JPH052689B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an underwater curable epoxy resin composition, and more particularly to a composition that can effectively prevent corrosion and staining of underwater structures. [Conventional technology] Construction and construction of oil drilling or oil stockpile purging associated with recent offshore development, steel structures such as offshore plant ships, piers of huge bridges constructed on the ocean, underwater steel structures of offshore airports, etc. However, it is almost impossible to move these from the installation area for maintenance purposes. Therefore, problems such as anti-corrosion coating, cleaning, maintenance, etc. occur in the underwater part of these marine steel structures or in the splash zone, and the need for maintenance at sea has become a major issue. One possible means to solve this problem is to form a coating with excellent corrosion resistance on the underwater parts and splash zone parts of these underwater structures using the same simple and easy means as on land. Conventionally known underwater coating compositions include epoxy resin-based compositions,
There are compositions in which a polyamide or polyamine is used as a hardening agent and a filler is added thereto. However, this known composition has weak adhesion and is easily washed away by waves during curing, and even if it is cured, the adhesion of the cured product is insufficient and long-term corrosion protection cannot be expected at all. It's something that doesn't exist. The present inventor focused on the above-mentioned drawbacks of conventional underwater coating-like compositions, and developed an underwater coating that can be easily coated underwater by the same operation as on land, and can form a coating with excellent adhesion and high corrosion resistance. We have been conducting intensive research to develop a composition for water treatment and, in turn, to develop a method that can effectively protect underwater structures using this composition. We have successfully developed a water-curable epoxy resin composition and have already applied for a patent. This composition consists of (a) a base resin obtained from an alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups and an epoxy resin, and (b) a curing agent for epoxy resin (hereinafter referred to as (referred to as the desired composition). In this prior application composition, by using an epoxy resin and an alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups (hereinafter simply referred to as alcohol ester) as the base resin, the original excellent coating film of the epoxy resin can be improved. In addition to maintaining the performance and curability as they are, the cooperative action of the alcohol ester and the epoxy resin provides extremely excellent adhesion in water.
For this purpose, when a composition consisting of (a) and (b) above is applied, the adhesion is extremely strong, so it will not be washed away by waves etc. before curing, and will cure as it is, and the cured film will have high adhesion. Therefore, it firmly adheres to underwater structures. In addition, since the cured coating film retains the original excellent properties of epoxy resin, it has extremely excellent corrosion resistance and many other properties.In the end, these characteristics combine to provide extremely excellent corrosion protection. This effectively protects underwater structures. It should be noted that the fact that the adhesion of epoxy resin in water can be significantly improved by using alcohol ester and epoxy resin together is a completely unknown and unknown fact, and has been the subject of many years of research by the present inventor. This is a surprising new fact discovered for the first time. [Problems to be developed by the invention] As the present inventor continued further research on the above-mentioned underwater curing composition, it was discovered that when the composition of the prior application further contains an inorganic cementitious material, the composition of this cementitious material It has been found that the adhesion between the cured product and the construction surface can be further improved by reacting with the water that has migrated inside and the water present on the construction surface. Furthermore, we discovered the following new facts. That is, a specific base resin from among the base resins used in the composition of the earlier application and a specific curing agent from among the curing agents also used in the composition of the earlier application are selected and combined. When used, the obtained underwater curable epoxy resin composition can be made into a putty-like composition with a high viscosity, but this putty-like composition hardly sticks to hands and is extremely workable. It has been discovered that a putty-like material with excellent hand-workability can be obtained, and that when an inorganic cementitious material is added to the putty-like material, the adhesion of the cured product can be further improved in the same manner as described above, and the present invention has been made. completed. It is known that this type of underwater curable epoxy resin composition can be made into a putty, and this will be briefly explained below. Such an underwater curable epoxy resin composition is
In still water or under humid conditions, resins and hardeners with relatively low viscosity can be used; however, they can be used in water with current or pressure, in locations of water leaks, or in marine structures such as piers and water gates. Underwater or in the splash zone,
