JPH09165438A - Method repairing molded article of crosslinked polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To offer a method for repairing a crosslinked polymer molded article used in a plumbing system to prevent water leakage. SOLUTION: In a crosslinked polymer molded article wherein whole or a part of the surface comes in contact with water, a water leaking portion which has occurred on the crosslinked polymer molded article is repaired by using a polyurethane adhesive, epoxy adhesive, vinyl ester adhesive or unsaturated polyester adhesive whose strain at tensile break after curing is not less than 5%, after the portion is overlaid with an FRP material or reinforced fibers or an it is.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a metathesis polymerization cyclic olefin-containing monomer liquid A (solution A) containing a metathesis polymerization catalyst system catalyst component and a metathesis polymerization containing a metathesis polymerization catalyst system activator component. Crosslinked polymer molding obtained by mixing a monomer liquid B (solution B) composed of a polar cyclic olefin, injecting the raw material mixed liquid into a mold, and causing polymerization and crosslinking reaction in the mold (hereinafter , Such a crosslinked polymer molded product may be simply abbreviated as a crosslinked polymer molded product), and relates to a repairing method in the case where water leakage occurs in a product for use around water.

[0002]

2. Description of the Related Art Monomer liquid A (solution A) consisting of a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer consisting of a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system A crosslinked polymer molded product obtained by mixing liquid B (solution B), injecting the raw material mixed liquid into a mold, and causing polymerization and crosslinking reaction in the mold is used for water-related applications such as septic tanks. It is well known to be used (for example, see Japanese Patent Laid-Open No. 7-137070). This crosslinked polymer molded article is hard to break and is durable, but if the resin breaks due to an impact from the outside and water leakage starts to occur, a method for repairing it has not been proposed yet.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a monomer liquid A (solution A) composed of a metathesis-polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and an activator component of the metathesis polymerization catalyst system. Water-related use obtained by mixing the monomer liquid B (solution B) containing the metathesis-polymerizable cyclic olefin contained therein, injecting the raw material mixed liquid into a mold, and causing the polymerization and crosslinking reaction in the mold. Another object of the present invention is to provide a method for repairing a water leakage part of a crosslinked polymer molded article for use in a product.

[0004]

As a result of intensive studies to solve the above-mentioned object of the present invention, the present inventor has found that the leaked part is an adhesive having an appropriate flexibility. By applying an adhesive whose agent is polyurethane type, epoxy type, vinyl ester type or unsaturated polyester type, and if necessary, the adhesive can be injected to the inside of the crack (leakage part) of the cross-linked polymer. It has been found that a repair exhibiting a strong water leakage resistance can be made by shaving and widening the surface and injecting the adhesive into the portion, and the present invention has been accomplished.

That is, the present invention is as follows: Monomer liquid A (solution A) containing a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and monomer liquid B containing a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system (solution B) ) Is mixed, and the raw material mixture is poured into a mold to cause a polymerization and a crosslinking reaction in the mold to obtain a crosslinked polymer molded article, In a product for use in which a part or all of the product comes into contact with water or an aqueous solution, the water leakage part generated in the crosslinked polymer molded product is replaced with a polyurethane adhesive, an epoxy adhesive, a vinyl ester adhesive or an unsaturated polyester adhesive. It is an agent and has a tensile fracture strain of 5% after curing
1. A repair method characterized by repairing with the above. The water leakage part is an FRP member (hereinafter referred to as “FRP member”, “fiber reinforced plastic member or semi-cured FR
P member "), and the FRP member and the crosslinked polymer molded product with a polyurethane adhesive, an epoxy adhesive, a vinyl ester adhesive or an unsaturated polyester adhesive. 2. The repair method according to the above 1, wherein the adhesive is bonded with a tensile fracture strain after hardening of 5% or more, and Cover the leaked part with reinforcing fiber or fill the leaked part with reinforcing fiber, and use polyurethane adhesive, epoxy adhesive, vinyl ester adhesive or unsaturated polyester adhesive with a tensile breaking strain of 5 after curing. %, The repairing method according to the above 1, wherein the leaking part is repaired together with the reinforcing fiber.

The present invention is applied to various cross-linked polymer molded products such as a septic tank which is a typical product for water use, a water tank, play equipment, a small boat and the like.

