acid or its acid anhydride (4) The above-mentioned esterified product can be obtained by a conventional esterification reaction, and the equivalent ratio of OH/COOH is 1 to 1.4. It is desirable to do so within the range of . Next, examples of the urethane compound include the following compounds. A urethane compound obtained by reacting a polyether obtained by adding an alkylene oxide (2) to a compound (1), preferably having an average molecular weight of 200 or more, with an organic diisocyanate (6) and a compound (5). Urethane obtained by reacting a polyether with an average molecular weight of 200 or more obtained by adding alkylene oxide (2) to compound (5), and organic diisocyanate (6), and adding compound (1) or (5) if desired. Compound The above esterified product and organic diisocyanate
Esterified product obtained by reacting (6) with compound (1) or (5) if desired The above esterified product and organic diisocyanate
A urethane compound obtained by reacting (6) with compound (1) or (5) if desired. The above ester compound and an organic diisocyanate.
A urethane compound obtained by reacting (6) with compound (1) or (5) if desired. The above ester compound and an organic diisocyanate.
A urethane compound obtained by reacting (6) with compound (1) or (5) if desired. The above ester compound and an organic diisocyanate.
A urethane compound obtained by reacting (6) with compound (1) or (5) if desired. The above ester compound and an organic diisocyanate.
A urethane compound obtained by reacting (6) with compound (1) or (5) if desired. The above urethane compound can be obtained by a conventional urethane reaction. It is preferable that NCO% is 10% or less.
If the NCO% is 10% or more, the amount of unreacted monomer may increase in some cases, which will have a negative effect on the subsequent kneading process, and a large amount will be eluted when the water-stopping material is immersed in water, so it is preferable. do not have. The most preferred urethane compound is a thermoplastic polyurethane with an NCO% close to or zero. As mentioned above, the esterified products, ether compounds, and urethanized products have 10% by weight or more of hydrophilic polyether bonds consisting of polyethylene oxide bonds in the molecule, and also have an average of one or more ethylenic polyether bonds in the molecule. Of course, it is preferable to prepare it so that it has an unsaturated bond. Furthermore, the water-swellable substance (2) of the present invention is not limited to the above-mentioned compounds, but compounds meeting the above-mentioned conditions can be appropriately produced and used. Examples of the active hydrogen-containing compound (1) having no ethylenically unsaturated bond include alcohol (1-1), polyol (1-2), amine (1-3), and mixtures thereof. Examples of the alcohol (1-1) include methanol, ethanol, isopropanol, propanol, butanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol,
3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tert-amyl alcohol, sec-isoamyl alcohol, neopentyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, isohexyl alcohol, 4-methyl- Examples include 2-pentanol, 3-methyl-2-pentanol, 2,3-dimethyl-2-butanol, pinacolyl alcohol, and mixtures thereof. Examples of the polyol (1-2) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol dioxyethyl ether, bisphenol dioxypropyl ether,
Neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, mixtures thereof, and the like can be mentioned. Examples of the amine (1-3) include monoethanolamine, diethanolamine, triethanolamine, diethylenetetramine, and the like. Examples of the alkylene oxide (2) include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epihalohydrin, allyl glycidyl ether, and mixtures thereof. Examples of the acid having an ethylenically unsaturated bond or its acid anhydride (3) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, angelic acid, tiglic acid, allyl acetate, ethyl crotonic acid, and undecenoic acid. , oleic acid, maleic acid, maleic anhydride, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid,
Examples include terraconic acid, allylmalonic acid, citraconic anhydride, and mixtures thereof. Examples of the acid having no ethylenically unsaturated bond or its acid anhydride (4) include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, 2-