In particular, it is desirable to select and use a composition that can be made into a putty-like composition in which the viscosity of the resin and curing agent is increased. This is because, if a compounding system with a low viscosity is used, there is a risk that the mixture may flow out or peel off due to hydraulic force while being cured at room temperature after lining, sealing, etc. are performed by mixing the two. Conventionally, underwater curable epoxy resin compositions consisting of such high viscosity formulations have been mixed by automatic means such as low viscosity formulations, by mixing means using stirring jigs, or by mechanical means during coating. It is difficult to find a suitable construction method, and so-called hand work is usually used, which involves mixing by hand and applying by hand. Particularly in the case of offshore structures, etc., which have complex structures and require work conditions that make it difficult to install permanent scaffolding, it is necessary to rely on such hand work methods. However, conventionally known compositions of this kind have a problem in that when mixing the resin system and the curing agent system, the mixture sticks to the hands and cannot be mixed sufficiently. This problem can be avoided to some extent by adding an oily substance such as vaseline to each formulation, but in this case, the water repellent action of the oily substance mentioned above makes it impossible to successfully adhere to the construction surface. This makes it impossible to achieve the original purpose. In addition, as another solution, we focused on the fact that underwater curing agents are difficult to dissolve in water and that the curing reaction is not easily affected by water. The wet hand method, which involves working while getting your hands wet, is being considered. However, even with this method, the following problems occur and the expected results are not obtained. That is, whenever you wet your hands with water, the water will migrate into the formulation within a short period of time, so you must frequently wet your hands with water during mixing. This becomes extremely inefficient during actual construction, and increases the amount of water that migrates into the compound, which may adversely affect the properties of the cured product. It is also conceivable to carry out the mixing operation itself in water as a means of constantly moistening hands with water, but deterioration of the properties of the cured product due to the contamination of a large amount of water is unavoidable. In this manner, an underwater curable epoxy resin composition that can be used without adhesion to hands during manual work has not been known at all, and was developed by the present inventor for the first time. The composition of the present invention comprises (1) (a) a base resin obtained from an alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups and an epoxy resin, (b) a curing agent for the epoxy resin, and (c) an inorganic cementum. An underwater curable epoxy resin composition characterized by containing a substance. (2)(a)' A base resin obtained from an alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups and a non-alicyclic epoxy resin. (b)' A curing agent whose main component is a polyamide amine having an average of about 1.7 or more primary or secondary amino groups per molecule, and (c) an inorganic cementitious substance. The invention relates to an underwater curable epoxy resin composition. [Function] In the present invention, the base resin used in the invention described in claim 1 (hereinafter referred to as the present invention-1) is obtained from an epoxy resin and an alcohol ester. The method for producing this base resin is as follows. First, to explain the blending ratio of both raw materials, epoxy resin and alcohol ester, the blending ratio of both is in principle such that the epoxy group remains, and usually 0.025 of alcohol ester per equivalent of epoxy group in the epoxy resin. The blending ratio is ~0.5 mole. In addition, it is preferable that the mixture ratio is such that an average of 0.05 mol or more, preferably 0.1 mol or more of alcohol ester is reacted and contained per 1 mol of the product obtained by heat treatment from both of them. It is preferable to set the blending ratio so that the equivalent weight is 3000 or less. A base resin is produced by heat-treating both raw materials blended in the above-mentioned predetermined proportions in the presence or absence of a solvent and, if necessary, in the coexistence of a catalyst. The heating temperature at this time is usually about 100 to 200℃, preferably 130 to 200℃.
The temperature is about 165°C, and the heating time is usually about 1 to 100 hours, preferably about 7 to 65 hours. Catalysts that may be used as necessary include, for example, dimethylbenzylamine, methylbenzylmethylamine,
Triethylamine, triethanolamine, 2-
Tertiary amines such as dimethylamino-2-hydroxypropane, tetramethylammonium chloride,
Quaternary ammonium salts such as trimethylmonoethyl ammonium chloride and tetramethylammonium fluoride; quaternary phosphonium salts such as tetramethylphosphonium iodide, tetramethylphosphonium bromide, tetramethylphosphonium chloride, and trimethylmonoethylphosphonium chloride; Examples include amine hydrochloride. Typical examples of the solvent include cyclohexanone, methyl cellosolve, butyl cellosolve, cellosolve acetate, cellosolve, etc.