The crosslinked polymer molded article applied to the present invention will be specifically described below. As the metathesis-polymerizable cyclic olefin for forming the crosslinked polymer applied to the present invention, those containing 1-2 metathesis-polymerizable cycloalkene groups in the molecule are used. Preferred are compounds having at least one norbornene skeleton in the molecule. Specific examples of these include dicyclopentadiene,
Tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,5,8-dimethano-
1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4,4a, 5,6,7,
8,8a-octahydronaphthalene, 1,4,5,8-
Dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, ethylene bis (5-norbornene) and the like can be mentioned, and a mixture thereof can also be used. In particular, dicyclopentadiene or a mixture containing 50 mol% or more, preferably 70 mol% or more thereof is suitably used. Further, if necessary, a metathesis polymerizable cyclic olefin having a polar group containing a different element such as oxygen or nitrogen can be used as a copolymer monomer.

Monomer liquid A (solution A) applicable to the present invention
The catalyst component of the metathesis polymerization catalyst system is contained therein. As such a catalyst component, salts such as halides of metals such as tungsten, rhenium, tantalum and molybdenum are used, and a tungsten compound is particularly preferable. As such a tungsten compound, tungsten hexahalide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, an organic ammonium tungstate or the like can be used. It has been found that such a tungsten compound immediately starts cationic polymerization when added directly to a monomer, which is not preferable. Therefore, such a tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene and the like in advance and solubilized by adding a small amount of an alcohol compound and / or a phenol compound to be used. Further, as described above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound in order to prevent undesired polymerization. Examples of such additives include acetylacetone, alkyl acetoacetates, tetrahydrofuran, and benzonitrile. In addition, the storage stability of the catalyst is further increased by adding a compound that traps hydrogen chloride produced as a by-product after catalyst preparation, such as dicyclopentadiene.

A monomer liquid A (solution A) is formed by dissolving the catalyst component thus prepared in the monomer. When a polar monomer is used, as described above, the polar monomer itself may be a Lewis base, and in some cases, the compound may have its action without adding any of the above compounds.
In this way, the monomer liquid A (solution A) containing the catalyst component has substantially sufficient stability.

On the other hand, the monomer liquid B (solution B) applied to the present invention contains an activator component of the metathesis polymerization catalyst system. This activator component is from I to
Organometallic compounds centered on alkylated Group III metals, especially tetraalkyltin, alkylaluminum compounds, and alkylaluminum halide compounds are preferred, and specifically, diethylaluminum chloride, diethylaluminum chloride, trioctylaluminum, dioctyl. Aluminum iodide, tetrabutyl tin, etc. can be mentioned. By dissolving the organometallic compound as an activator component in a monomer, a monomer liquid B (solution B) is formed.

Basically, a crosslinked polymer molded article can be obtained by mixing the solution A and the solution B and injecting them into a mold. However, with the above composition, the polymerization reaction is very fast. Since it is started, curing may occur while it does not flow sufficiently into the molding die, which may be a problem. Therefore, it is preferable to use an activity regulator. As such a regulator, Lewis bases are generally used, and above all, ethers, esters, nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like. Such a regulator is generally used by being added to the solution (solution B) of the component of the activator of the organometallic compound. When a monomer having a Lewis base is used as described above, it can also serve as a regulator.

The molded article applied to the present invention basically comprises
It can be obtained by mixing the above-mentioned solution A and solution B and injecting them into a mold. At that time, the catalytic activity of the metathesis catalyst system formed by mixing the solution A and the solution B can be expressed by the time from when the two solutions are mixed to when the mixed solution loses fluidity. That is, if the time until the fluidity is lost is defined as the time from when both solutions are put in a glass container equipped with a stirrer until the solution gels and entangles with the stirring shaft of the stirrer, The solution A and the solution B of the present invention have a liquid loss at the initial stage of mixing and an environmental temperature of 30 ° C.
It is preferably ˜120 seconds, more preferably 2 to 100 seconds.

