JPS6012380B2 - Joint filling method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a joint filling method using a novel caulking material.

Conventionally, in the fields of civil engineering and construction, butyl rubber, acrylic, epoxy, urethane, etc. have been used for the purpose of sealing various problems, maintaining airtightness, or waterproofing.

However, these caulking materials do not sufficiently achieve their sealing effect. For example, when such a caulking material is used in segment waterproofing work, etc., it tends to collapse easily and create gaps, making it impossible to sufficiently prevent water leakage. Furthermore, acrylic caulking materials used in construction work etc. lack alkali resistance and adhesion, and are prone to cracking and peeling after construction. The purpose of the present invention is to
It is an object of the present invention to provide a method for filling joints using a novel caulking material that has good swelling properties, adheres closely to sealed parts, maintains elasticity, and has good waterproof and airtight properties.

Another object of the present invention is to provide a method for filling joints with a caulking material that does not deteriorate over a long period of time after construction, does not crack when immersed in water, and has excellent alkali resistance. . In the joint filling method of the present invention, a prepolymer containing terminal isocyanate groups obtained by reacting a polyether polyol and a polyisocyanate, and a
A two-component swellable polyurethane resin obtained from an active hydrogen-containing compound having 2 to 6 active hydrogen groups per molecule and having an average molecular weight per active hydrogen group of 30 to 6,000, consisting of a polyol, a polyamine, or a mixture thereof. The joints are filled with a caulking material containing 30 to 50 parts by weight of asphalt and a plasticizer per 10 parts by weight of the polyurethane resin.

A typical example of a swellable urethane resin is the general formula R[(OR,)nOH]p (where R is a polyhydric alcohol residue; (OR,)n is an oxyethylene group and a carbon number of 3 to 3). A polyoxyalkylene chain consisting of an oxyalkylene group having 4 alkylene groups,
However, the proportion of oxyethylene groups is 10 to 100% of the molecular weight.
occupies: n is a number indicating the degree of polymerization of the oxyalkylene group and corresponds to a hydroxyl group equivalent of 200 to 2500; p
Examples of polyether polyols include those obtained by using one or a mixture of two or more polyether polyols represented by 2 to 8, preferably 2 to 4.

Preferred examples of the polyhydric alcohol for R (polyhydric alcohol residue) in the above general formula include aliphatic dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,4-butylene glycol, neobentyl glycol, ), trihydric alcohols (e.g. glycerin, trioxyisobutane, 11213-butanetriol, 112
・Tri-knocked pentanetriol, 2-methyl-1'2,3-
Propanetriol, 2-methyl-213,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,314-bentanetriol, 2,3,4-hexanetriol, 4-probyl-314,5 -Hebutanetriol, 2,4-dimethyl-213,4-pentanetriol, pentamethylglycerin "Bentaglycerin, 112,4-butanetriol, 1,214-bentanetriol, trimethy.