Used in an amount of 50% by weight. The epoxy resin used as a raw material for the base resin in the present invention-1 has the following formula: Typical examples include those having at least one substituted or unsubstituted glycidyl ether group in the molecule (where Z represents a hydrogen atom, methyl group, or ethyl group), such as diglycidyl ether of bisphenol A. , diglycidyl ether of bisphenol F, phenol novolac epoxy resin, diglycidyl ether of alkylene oxide adducts of bisphenols, etc. can be used, and the epoxy equivalent is not particularly limited, but preferably the epoxy equivalent is 200 to 200. Something around 1000 is good. The alcohol ester used in the present invention-1, more specifically the alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups in the molecule, is an ester of the above-mentioned polyhydric phenol carboxylic acid and alcohol, preferably the above-mentioned alcohol ester. It is an ester of polyhydric phenocarboxylic acid and polyhydric alcohol. As the polyhydric phenol carboxylic acid having adjacent hydroxyl groups used here, those having one or more carboxyl groups are used, such as catechol-3-carboxylic acid, catechol-4-carboxylic acid (protocatekylic acid), gallic acid (3, 4,
5-trioxybenzoic acid), m-digallic acid, pyrogallol-4-carboxylic acid, pyrogallol-
Preferred examples include 4,6-dicarboxylic acid and tannic acid. It is essential to use a polyhydric phenolcarboxylic acid having adjacent hydroxyl groups; polyhydric phenolcarboxylic acids having non-adjacent hydroxyl groups are not preferred because their adhesion in water decreases. The hydroxyl groups present in the polyhydric phenol carboxylic acid are mainly consumed in the reaction with the epoxy resin, and the carboxyl groups are necessary for the ester with the alcohol. Furthermore, although a monohydric alcohol can be used as the alcohol used to form the ester, a polyhydric alcohol having a dihydrity or more is preferable. Specific examples include aliphatic monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, diols such as ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , pentaerythritol, sorbitol, glycose, and other polyols having a valence of 4 or more. The ester reaction between a polyhydric phenol carboxylic acid having adjacent hydroxyl groups and an alcohol can be carried out according to a conventional method. As a typical structure of the ester produced in this way, for example, the case of an ester of glycerin and protocatechuic acid is shown. The example is as follows. However, it is thought that other higher-order condensates are also included. As the curing agent used in the present invention-1, all curing agents for ordinary epoxy resins can be used in a wide range, such as aliphatic polyamines, aromatic modified polyamines, alicyclic polyamines, polyamides, Examples include amino resins and carboxylic acids. The amount of these curing agents used is also sufficient as the amount used as a normal curing agent. When protecting an underwater structure using the present invention-1, the present invention-1 is applied to the underwater part or splash part of the underwater structure. As the coating means at this time, any of the various means similar to those used on land can be effectively used, such as brush coating, roll coating, spatula coating, mechanical coating, etc. 20 to 500 poise for brush application and roll application, 500 to 500 poise for spatula application
The viscosity is preferably about 2000 poise. In the present invention-1, an inorganic cementitious material is blended. Inorganic cementitious materials include various types of cement commonly referred to as cement, as well as inorganic materials exhibiting binding properties such as gypsum and dolomite. Examples of this cement include ordinary Portland cement, early strength Portland cement, super early strength Portland cement, white Portland cement, moderate heat Portland cement, phosphoric acid cement, silica cement, blast furnace cement, fly ash cement, alumina cement, expanded cement, and ultrafast Portland cement. Examples include hard cement, sulfate-resistant cement, oil well cement, and colloidal cement. Among these, ordinary Portland cement, early strength Portland cement, ultra early strength Portland cement, and white Portland cement are particularly preferred. The amount of cementitious material added is 5 to 50% of the total amount of the composition, that is, the total amount of base resin and curing agent.
It should be expressed as % by weight. If less than 5% by weight is added, the properties of the cured product deteriorate because the effect of fixing free water through mixing or underwater curing is insufficient. Additionally, if the addition exceeds 50% by weight, the cementitious material will harden due to moisture in the air in the storage state before mixing the base resin and curing agent.
This is not suitable because it is impossible to mix both blending systems. When adding cementitious substances, it is not good to add them in a way that only creates a mixture of the cementitious substances and the base resin; other methods, such as adding them to the hardener, or to a mixture of the hardener and the base resin, or to It is preferable to mix the two at the same time. In the present invention, the base resin used in the invention described in claim 2 (hereinafter referred to as the present invention-2) is a non-alicyclic epoxy resin selected from among epoxy resins. , obtained from this and an alcohol ester. The method for producing this base resin is as follows. The blending ratio of the non-alicyclic epoxy resin and the alcohol ester is the same as the blending ratio of the epoxy resin and alcohol ester of the present invention-1.