The molded product of the cross-linked polymer used in the present invention may further contain various additives depending on the purpose in order to improve or maintain its properties in practical use. Such additives are non-reactive with the metathesis-polymerizable cyclic olefin of the monomer, and may be soluble or insoluble in the monomer. Additives may be those capable of improving or imparting a certain function by blending it with a molded product, and those generally used as additives for resins are used, fillers, reinforcing agents, Antioxidant, heat stabilizer, pigment, light stabilizer, ultraviolet absorber, lubricant, antistatic agent, flame retardant,
Examples include foaming agents, softening agents, tackifiers, plasticizers, release agents, deodorants, fragrances and extenders. These may be used alone or in combination of two or more. Such additives cannot be added after the crosslinked polymer of the present invention has been molded, and therefore, when added, it is necessary to add them to the above-mentioned raw material solution in advance.

Further, the molded product applied to the present invention can be obtained by adding another polymer in a monomer solution state. As such a polymer additive, an elastomer is effective in increasing the impact resistance of a molded product and adjusting the viscosity of a solution. Examples of the elastomer used for such purpose include a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-diene-polymer and nitrile rubber. You can

The blending ratio of these additive components depends on the kind thereof, but is in the range of 0.01 to 50% by weight, preferably 0.1 to 30% by weight, based on the crosslinked polymer phase to be blended. Appropriate.

The material of the mold for molding the crosslinked polymer molded article to which the present invention is applied is steel, cast or forged aluminum, zinc alloy casting, or thermal spraying,
Examples include electroforming of nickel and copper and resins.
Also, the structure of the mold is simple enough because the pressure generated in the mold at the time of molding is several kg / cm ² , which is extremely low compared to other molding methods, and is therefore cheaper than other molding methods. Can be built into

Next, the repairing method of the present invention will be described as a model with reference to FIGS. FIG. 1 shows a plate-shaped body 1 obtained by cutting out a part of a crosslinked polymer molded product for water use product, and having cuts 2 formed therein. Cut 2 is a model of a crack (water leakage part) generated in the crosslinked polymer molded product of a water application product. In FIG. 1, the upper surface 3 is a surface that comes into contact with water or an aqueous solution. The water leakage part may be repaired on the side in contact with water or the aqueous solution or on the opposite side.However, for convenience of explanation, in the following figures and examples, all repairs are performed on the surface in contact with water or the aqueous solution. ing.

FIG. 2 shows a state in which FIG. 1 is repaired by one of the methods according to the present invention (when neither the FRP member for overlaying nor the reinforcing fiber is used). The number 4 in FIG. 2 represents the adhesive according to the present invention applied to the space and the upper surface of the cut 2 of the plate-shaped body in FIG. Other numbers in FIG. 2 are the same as those in FIG.

For adhesion, it is important that the adhesive sufficiently penetrates into the cracks of the crosslinked polymer molded product and that the adhesive has a chemical affinity with the crosslinked polymer molded product. In order to facilitate the penetration of the adhesive, it is desirable to insert the adhesive after shaving the cracked portion if necessary. This ensures that the inserted adhesive comes into contact with the cross-linked polymer molded product in a wide range of the crack cross-section, and the recurrence of water leakage can be prevented.

Here, the adhesive used in the present invention is a polyurethane adhesive, an epoxy adhesive, a vinyl ester adhesive or an unsaturated polyester adhesive having a tensile breaking strain after curing of 5% or more. It is a thing.

In general, products for water use are easily affected by the water pressure caused by the contacting water or aqueous solution, and further, the products buried in the soil are constantly affected by the earth pressure. On the other hand, a monomer solution A composed of a metathesis-polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a monomer solution B composed of a metathesis-polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system.
The crosslinked polymer molded product obtained by mixing (solution B) and injecting the raw material mixed solution into a mold to cause a polymerization and a crosslinking reaction in the mold usually has a tensile yield yield of 4 to 5%. It has strain and a tensile elastic modulus of 160 to 220 kgf / mm ² . Therefore, it is more likely to be deformed than the glass-reinforced unsaturated polyester resin which is similarly applied to water products, and when continuously or repeatedly subjected to a load and the deformation is continued or repeated, it adheres to the crosslinked polymer molded product. It has been found that cracks may occur at the interface of the agent and water leakage may occur again, and as a result of studying this, polyurethane-based adhesives, epoxy-based adhesives, vinyl ester-based adhesives can be used to solve these problems. It has been found that an adhesive or an unsaturated polyester-based adhesive having a tensile breaking strain after curing of 5% or more is suitable. Polyurethane-based adhesives and epoxy-based adhesives are referred to by various names as adhesives, repair agents, and paints depending on the application, but polyurethane-based resins and epoxy-based adhesives have an adhesive function and are cured. As long as the subsequent tensile fracture strain is 5% or more, any kind may be used, regardless of their names.