tetrahydric alcohols (e.g. erythritol, bentaerythritol, 1.203.4-pentanetetrol)
・3,5-bentanetetrol, 1131405-hexanetetrol, etc.), pentahydric alcohols (e.g., adonite, arabite, xyrite, etc.). Hexahydric alcohol (e.g.
sorbitol, mannitol, iditsuto, etc.).
In addition, the polyether polyol represented by the above general formula can be prepared by adding ethylene oxide,
Alternatively, it can be produced by adding both an alkylene oxide having 3 to 4 carbon atoms and ethylene oxide so that the desired molecular weight and the desired ethylene oxide group content are obtained. . Further, alkylene oxide having 3 to 4 carbon atoms and ethylene oxide can be added in random or block form. The ratio of oxyethylene groups to the molecular weight of the polyether polyol is in the range of 10 to 100% (by weight), but if it is less than 10%, the swelling rate of the polyurethane resin obtained by reacting the polyisocyanate will be low and the waterproof property will be poor. The polyisocyanate used in the present invention may be any type of polyisocyanate, such as 1.4
-Butane diisocyanate "IG6-hexane diisocyanate, dicyclohexylmethane diisocyanate,
Cyclohexasodiisocyanate, 105-bisisocyanato-1,313-trimethylcyclohexane, 1
-3-bis-(isocyanatomethyl)-benzene and methylcyclohexane diisocyanate. Aliphatic triisocyanates can be used partially in combination. Aromatic polyisocyanates include any aromatic diisocyanates, such as 2,4- or 2,6-tolylene diisocyanate or isomer mixtures thereof, 414'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4・4'-diisocyanate, m- or p
- Phenyl diisocyanate, 115-naphthylene diisocyanate and their isomers are suitable carbodiimides, uretdiones, urethanes, uretimines -
, a biuretto group, or an aromatic polyisocyanate containing an isocyanate ring can be used or used in combination. The caulking material used in the present invention contains such a swellable polyurethane resin, asphalt, and/or a plasticizer, but
Preferred examples of the asphalt include natural asphalt, straight asphalt, and blown asphalt.

Preferred plasticizers include phthalate esters (e.g. dibutyl phthalate, dioctyl phthalate),
Oils (eg, animal and vegetable oils and fats whose main component is fatty acid glyceride, petroleum whose main component is hydrocarbons, aromatic oils consisting of alcohols, ketones, aldehydes, etc.), etc. The above-mentioned asphalts or plasticizers may be used alone or in combination of two or more components in any proportion.

The asphalt and/or plasticizer is used in an amount of 30 to 50 parts by weight, preferably 50 to 10 parts by weight, based on 10 parts by weight of the swellable polyurethane resin. As an embodiment of the present invention, [11] a prepolymer containing terminal isocyanate groups obtained by reacting a polyether polyol and a polyisocyanate, a polyol, a polyamine or a mixture thereof as a curing agent, and an asphalt and/or a plasticizer. A method of filling the joints with a composition containing the above and curing it in the joints to form a swellable polyurethane resin, '2) curing and molding the above composition in advance to form a swellable polyurethane resin; Examples include a method of pushing it into the joint.

The above filling method (2) is preferable when the cross-sectional dimensions of the joint are approximately constant, and is also applicable when hardening in the joint has an unfavorable effect on the inner surface of the joint. be able to.

The active hydrogen-containing compound used in the present invention is a polyol, a polyamine, or a mixture thereof having 2 to 6 active hydrogen groups per molecule and an average molecular weight per active hydrogen group of 30 to 6,000. For example, low molecular weight di- or triols such as ethylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, polyalkylene glycols such as polypropylene glycol, ethylene oxide-propylene oxide copolymer,
Alkylene oxides such as ethylene oxide-propylene oxide and low molecular weight triols such as glycerin, trimethylolpropane, 1,2,6-hexanetriol or low molecular weight tetraols such as pentaerythritol or low molecular weight hexaols such as solpitol. , polyamines such as ethylenediamine, 4,4-methylenebis-1-chloroaniline, and polymers of these and the above alkylene oxides.

The isocyanate group-containing prepolymer used in the present invention is preferably a prepolymer containing 1 to 12% of terminal CO groups, obtained by reacting the above-mentioned polyIJ ether polyol with the above-mentioned polyisocyanate. A content of 2 to 7% is preferred.

In the reaction between the isocyanate group-containing prepolymer and the active hydrogen-containing compound, a conventionally known catalyst that promotes the reaction between the isocyanate group and the active hydrogen-containing compound,
For example, triethylamine, triethylenediamine,
N-morpholine, stannath octoate, dibutyl dilaurate, etc. can be added.

The ratio of the poly-IJ isocyanate and active hydrogen-containing compound used in the polyurethane composition in the method of the present invention is such that the [NCO/[H+] ratio is 0.8 to 1.4, preferably 1.
．． It is in the range of 0 to 1.2.