Methylbutanoic acid, pivalic acid, hexanoic acid, isocaproic acid, 2-ethylbutanoic acid, dimethylbutyric acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, malonic acid, succinic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, dimethylsuccinic acid, succinic anhydride, tricarballylic acid, aconitic acid , camphoronic acid, and mixtures thereof. Examples of the active hydrogen-containing compound (5) having an ethylenically unsaturated bond include butenediol, hexenediol, allyl alcohol, crotyl alcohol, allyl glycol, 3-penten-1-ol, 2-methyl-3-butene- 1-all, 3
-hexen-1-ol, 4-hexen-1-ol, 2,4-hexadien-1-ol, 1,
4-hexadien-3-ol, 1,3-hexadien-5-ol, 3-hepten-2-ol, 2-octen-4-ol, 2-methyl-6
-penten-2-ol, 6-methyl-2-penten-6-ol, and formula HO (-CH ₂ -CH=CH
-CH ₂ -) _o OH (where n is the molecular weight of 1000 to 100000)
), as well as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxyethylacrylamide, methacrylic acid-t
-butyl-aminoethyl, mixtures thereof, and the like. Examples of the organic diisocyanate (6) include aliphatic diisocyanates such as hexamethylene diisocyanate, aromatic diisocyanates such as diphenylmethane-4,4' diisocyanate and toluylene diisocyanate, hydrogenated aromatic diisocyanates, and fatty acids such as isophorone diisocyanate. Various organic diisocyanates such as cyclic diisocyanates can be mentioned. The rubber used in the present invention includes natural rubber, synthetic rubber, or recycled rubber, such as natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene diene terpolymer, butyl rubber. and recycled rubber, etc., which are selected depending on the use and purpose. The water-swellable substance () is used in an amount of 10 to 500 parts, preferably 10 to 300 parts, per 100 parts (by weight, the same applies hereinafter) of the rubber (). Substances that create cross-linking between molecules () used in the present invention are water-swellable substances (), rubber ()
Rubber vulcanizing agents such as sulfur, sulfur chloride, organic peroxides, organic sulfur compounds, metal oxides, alkylphenol resins, and polythiol compounds. can be used. Particular preference is given to crosslinking with sulfur and organic peroxides. Sulfur is preferably powdered sulfur, and suitable organic peroxides include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl perbenzoate, t-
Butyl hydroperoxide, t-butylbenzene peroxide, cumene hydroperoxide, t-
Examples include butyl peroctoate. Suitable organic sulfur compounds include tetramethylthiuram disulfide (TT), N,N'-dithiobismorpholine, and the like. Suitable metal oxides include zinc white, magnesia, litharge, and the like. Suitable alkylphenol resins include alkylphenol formaldehyde resins containing 7 to 10% methylol groups. Suitable polythiol compounds include trimethylolpropane trithioglycolate, trimethylolpropane tri(3-mercaptopropionate), glycol dimercaptopropionate,
Examples include glycol dimercaptoacetate, pentaerythritol tetra(3-mercaptopropionate), petaneerythritol tetrathioglycolate, dipentaerythritol hexa(3-mercaptopropionate), and the like. The above-mentioned cross-linking agents () can be used alone or in a suitable combination of two or more, and the amount thereof is suitably 0.5 to 10 parts per 100 parts of the rubber (). A cross-linking agent () is added to the above water-swellable substance () and rubber (), and a vulcanization accelerator, a vulcanization aid,
General rubber compounding agents such as softeners, anti-aging agents, and adhesives are appropriately selected and blended, and then kneaded using a kneading roll, a Banbury mixer, or the like. If necessary, after molding, press, vulcanize, etc.
A vulcanization treatment (usually at 120° C. or higher) is performed to obtain the water-swellable waterproof material of the present invention. The vulcanization treatment is not limited to heat vulcanization, steam vulcanization, or hot air vulcanization, but may also be natural vulcanization, hot water vulcanization, or cold vulcanization. As described above, the water-swellable water stop material of the present invention is characterized in that the water-swellable substance (2) and the rubber (2) are integrally crosslinked with each other. Furthermore, the water stop material of the present invention can be applied in an amorphous or putty form before crosslinking, and can be used in a state where it is hardened by natural crosslinking (natural vulcanization).