As the polyurethane adhesive for this purpose, a commercially available polyurethane adhesive can be used. As a component of the polyurethane adhesive, as an isocyanate component,
Isophorone diisocyanate, an aliphatic isocyanate
Aromatic isocyanate tolylene diisocyanate (TDI), 3,3'-tolylene-4,4 ', such as hydrogenated tolylene diisocyanate, hexahydrometaxylylene diisocyanate, dicyclohexadiisocyanate, etc.
Diisocyanate, diphenylmethane diisocyanate (MDI), crude MDI, polymeric diphenylmethane diisocyanate, triphenylmethane triisocyanate, tolylene dimer, naphthalene diisocyanate, tris (4-phenylisocyanate) thiophosphate, TDI trimer, metaxylylene diisocyanate, trimethylpropane- Examples thereof include 1-methyl-2-isocyano-4-carbamate, polymethylene polyphenyl isocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate and diphenyl ether triisocyanate.

As the polyol component, low molecular weight polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, polyether polyol polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyester polyol are used. Examples thereof include polycaprolactone, polyesters from diols and dibasic acids, and the like.

These components are the basic raw materials of the polyurethane adhesive, and further, a catalyst, a stabilizer, a pigment, a filler, a tackifier, etc. are added depending on the type of the adhesive.

Polyurethane adhesives composed of these components can be classified into two types, one-pack type and two-pack type, depending on the usage form. Examples of the one-liquid type include a combination of an isocyanate compound and water, a prepolymer having an NCO group terminal and water, and the like. As the two-pack type, for example, a combination of an isocyanate compound and a synthetic rubber polymer,
Examples include combinations of NCO group-terminated prepolymers and polyols, and combinations of isocyanate compounds and OH group-terminated thermoplastic polymers.

As the epoxy-based adhesive, a commercially available epoxy-based adhesive can be used. The constituents of the epoxy adhesive include, as the main component, bisphenol type epoxy resin, phenol type epoxy resin, novolac type epoxy resin, glycidyl type epoxy resin, and the like, and the curing agent components thereof include diethylenetriamine and triethylene. Ethylene tetramine, N-aminoethylpiperazine, metaxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, polyamide, paramenthanediamine, metaphoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 2- Aliphatic amines such as ethyl-4-methylimidazole, metaphenylenediamine, 4,4'-
Aromatic amines such as diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, dicyandiamide,
Examples thereof include carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic acid anhydride, and pyromellitic acid anhydride, thiochol, alcohols, and compounds containing two or more phenolic hydroxyl groups.

These components are basic raw materials in the epoxy adhesive, and further, a catalyst, a stabilizer, a pigment, a filler, a tackifier, etc. are added depending on the type of the adhesive.

The vinyl ester-based adhesive is obtained by a ring-opening addition reaction between an epoxy group and a carboxyl group. Generally, the epoxy component is bisphenol A type, novolac type, cycloaliphatic type, glycidyl ester type. Examples of the acid component include acrylic acid and methacrylic acid. As a curing agent for vinyl ester adhesives, methyl ethyl ketone peroxide / cobalt naphthenate type and benzoyl peroxide / dimethylaniline type are generally used.

The vinyl ester-based adhesive has these components as basic raw materials, and further, depending on the type of adhesive, a catalyst,
Stabilizers, pigments, fillers, tackifiers, etc. are added.

The unsaturated polyester adhesive is composed of an unsaturated polybasic acid, a saturated polybasic acid, glycols, monomers also serving as a solvent / crosslinking agent, a polymerization accelerator, and the like, and the unsaturated polybasic acid is anhydrous. Maleic acid, fumaric acid, itaconic acid and the like can be mentioned. Examples of the saturated polybasic acid include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenephthalic anhydride, adipic acid, sebacic acid, het acid, and tetrabromophthalic anhydride. To be Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3 butanediol, 1,6 hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, and dibromoneopentyl glycol. , Pentaerythritol allyl ether, allyl glycidyl ether, and the like. The tensile fracture strain after hardening often has a correlation with the ratio of the saturated polybasic acid to the unsaturated polybasic acid, and generally, when the ratio is large, the tensile strain after hardening also becomes large.