Further, the conditions for producing the base resin from these two raw materials may be the same as in the case of the present invention-1. Non-alicyclic epoxy resins used in the present invention-2 include, for example, the following: epoxidized cyclic silanes, epoxidized soybean oil, polyglycidyl esters of polycarboxylic acids, epoxidized polyolefins, and glycidyl ethers. resin. Among these, glycidyl ether resin is preferred. Examples of polycarboxylic acid polyglycidyl esters include diglycidyl esters such as linolein dimer and triglycidyl esters such as linolein trimer. Glycidyl ether resins include polyallyl glycidyl ether, diglycidyl ether of chlorendiol, diglycidyl ether of dioxanediol, diglycidyl ether of endomethylene cyclohexanediol, epoxy novolac resin, alkanediol diglycidyl ether, and alkanetriol triglycidyl. There is ether etc. More preferred glycidyl ether resins include alkanediol glycidyl ethers represented by the formula: (wherein, X is alkylene or alkylidene having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms,
n is 1-20, preferably 1-15. ) Suitable alkanediol diglycidyl ethers include ethylene glycol diglycidyl ether,
Examples include propylene glycol diglycidyl ether and butanediol diglycidyl ether. Other more desirable glycidyl ether resins include alkane triol triglycidyl ethers having alkanes having 2 to 10 carbon atoms, especially 3 to 10 carbon atoms, such as glyceryl triglycidyl ether,
Examples include triglycidyl ether of trimethylolpropane. Still other more desirable glycidyl ether resins are di- and polyglycidyl ethers of bisphenols represented by the following formula. (wherein R is a divalent radical containing 1 to 8 atoms of at least one selected from the group consisting of C, O, S, and N, preferably an alkylene or alkylidene group having 1 to 8 carbon atoms, (Preferably, it is an alkylene or alkylidene group having 1 to 6 carbon atoms.) Among the above, suitable bisphenols include methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, and bisphenol sulfur. ido, bisphenol sulfone, bisphenol ether, and bisphenolamine. In particular, excellent results were obtained using isopropylidene bisphenol. Suitable di- and polyglycidyl ethers include the di- and polyglycidyl ethers of isopropylidene bisphenol. Further, as the alcohol ester used in the present invention-2, more specifically, as the alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups in the molecule, any of those used in the present invention-1 can be used. As the curing agent for the epoxy resin used in the present invention-2, a curing agent whose main component is a polyamide amine having an average of about 1.7 or more primary or secondary amino groups per molecule is particularly selected. The polyamide amine that constitutes the main component of the curing agent compound system of the present invention-2 has an average of about 1.7 or more primary or secondary amino groups per molecule, and generally has an amino value of 80 to 400. be done. Examples of this include polymerized fatty acids such as dimer acid and trimer acid obtained by polymerizing fatty acids having unsaturated bonds in the molecule such as linoleic acid, oleic acid, linoleic acid, elaidic acid, and ricinoleic acid, and polyamines; Particular mention may be made of condensation reaction products with aliphatic polyamines. The above-mentioned polyamine is a polyamine having two or more amino groups having at least one active hydrogen atom in one molecule, and preferable examples include aliphatic diamines that do not contain a ring structure in the molecule. , alkylene polyamines, branched polymethylene diamines, polyalkylene polyamines, aliphatic diamines containing aromatic residues as a ring structure, aliphatic diamines containing aliphatic residues as a ring structure, hetero Examples include aliphatic amines containing a ring residue as a ring structure. These polyamines may be used alone or as a mixture of two or more thereof for the condensation reaction. Examples of aliphatic diamines that do not contain a ring structure in the molecule include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, and undecamethylenediamine. Examples of alkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethyleneheptamine, di(hexamethylene)triamine, tri(hexamethylene)tetramine,
Examples include tetra(hexamethylene)pentamine, tripropylenetetramine, and tetrapropylenepentamine. Branched polymethylene diamines include 2-methyl-2,4-diaminopentane, _CH3H2N ( _CH2 ) _nCHNH2 ( _n : an integer from 1 to 8)
Examples include. As polyalkylene polyamines, iminobispropylamine [H ₂ N (CH ₂ ) ₃ NH
(CH ₂ ) ₃ NH ₂ ], methyliminobispropylamine

〔Effect of the invention〕

In the present invention-1, by using an epoxy resin and an alcohol ester of polyhydric phenol carboxylic acid having adjacent hydroxyl groups as the base resin, the original excellent coating performance and curability of the epoxy resin can be maintained as is. In addition to this, extremely excellent adhesion in water is developed due to the cooperative action of the alcohol ester and the epoxy resin. For this purpose, when a composition consisting of (a) and (b) above is applied, it has extremely high adhesion, so it will not be washed away by waves etc. before curing, and will harden as it is, and the cured film will have high adhesion. Therefore, it firmly adheres to underwater structures. In addition, the cured coating film retains the original excellent properties of epoxy resin, so it has extremely excellent corrosion resistance and many other properties.