It can also be preferably applied to locations where the shape is complex and a regular sealing material cannot be applied. The water-swellable waterproof material of the present invention exhibits excellent water-swellability (swelling rate of 10 to 300%), and in particular, substances do not elute into the water during immersion in water and do not contaminate the water. Therefore, it can be used not only as a general sealing material, water-stopping material, caulking material, and sealing material, but also especially for waterworks where water contamination is averse. In addition, the water-swellable water-stop material of the present invention has excellent waterproofness and water-stopping properties, as well as excellent workability, mechanical strength, and stability. The water-swellable waterproof material of the present invention may also include carbon black, silica, calcium silicate, calcium carbonate, clay, alumina, barite,
It is also possible to mix and use fillers such as zinc oxide, carbonate, magnesium carbonate, talc, glass microspheres, glass fibers, carbonate fibers, and asbestos in appropriate amounts. Next, examples of the present invention will be shown. Production Examples Water-swellable substances used in Examples and Comparative Examples ()
As shown below, crosslinked polyols A, B, C,
Crosslinked urethane resins A, B, and C, non-crosslinked comparative polyols D and E, and non-crosslinked comparative urethane resins D and E were produced. Cross-linked polyol A A polymer with an average molecular weight of 3,550 made by randomly adding ethylene oxide and propylene oxide to propylene glycol, and a polymer with an average molecular weight of 3,658 made by reacting 1 mole of polyether containing 60% ethylene oxide groups with 1.5 moles of acrylic acid. . Cross-linked polyol B: 1 mole of polyether made by adding propylene oxide to propylene glycol and then adding ethylene oxide to give an average molecular weight of 1220 and 72% ethylene oxide groups, and ethylene glycol
A polymer with an average molecular weight of 5500 made by reacting 0.5 mol and 1.4 mol of itaconic acid. Crosslinked polyol C 1.15 mol of diethylene glycol and maleic acid
Average molecular weight 2300 obtained by reacting with 1.02 mol
A polymer with an average molecular weight of 6500, made by adding ethylene oxide to polyester. Cross-linked urethane resin A Average molecular weight of propylene glycol with ethylene oxide and propylene oxide added
7050, polyether with 78% ethylene oxide groups
A urethane resin obtained from the reaction of 1.2 moles of allyl alcohol, 1.4 moles of allyl alcohol, and 1.9 moles of toluylene diisocyanate. Crosslinked urethane resin B A urethane resin obtained by the reaction of 1.5 mol of crosslinked polyol B, 0.3 mol of butylene glycol, and 1.8 mol of diphenylmethane-4,4'-diisocyanate. Cross-linked urethane resin C Average molecular weight made by randomly adding ethylene oxide and propylene oxide to glycerin
4200, polyether with 45% ethylene oxide groups
Urethane resin obtained by reacting 1.0 mol with 3.0 mol of TDI and then reacting with 1.1 mol of butenediol. Comparative Polyol D A polymer made by randomly adding ethylene oxide and propylene oxide to propylene glycol and having an average molecular weight of 3550 and 60% ethylene oxide groups. Comparative polyol E 1.15 mol of diethylene glycol and adipic acid
Average molecular weight 2300 obtained by reacting with 1.02 mol
A polymer with an average molecular weight of 6500, made by adding ethylene oxide to polyester. Comparative urethane resin D Average molecular weight of propylene glycol with propylene oxide and ethylene oxide added
7050, polyether with 78% ethylene oxide groups
A urethane resin obtained by the reaction of 1.2 mol of toluylene diisocyanate with 1.2 mol of toluylene diisocyanate. Comparative Urethane Resin E A urethane resin obtained by reacting 1.0 mol of polyether with an average molecular weight of 4200 and 45% ethylene oxide groups, which is obtained by adding ethylene oxide and propylene oxide to glycerin, and 3.0 mol of toluylene diisocyanate. Examples 1 to 3, Comparative Examples 1 to 2 The rubber compound shown below was kneaded using a 20 cm open roll to create a rubber compound product-1. Rubber compound - 1 Natural rubber 100 parts by weight Zinc white 5 Sterionic acid 1 HAF (high abrasion furnace) carbon black 30 Calcium carbonate 50 Sulfur 3 ^* Vulcanization accelerator CZ 1.5 Water-swellable substance 55 (*) N-cyclohexyl -2-Benzothiazole sulfenamide This rubber compound product-1 was press-vulcanized at 145°C for 30 minutes to obtain a 2 mm thick sheet. The presence or absence of blooming on the sheet, tensile test (measurement method: JIS
K6301), swelling rate when immersed in water (7 days and 30 days of immersion)
Measure daily weight change rate and examine changes),
KMnO ₄ consumption (measurement method: JIS K6353) was measured. Example 1 Rubber compound product-1 using a crosslinked hydrophilic polyol as a water-swellable substance
~3 Comparative Examples 1 and 2 were those using a non-crosslinked hydrophilic polyol, and the results are summarized in Table 1.