These components are the basic raw materials of the unsaturated polyester adhesive, and further, a catalyst, a stabilizer, a pigment, a filler, a tackifier, etc. are added depending on the type of the adhesive.

Among the adhesives applicable to the present invention, strength,
From the viewpoints of tensile fracture strain and adhesiveness after curing, polyurethane adhesives, epoxy adhesives and vinyl ester adhesives are more desirable, and polyurethane adhesives and epoxy adhesives are even more desirable.

FIG. 3 shows a state of repair by one of the methods according to the present invention (when an FRP member for overlay is used). In this repair method, when the water leakage opening is large, or in an environment where repeated variable loads are applied again after repair, the adhesive itself, not the interface between the crosslinked polymer molded product and the adhesive, is not strong enough. Therefore, in such a case, after applying the adhesive, the FRP member is overlaid on the repair surface (5 in FIG. 3), and the same adhesive is applied to the interface between the FRP member and the crosslinked polymer. To reinforce in strength.

In FIG. 3, reference numeral 4 represents an adhesive according to the present invention applied to the space and the upper surface of the cut 2 of the plate-like body in FIG. 1, and reference numeral 5 represents an FRP member for overlay. Other numbers in FIG. 3 are common to those in FIG.

Here, examples of the reinforcing fiber in the FRP member include glass fiber, carbon fiber, aramid fiber, nylon fiber, polyester fiber, silicon carbide, and the like, and preferably glass fiber is used. In addition, F
As the fiber reinforced plastic of the RP member, a thermosetting resin such as a fiber reinforced unsaturated polyester, a general thermoplastic resin such as a fiber reinforced polypropylene, and a reinforced fiber such as a glass fiber are mainly used. The semi-cured FRP member refers to a resin which is a thermosetting resin such as a fiber reinforced unsaturated polyester that has been allowed to proceed to a certain extent without being completely cured. In this case, needless to say, it is necessary to heat the semi-cured FRP member with a hair dryer or the like after the repair.

The adhesive used in FIG. 3 is a polyurethane adhesive, an epoxy adhesive, a vinyl ester adhesive or an unsaturated polyester adhesive as in the other cases, and the tensile strength after curing is Breaking strain is 5%
The above is used.

When overlaying with an FRP member,
A polyurethane adhesive, an epoxy adhesive, a vinyl ester adhesive, or an unsaturated polyester adhesive does not penetrate deeply into the crack portion of the cross-linked polymer product, and the portion of 4 in FIG. Even if the adhesive is not present in (1), there is no problem as long as the FRP member and the crosslinked polymer product are sufficiently adhered. At this time, in order to increase the adhesive strength, sanding the surface of the crosslinked polymer molded article further improves the adhesive strength.

FIG. 4 shows a state repaired by one of the methods according to the present invention (when the water leak portion is covered with reinforcing fibers and the reinforcing fibers are bonded together with an adhesive). This repair method is a method in which reinforcing fibers are directly applied to a repaired part and an adhesive is applied to the part to simultaneously form an adhesive and a reinforcing body at the same time, and it is difficult to attach an FRP member for overlay to repair on a large uneven surface. It is also suitable for repairing an opening (such as the cut line 2 in FIG. 1) where the FRP member for overlay cannot be adhered.

In FIG. 4, numeral 6 represents the adhesive according to the present invention applied to the space of the cut 2 and the upper surface 3 of the plate-like body in FIG. 1, and numeral 7 represents the reinforcing fiber. The repair is carried out by applying reinforcing fibers directly to the repaired part before applying the adhesive to the surface 3 and applying the adhesive to the part to simultaneously form an adhesive and a reinforcing body, but other methods are available. It doesn't matter.