In the end, all of these features collectively demonstrate an extremely excellent anti-corrosion effect, effectively protecting underwater structures. In particular, by incorporating inorganic cementitious substances, the above physical properties are not impaired at all.
It has the effect of greatly improving the curing properties of the cured product, especially the adhesive strength. In addition, in the present invention-2, by adopting the wet hand method during mixing and application, polyamide amine, which is a hardening agent, has excellent affinity with water, so it adheres to hands with a surfactant-like action. It is eluted and separated by water to form a lubricating layer on the surface of the hands, and this lubricating layer allows the formulation to be easily removed from the hands and prevents the formulation from adhering to the hands. Furthermore, by using an epoxy resin and an alcohol ester of a polyhydric phenol carboxylic acid having adjacent hydroxyl groups as a base resin, the original excellent coating performance and curability of the epoxy resin can be maintained, and the above alcohol ester can also be used. The synergistic action of the epoxy resin and the epoxy resin results in extremely excellent adhesion. Furthermore, the cement added to the mixture reacts with the water that migrates into the mixture and the water that is present on the construction surface during construction, fixing free water, which reduces the deterioration of the properties of the cured product due to moisture migration. The major feature of this method is that it provides good adhesion between the cured product and the surface to which it is applied. [Example] The present invention will be specifically explained with reference to Examples below. However, in the following examples, parts indicate parts by weight. Example 1 20 parts of protocatechuic acid triester of glycerin (MW = 500), 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 190), 60 parts of ethyl cellosolve, and 0.15 parts of dimethylbenzylamine as a catalyst were added and stirred. while heating at 150℃
A reaction was carried out for 7 hours to obtain a base resin (1). 45 parts of the base resin (1), 50 parts of talc S, and 5 parts of colloidal silica were mixed at 5° C. in a stirring mixing pot to prepare an epoxy resin blend system. On the other hand, 15 parts of polyamide amine-1 (amine value 400, active amine hydrogen equivalent 110, average number of amino groups per molecule 5.5), polyamide amine-2 (amine value 235, active amine hydrogen equivalent 178, average number of amino groups per molecule) 25 parts of base number 7), 35 parts of talc S, 5 parts of colloidal silica, and 20 parts of ordinary Portland cement were mixed at 50°C in a stirring mixing pot to prepare a curing agent compounding system. A two-component water-curable epoxy resin composition of the present invention was obtained by mixing this curing agent blend system and the above-mentioned epoxy resin blend system at a mixing ratio (by weight) of 1:1. Initial adhesion when this composition was applied to a steel plate by the wet hand method to a dry film thickness of 2 to 3 mm, adhesion after curing,
Destruction rate and rust occurrence were measured. The results are shown in Table 1 below. However, the steel plate used was a steel plate that had been immersed in 3% common salt for 4 hours immediately after shot blasting. Example 2 150 parts of bisphenol A glycidyl ether (epoxy equivalent = 190), 50 parts of diglycidyl ether of bisphenol A propylene oxide adduct (epoxy equivalent 340), 50 parts of m-digallic acid ester of glycose, cellosolve acetate 100
1 part and 0.5 part of triethylamine as a catalyst,
The reaction was carried out at 150°C for 16 hours to obtain base resin (2). 45 parts of the base resin (2), 50 parts of talc S, and 5 parts of colloidal silica were mixed in a stirring mixing pot at 50°C to prepare an epoxy resin blend system. On the other hand, the curing agent combination system is
Using the same curing agent compounding system as in Example 1,
A two-component underwater curable epoxy resin material of the present invention is obtained by mixing this curing agent blend system and the epoxy resin blend system at a mixing ratio (weight ratio) of 1:1,
It was treated in the same manner as in Example 1. Example 3 150 parts of bisphenol F diglycidyl ether (epoxy equivalent = 240) and 50 parts of pyrogallol-4-carboxylic acid diester of diethylene glycol,
Add 100 parts of cyclohexanone and 1 part of triethanolamine as a catalyst and heat at 135°C for 12 hours with stirring.