[Table] Examples 4 to 6, Comparative Examples 3 to 4 The rubber compound shown below was kneaded using a 20 cm open roll to create a rubber compound product-2. Rubber compound product-2 Ethylene propylene diene terpolymer
100 parts by weight Zinc white 5 Sterionic acid 1 SRL (Semi-Reinforced Furnace)
Carbon black 30 Calcium carbonate 50 Dicumyl peroxide 8 Water-swellable substance 90 This rubber compound product-2 was press-vulcanized at 150°C for 30 minutes to obtain a 2 mm thick sheet. The same tests as in Examples 1 to 3 were conducted on the sheets. Example 4: Rubber compound product-2 in which a cross-linked hydrophilic urethane resin was used as the water-swellable substance
-6 Comparative Examples 3 and 4 used a non-crosslinked hydrophilic urethane resin, and the results are summarized in Table 2.

【table】

[Table] Examples 5 to 6 A 2 mm thick sheet was prepared in the same manner using a crosslinked hydrophilic urethane resin as the water-swellable material in the rubber compound product-1 shown in Examples 1 to 3. The results of similar tests are summarized in Table 3.

[Table] From the results in Tables 1 to 3, when rubber is crosslinked with a water-swellable substance, there are changes in blooming, tensile strength, and swelling rate when immersed in water, compared to when there is no crosslinking.
Improvement effects were observed in terms of KMnO ₄ consumption, etc. Example 7 (Example of etherified product) _{Polybutadiene} polyol (trade name R _{- 45M} ,
Manufactured by ARCO Chemical; hydroxyl value 42mgKOH/g,
A polyether polyol with a hydroxyl value of 14.3 was synthesized by addition polymerizing ethylene oxide to a polyol with an iodine value of 398. The molecular weight of this polyol is approximately
7850, the ethylene oxide content was 66%, and the iodine value was 135. 70 parts of this polyol, 100 parts of chloroprene rubber
10 parts HAF carbon black, 50 parts calcium carbonate, 3 parts sulfur, 5 parts zinc white, vulcanization accelerator
After kneading 1.5 parts of CZ with an open roll, the temperature is 145℃.