Here, glass fibers, carbon fibers, aramid fibers, nylon fibers, polyester fibers, silicon carbide and the like can be used as the reinforcing fibers. Preferably, glass fiber is used, and the adhesive is polyurethane adhesive, epoxy adhesive, vinyl ester adhesive or unsaturated polyester adhesive as in other cases, and the tensile fracture strain after curing. Of 5% or more is used.
At this time, in order to increase the adhesive strength, sanding the surface of the crosslinked polymer molded article further improves the adhesive strength.

[0041]

EXAMPLES The present invention will be described below with reference to examples. It should be noted that the embodiments are for explanation, and the present invention is not limited to these.

Reference Example 1 (Preparation of Monomer Solution) (a) Preparation of Solution A Twenty-eight parts by weight of tungsten hexachloride was added to 80 parts by weight of dry toluene under a nitrogen stream, and then t-butanol.1.
A solution prepared by dissolving 3 parts by weight in 1 part by weight of toluene was added and stirred for 1 hour, and then a solution of 18 parts by weight of nonylphenol and 14 parts by weight of toluene was added and stirred for 5 hours under a nitrogen purge. Further, 14 parts by weight of acetylacetone was added. While the hydrogen chloride gas produced as a by-product was driven out, stirring was continued overnight under a nitrogen purge to prepare a polymerization catalyst solution.

Next, ethylene was added to a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene (purity 99.7% by weight, the same applies hereinafter) and 5 parts by weight of purified ethylidene norbornene (purity 99.5% by weight, apply similarly below). 70
To a solution prepared by adding 3 parts by weight of ethylene-propylene-ethylidene norbornene copolymer rubber (mol%) and 2 parts by weight of Etanox 702 as an oxidation stabilizer, the above polymerization catalyst solution was added so that the tungsten content was 0.01 mol / l. In addition, a monomer liquid (solution A) containing a catalyst component was prepared.

(B) Preparation of Solution B To a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene,
A mixture of 3 parts by weight of ethylene-containing 70 mol% ethylene-propylene-ethylidene norbornene copolymer rubber dissolved in a solution of trioctylaluminum 85, dioctylaluminium iodide 15 and diglyme 100 in a molar ratio to prepare a polymerization activator mixture. The solution was added at a rate such that the aluminum content was 0.03 mol / liter to prepare a monomer solution B (solution B) containing an activator component.

Reference Example 2 (Molding) For molding, an aluminum mold in which upper and lower parts of the septic tank shown in FIG. 5 were engraved was used. The dimensions of the septic tank components were as follows. A = 390 mm B = 520 mm C = 490 mm D = 340 mm E = 520 mm F = 2260 mm G = 950 mm H = 800 mm I = 260 mm J = 1140 mm

This mold is heated to a cavity mold of 90 ° C. and a core mold of 60 ° C., and the mold is closed. Then, an equal amount of solution A and solution B is mixed in the mold using a RIM molding machine.
Was collision-mixed and injected. Two minutes after the liquid injection and filling, the mold was opened and five minutes later, the crosslinked polymer product was taken out.

Reference Example 3 (Crack Generation Test) The upper and lower septic tank portions of the crosslinked polymer molding obtained in Reference Example 2 were fixed with bolts and adhesives via the flanges to obtain a product for evaluation. In the usual usage of the product, three FRP partition plates are previously fixed inside the septic tank with bolts and an adhesive. Here, the following steps were performed so that cracks are likely to occur.

FIG. 6 shows equipment for promoting deterioration used in the evaluation of the present invention. Note that FIG. 6 is shown in a sectional view in which the septic tank is cut in half for easy understanding.

(1) No FRP partition plate was used in the septic tank of FIG. 6 in order to increase the degree of deformation of the wall surface of the septic tank.

(2) 3 cmX on the side wall of the septic tank in advance
Seven scratches (wedge-shaped) having a width of 2 mm and a depth of 2 mm and not penetrating the septic tank wall were placed as indicated by numbers 14 to 20 in FIG.

(3) Absolute pressure 18 ± 5 kgf / cm ² (saturation temperature 197 after water was put into 70% of the septic tank)
(° C) steam is injected near the bottom of the septic tank using the steam injection pipe 11, and the water in
The temperature was maintained at 0 ° C. and maintained for a predetermined period.