Furthermore, the caulking material used in the present invention contains, in addition to the above-mentioned elastomeric urethane resin as an essential component, other polymeric substances such as urethane resin, epoxy resin, and acrylic resin, as well as these. Additives may be included, such as tar calcium carbonate, silica, aluminum silicate, talc, or titanium dioxide.

It may also contain appropriate amounts of colorants and antioxidants. The effects of the present invention can be achieved by making the overall swelling ratio of the composition 10% or more.

Therefore, when the above-mentioned swellable polyurethane resin is used alone, it is sufficient that the swelling rate of the swellable material is 10% or more, and when used in combination with other non-swellable polymeric substances and other additives, It is preferable to use a swellable polyurethane resin having a high swelling rate so that the swelling rate of the entire composition is 10% or more. The effect of the present invention is that it has good swelling properties, adheres closely to the sealing part, and maintains elasticity.

The object of the present invention is to provide a method for filling joints using a novel caulking material that has good waterproof and airtight properties. Also,
Other effects of the present invention are that it does not deteriorate over a long period of time after installation, has no cracks, and has excellent alkali resistance.
The object of the present invention is to provide a method for filling miyaji using caulking material. The effects of the present invention will be explained in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

In the examples, "parts" indicate "parts by weight." Test method The water leakage test of the present invention was actually confirmed using segment waterproofing.

In other words, the segment waterproofing test involves assembling segments and filling the joints of the segments with caulking agent.If water leakage is observed, the water leaks, and if the water stops, the water stops.
Moreover, the swelling rate referred to here indicates the percentage increase in weight after the cured product was immersed in tap water for 7 days. Example 1 Molecular weight 3000 obtained by randomly adding propylene oxide and ethylene oxide to glycerin,
Trifunctional polyether 4 with 50% oxyethylene group content
Using Ikaribe and 3 parts of a bifunctional bolyether with a molecular weight of 200 u and an oxyethylene group content of 60% obtained by randomly adding propylene oxide and ethylene oxide to propylene glycol, tolylene diisocyanate was added, and the mixture was prepared by a conventional method. The reaction was carried out at 90 qo for about 2 hours to produce an isocyanate group-containing prebolimer (UPX-1) with an NCO content of 3.1%.

The proportion of oxyethylene groups is 56%. UPX-11
00 parts liquid curing agent-1 [glycerin, base polyether polyol (containing 50% oxyethyl steering group)]
4'-methylenebis-1-chloroaniline (MOCA)
Added and dissolved, 25 parts of MOCA content 30%), 45 parts of tar (manufactured by Yoshida Refinery, Tarclon #180), 4 parts of petroleum asphalt (2-trate, asphalt penetration 120), added, 2yo left in the atmosphere of ``20
It was completely cured by curing for a day, and the swelling rate was determined to be 350%. After being immersed in tap water for 20 days, no abnormalities were observed in the appearance, no cracks were observed, and the bond retained its elasticity. Fill the segment joints with this composition,
When we conducted a segment waterproof test, no water leakage was observed. In other words, the water stopped. Example 2 Molecular weight 4000 obtained by randomly adding propylene oxide and ethylene oxide to glycerin
Trifunctional polyether 3 with 50% oxyethylene group content
Ikariku and - obtained by adding propylene oxide to propylene glycol and then adding ethylene oxide, with a molecular weight of 200 or more and an oxyethylene group content of 50%.
An isocyanate group-containing prepolymer (UPX-2) with an NCO content of 2.9% was prepared by adding tolylene diisocyanate and reacting for about 2 hours at 90 oo by a conventional method. .