Press vulcanization was carried out for 10 minutes to obtain a sheet with a thickness of 2 mm. This sheet had a tensile strength of 120 Kgf/cm ² , a water swelling rate of 78% (7 days immersion in water), and a potassium permanganate consumption of 6 in a water quality test, showing good physical properties and no blooming. Example 8 (Example of urethane compound) Propylene oxide in propylene glycol
1 mole of polyether polyol with a hydroxyl value of 22.5 mgKOH/g obtained by addition polymerization at a ratio of 30% by weight and 70% by weight of ethylene oxide was reacted with 2 moles of toluylene diisocyanate to form a urethane prepolymer with an isocyanate content of 1.5%. Synthesized. 100 parts of this urethane prepolymer and Example 7
50 parts of a mixture of 48 parts of polybutadiene polyol (equivalent ratio 1:1) and thickened by stirring, 50 parts of acrylonitrile butadiene rubber, 50 parts of natural rubber, FEF
(Fight extruding furnace)
After kneading 10 parts of carbon black, 50 parts of calcium carbonate, 3 parts of sulfur, 5 parts of zinc white, and 1.5 parts of vulcanization accelerator CZ on an open roll, press vulcanization was performed at 150°C for 10 minutes to form a 2 mm thick sheet. I got it. This sheet had a tensile strength of 116 Kgf/cm ² , a water swelling rate of 62% (7 days immersion in water), a potassium permanganate consumption of 5 in a water quality test, and no blooming indicating good physical properties. Example 9 (Example of urethane compound) Propylene oxide in propylene glycol
1 mole of polyether polyol with a hydroxyl value of 22.5 mgKOH/g obtained by addition polymerization at a ratio of 30% by weight and 70% by weight of ethylene oxide, 3 moles of butenediol, 4 moles of toluylene diisocyanate, and 5 g of butyltin dilaurate as a catalyst. The mixture was stirred and mixed, poured into a pallet, and aged in an oven at 100°C for 1 hour to produce thermoplastic polyurethane rubber. Add 100 parts of this and styrene-butadiene rubber.
50 parts, FEF carbon black 20 parts, fatty acid treated calcium carbonate 70 parts, sulfur 4 parts, zinc white 5 parts
After kneading 1.5 parts of the vulcanization accelerator CZ with an open roll, press vulcanization was performed at 150°C for 20 minutes to obtain a sheet with a thickness of 2 mm. This sheet had a tensile strength of 128 Kgf/cm ² , a water swelling rate of 115% (7 days immersion in water), and a potassium permanganate consumption of 5 in a water quality test, showing good physical properties and no blooming. Example 10 50 parts of the thermoplastic polyurethane rubber of Example 9, 100 parts of natural rubber, 5 parts of zinc white, 15 parts of HAF carbon black, 50 parts of calcium carbonate, 5 parts of pentaerythritol tetra(3-mercaptopropionate)
1 part and 0.5 part of benzoyl peroxide were kneaded using an open roll, and press vulcanization was performed at 120°C for 15 minutes to obtain a sheet with a thickness of 2 mm. This sheet had a tensile strength of 106 Kgf/cm ² , a water swelling rate of 58% (7 days immersion in water), and a potassium permanganate consumption of 4 in a water quality test, showing good physical properties and no blooming. Example 11 1 mole of the liquid polybutadiene polyol of Example 7, 3 moles of toluylene diisocyanate, and 4 moles of monool with a molecular weight of 1500 by adding ethylene oxide to allyl alcohol were reacted to synthesize a water-soluble polymer with terminal allyl groups. . Liquid butadiene-acrylonitrile rubber (Nipole) diluted with 100 parts of this polymer, 10 parts of triallylisocyanurate, and toluene to a resin content of 70%
1312, manufactured by Nippon Zeon) 40 parts, pentaerythritol tetra (3-mercaptopropionate) 15
1 part and 2 parts of benzophenone were mixed with thorough stirring. This material was coated on a Teflon plate to a thickness of 100 μm using a percoater, and immediately cured when exposed to ultraviolet light. This coating has a tensile strength of 68Kgf/cm ² and a water swelling rate.
168% (after 7 days of water immersion), and the potassium permanganate consumption was 9 in the water quality test, showing good physical properties.

Claims (1)

[Claims] 1. For 100 parts by weight of rubber, 10 to 500 parts by weight of a water-swellable etherified product, esterified product, or urethanized product having a molecular weight of 200 or more and having a polyethylene oxide bond and an ethylenically unsaturated bond in the molecule is used as rubber. 1. A water-swellable waterproofing material characterized by containing a substance crosslinked with 0.5 to 10 parts by weight of a crosslinking agent consisting of a vulcanizing agent or (and) a polythiol compound.