(4) The occurrence of cracks was observed after the treatment of (3) above. One month after the start of the first test, all the scratches 14 to 20 in the septic tank were cracked through a wall having a length of 1 cm to 2 cm and leaked.

[Example 1] After the cracks were generated one month after the start of the first test in (4) above, the hot water in the septic tank was discharged, and the scratches 14 were entirely removed by the method shown in FIG. The crack was repaired so that it was covered with the adhesive. Here, Epomic T-1243 (epoxy type: manufactured by Mitsui Petrochemical Industry Co., Ltd.) was used as an adhesive. Then, the crack generation test (3) was repeated again and the state of water leakage was observed one month later, but no water leakage occurred in that portion. Separately, the cured Epomic T
The tensile breaking strain of -1243 was 12% as a result of the tensile test by the Instron universal testing machine.

[Embodiment 2] Araldite Rapid (epoxy type: manufactured by Ciba-Geigy Co., Ltd.) was used as an adhesive, and the crack was repaired under the same conditions as in Embodiment 1, except that the crack was repaired for the scratch 15. When the test (3) was conducted, water leakage started again from the repair department on the 7th day. Therefore, after repairing again with Araldai Rapid, an F of 5 cm × 3 cm × 3 mm was placed on the scratch by the method shown in FIG.
The repair surface was reinforced by overlaying an RP member (unsaturated polyester). At the interface between the FRP member and the cross-linked polymer molded product, a vinyl ester-based adhesive (Yupika 8250P
T: manufactured by Nippon Yupica Co., Ltd.). After that, the above crack generation test (3) was carried out again, and the leak was checked for up to 1 month, but no leak occurred. In addition, separately
The tensile fracture strain of Araldite Rapid after curing was determined by a tensile test using an Instron universal testing machine.
%Met.

[Example 3] Tanabe Epicoton TP-50 (epoxy type: manufactured by Tanabe Chemical Industry Co., Ltd.) was used as an adhesive and repaired under the same conditions as in Example 1 except that the cracks on the scratch 16 were repaired. After the treatment, the crack generation test (3) was carried out and the leak was checked for up to 1 month, but no leak occurred. The tensile breaking strain of the cured Tanabe epicoaton TP-50 was 12% as a result of a tensile test by an Instron universal testing machine.

[Example 4] Penguin seal 952 as an adhesive (one-component urethane type: manufactured by Sunstar Giken Co., Ltd.)
After the repair treatment under the same conditions as in Example 1 except that the crack was repaired for the scratch 17, the above crack generation test (3)
As a result, water leakage started again from the repair department on the 4th day. Then, after repairing again with the penguin seal 952, 5 cmX3 cmX3 was placed on the scratch by the method shown in FIG.
mm of FRP member (unsaturated polyester) was overlaid to reinforce the repair surface. At the interface between the FRP member and the crosslinked polymer, a urethane adhesive (Mighty Grip 30
00: manufactured by Japan Synthetic Rubber Co., Ltd.). After that, the crack generation test (3) was performed again, and the leak was checked for up to 1 month, but no leak occurred. In addition,
Separately, the tensile breaking strain of the cured penguin seal 952 was determined by a tensile test using an Instron universal testing machine, and as a result, it was 100% or more.

[Example 5] Mighty grip 3000 (two-component urethane type: manufactured by Japan Synthetic Rubber Co., Ltd.) was used as an adhesive agent, and repaired under the same conditions as in Example 1 except that the cracks on the scratch 18 were repaired. After that, the above crack generation test (3) was carried out, and the leak was checked for up to one month, but no leak occurred. Separately, the tensile breaking strain of the Mighty Grip 3000 after curing was determined by a tensile test using an Instron universal testing machine, and as a result, it was 100% or more.

[Example 6] After a repair treatment was performed under the same conditions as in Example 1 except that a vinyl ester-based adhesive (Yupica 8250PT: manufactured by Nippon Yupica Co., Ltd.) was used as the adhesive and the cracks on the scratch 19 were repaired. When the crack generation test (3) was carried out, water leakage started again from the repaired part on the 6th day. Then, after repairing again with Yupica 8250PT, 5 cmX3 cmX3 was placed on the wound by the method shown in FIG.
mm of FRP member (unsaturated polyester) was overlaid to reinforce the repair surface. The interface between the FRP member and the crosslinked polymer molded product was coated with Yupica 8250PT. After that, the above crack generation test (3) was performed again, and the leak was checked for up to one month, but no leak occurred. Separately, the tensile breaking strain of the cured Upika 8250PT was 5.1% as a result of a tensile test using an Instron universal testing machine.