The proportion of oxyethylene groups is 50%. UPX-2
100 parts, 61 parts of liquid curing agent-2 [trifunctional polyether with a molecular weight of 3000 and an oxyethylene group content of 40% obtained by adding propylene oxide to glycerin and then adding ethylene oxide], Dibutyltin dilaurate 0.1 part, U-Rex #200
(Tokyo Jushi) 5 foundations dibutyltin dilaurate 0.
Added 1 part of U-Rex #200 (manufactured by Tokyo Jushi Co., Ltd.) 5 parts of anchor and 1 part of dibutyl phthalate (DBP) and completely cured it in an atmosphere of 25 qo.
80%, and after 20 days of immersion in tap water, no abnormality was observed in the appearance, no cracks were observed, and elasticity was maintained. When this composition was filled into the segment joints and a segment waterproofing test was conducted, no water leakage was observed.
In other words, water stopped. Example 3 UPX-2 obtained in Example 3 10 anchors Example 1
25 parts of the liquid curing agent used in 1, 3 parts of dioctyl phthalate, and 2 parts of soybean oil were added, and the mixture was poured into a mold having a width of 2 mm, a depth of 1 m, and a length of 5 m, and hardened.

The swelling ratio of the cured product was measured and was 330%. After immersion in tap water for 20 days, no abnormality was observed in the appearance, no cracks were observed, and elasticity was maintained.

When a segment waterproofing test was conducted on the Western-type cured product, no water leakage was observed. In other words, the water stopped. Comparative Example 1 20 parts of a trifunctional polyether with a molecular weight of 3,000 obtained by adding propylene oxide to glycerin and 8 parts of a bifunctional polyether with a molecular weight of 2,000 obtained by adding propylene oxide to topropylene glycol were mixed. Tolylene diisocyanate was added to the mixture and reacted in a conventional manner at 90 oo for about 2 hours to obtain NC.
A prepolymer with an isocyanate group content of 3.1% (
UPX-3) was obtained.

The proportion of oxyethylene groups is 0%. UPX-3
Liquid curing agent-3 (molecular weight 20 obtained by adding propylene oxide to propyreso glycol)
00 polyether, MOCA added and dissolved, MOCA 30%] 25 parts, tar (Turclone #i8
0) After adding 50 parts and completely curing in the atmosphere at 25°C, the swelling rate was measured to be 1.2%, and no abnormality was observed in the appearance after dilution with tap water for 20 days. It retained its elasticity. When this composition was filled into the segment joints and a segment waterproofing test was conducted, water leakage was observed. Comparative Example 2 UPX-2 obtained in Example 3 61 parts of liquid curing agent-2, 0.0 parts of dibutyltin dilaurate.
When 1 part was added and completely cured in the atmosphere at 25q0, the swelling ratio was measured and found to be 305%.

After soaking in tap water for 20 days, cracks had formed inside the resin.

Claims (1)

[Scope of Claims] 1. An isocyanate group-containing prepolymer with a terminal NCO group content of 1 to 12% obtained by reacting a polyether polyol and a polyisocyanate, and having 2 to 6 active hydrogen groups per molecule; An active hydrogen-containing compound consisting of a polyol, polyamine, or a mixture thereof having an average molecular weight per active hydrogen group of 30 to 6000 [NCO]/
A two-component swelling polyurethane resin obtained by using a [H^+] ratio in the range of 0.8 to 1.4, and 30 to 500 parts of asphalt and/or plasticizer per 100 parts by weight of the polyurethane resin. A joint filling method characterized by filling the joints with a caulking material containing parts by weight. 2 The polyether polyol has the general formula R[(OR_1)_nOH]_p (where R is a polyhydric alcohol residue: (OR_1)_n is an oxyalkylene group having an oxyethylene group and an alkylene group having 3 to 4 carbon atoms. A polyoxyalkylene chain consisting of, however, the proportion of oxyethylene groups is 10% of the molecular weight
occupies ~100%: n is a number indicating the degree of polymerization of the oxyalkylene group and corresponds to a hydroxyl equivalent of 200 to 2500; p is 2 to 8, preferably 2 to 4) of the polyether polyol represented by The joint filling method according to claim 1, which is one type or a mixture of two or more types.