The reaction was continued for hours to obtain a base resin (3). 45 parts of the base resin (3), 50 parts of talc S, and 5 parts of colloidal silica were mixed at 50° C. in a stirring mixing pot to prepare an epoxy resin blend system. On the other hand, the curing agent compounding system used was the same as in Example 1, and the mixing ratio (weight ratio) of this curing agent compounding system and epoxy resin compounding system was 1:1, resulting in two-component underwater curability. An epoxy resin composition was prepared and treated in the same manner as in Example 1. Comparative Example 1 45 parts of unmodified bisphenol A diglycidyl ether (epoxy equivalent = 190), 50 parts of talc S,
Five parts of collodyl silica were mixed at 50°C in a stirring mixing pot to form an epoxy resin compound system. On the other hand, for the curing system, the same curing agent system as in Example 1 was used, and the curing system and the epoxy resin system were mixed at a mixing ratio (weight ratio) of 1:1. A liquid type underwater curable epoxy resin composition,
The same treatment as in Example 1+ was carried out. Comparative Example 2 45 parts of unmodified bisphenol A diglycidyl ether (epoxy equivalent = 190), 50 parts of talc S,
Five parts of collodyl silica were mixed in a stirring mixing pot at 50°C to form an epoxy resin compound system. On the other hand, 15 parts of polyamide amine-1, 25 parts of polyamide amine-2, 55 parts of talc S, and 5 parts of collodyl silica were mixed at 50° C. in a stirring mixing pot to prepare a curing agent compounded system. A two-component underwater curable epoxy resin composition was prepared by mixing this hardening agent and the epoxy resin at a mixing ratio (weight ratio) of 1:1, and treated in the same manner as in Example 1.

[Table] However, the measurement methods for each physical property in Table 1 are as follows. Steel plate: Dull steel plate of 9 x 100 x 100 mm Coating method: After the above-mentioned steel plate was immersed for a predetermined time, the composition was applied by a wet hand method while the steel plate was immersed, and cured in a vertical position. Initial adhesion method: The quality of workability (adhesion) when applying by wet hand method was observed and evaluated according to the following criteria. ○...Good (adheres easily) ×...Poor (does not stick unless rubbed many times) Adhesion after curing: After 6 months, the immersed paint sample is taken out into the atmosphere (23℃, 65%RH) After one day, the coating film was cut with a cutter, a measurement dolly was attached using adhesive, and after 30 minutes it was heated to 23℃ and 60%.
Measurement was performed using an ercometer under RH. Occurrence of rust: Observe the surface with the naked eye to determine the presence or absence of rust. Example 4 100 parts of an alicyclic epoxy resin (epoxy equivalent: 131) obtained from cyclohexane and m-
70 parts of digallic acid ester, cellosolve acetate
100 parts and 0.5 part of triethylamine as a catalyst were added, and the reaction was carried out at 150°C for 15 hours to obtain a base resin (4). 45 parts of the base resin (4), 50 parts of talc S, and 5 parts of colloidal silica were mixed in a stirring mixing pot at 50°C,
It is an epoxy resin compound system. On the other hand, the curing agent compounding system used was the same as the curing agent compounding system of Example 1,
A two-component underwater curable epoxy resin composition of the present invention was obtained by mixing this curing agent blend system and the epoxy resin blend system at a mixing ratio (weight ratio) of 1:1, and treated in the same manner as in Example 1. . Example 5 45 parts of base resin (4) of Example-4, talc S50
and 5 parts of colloidal silica were mixed at 50°C in a stirring mixing pot to form an epoxy resin compound system, while a curing agent compound system consisted of 65 parts of modified aliphatic polyamine (active amine hydrogen equivalent: 210, amine value 185), and ordinary Portland cement. 25 parts, talc S5 parts, colloidal silica
10 parts were mixed at 50°C in a stirring mixing pot to form a curing agent blend system. A two-component underwater curable epoxy resin composition of the present invention was obtained by mixing this curing agent blend system and the epoxy resin blend system at a mixing ratio (by weight) of 1:1. It was treated in the same manner as in Example 1. The results of Examples 4 and 5 above are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1. (a) a base resin obtained from an alcohol ester of polyhydric phenolcarboxylic acid having adjacent hydroxyl groups and an epoxy resin, (b) a curing agent for the epoxy resin, and (c) an inorganic cementitious material. An underwater curable epoxy resin composition comprising: 2 (a)' A base resin obtained from an alcohol ester of a polyhydric phenol carboxylic acid having adjacent hydroxyl groups and a non-alicyclic epoxy resin (b)' An average of about 1.7 primary or secondary amino groups per molecule 1. A water-curable epoxy resin composition comprising: a curing agent whose main component is a polyamide amine having at least 100% polyamide, and (3) an inorganic cementitious material.