[Comparative Example] A polyester adhesive having a tensile breaking strain of 2% after curing was used as an adhesive,
After the repair treatment under the same conditions as in Example 1 except that the crack was repaired, the crack generation test (3) was carried out, and water leakage started again from the repaired part on the second day.

Therefore, after repairing again with the same 2% polyester adhesive, 5 cm above the scratch by the method shown in FIG.
X3cmX3mm FRP member (unsaturated polyester)
To reinforce the repair surface. The interface between the FRP member and the crosslinked polymer was coated with a polyester adhesive having a tensile breaking strain after curing of 2%. After that, when the crack initiation test (3) was performed again, it was 3
Water leakage started again from the repair department on the first day.

[0061]

INDUSTRIAL APPLICABILITY By applying the repair method according to the present invention to the repair of a crosslinked polymer molded article related to water use, or by applying a combination of such repair methods, water leakage may occur. Even if there is, it is possible to stop the water leakage and continue to use the crosslinked polymer molded article by the repair.

[Brief description of the drawings]

FIG. 1 shows a plate-like body in which a notch representing a crack as a model is shown to show a bonding method in the present invention.

FIG. 2 shows an example of repairing a plate-like body having a notch representing a crack as a model to repair the bonding method according to the present invention with only an adhesive.

FIG. 3 shows an example of repairing a plate-like body in which a notch which represents a crack as a model is repaired with an adhesive and an FRP member for overlay in order to show the bonding method in the present invention.

FIG. 4 shows an example of repairing a plate-like body in which a notch representing a crack as a model is repaired with an adhesive and a reinforcing fiber to show the bonding method in the present invention.

FIG. 5 shows upper tank parts and lower tank parts used in the evaluation of the present invention, where A is a front view and B is a side view.

FIG. 6 shows equipment for promoting thermal deterioration used in the evaluation of the present invention.

[Explanation of symbols]

1 Plate-shaped body obtained by cutting out a part of cross-linked polymer molded product 2 Cut line of plate-shaped body obtained by cutting out a part of cross-linked polymer molded product 3 Surface 4 Adhesive according to the present invention 5 FRP member for overlay 6 Adhesive according to the present invention 7 Reinforcing fiber 8 Septic tank upper tank portion 9 Flange 10 Septic tank lower tank portion 11 Steam injection pipe 12 Liquid surface 13 Soil surface 14 to 20 Purification tank side Scratches on the wall

Claims (3)

[Claims] 1. A monomer liquid A (solution A) containing a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer containing a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system. A crosslinked polymer molded article obtained by mixing liquid B (solution B), injecting the raw material mixed liquid into a mold, and causing polymerization and crosslinking reaction in the mold. In a product for use in which a part or all of the surface of a molded product comes into contact with water or an aqueous solution, the water leakage part generated in the crosslinked polymer molded product is treated with a polyurethane adhesive, an epoxy adhesive, a vinyl ester adhesive or A repair method comprising repairing with an unsaturated polyester adhesive having a tensile fracture strain after curing of 5% or more. 2. A polyurethane-based adhesive or an epoxy-based adhesive, wherein the water leakage portion is overlaid with a fiber reinforced plastic member or a semi-cured FRP member, and the fiber reinforced plastic member or the semi-cured FRP member and the crosslinked polymer molded product are combined. The repair method according to claim 1, wherein the adhesive is a vinyl ester adhesive or an unsaturated polyester adhesive having a tensile strain at break of 5% or more after curing. 3. A polyurethane-based adhesive, an epoxy-based adhesive, a vinyl ester-based adhesive or an unsaturated polyester-based adhesive, which is coated with a reinforcing fiber or is filled with a reinforcing fiber in the water-leaking part, after curing. The repair method according to claim 1, wherein the water leakage portion is repaired together with the reinforcing fibers with a tensile breaking strain of 5% or more.