JPS5936929B2 - Underwater curing method for epoxy resins and amine-terminated liquid polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an underwater curable composition comprising at least one non-alicyclic epoxy resin and at least one liquid polymer having an amine terminal group and a C-C main chain. Concerning a curing method.

Underwater curable paints are already known in the art (e.g. DriskO.PaintanbVarnish
Pr-duct10n. Volume 58 P3l, 1968 7
(See monthly issue).

Such coatings usually consist of amine-terminated polyamide resins and liquid epoxy resins. These known coatings cure rather slowly and possess moderate adhesive strength and flexibility. There is a need in the art for underwater curable compositions that have fast curing speeds and improved adhesive strength and flexibility. The present invention satisfies such demands, and includes at least 100 parts by weight of at least one non-alicyclic epoxy resin and a liquid polymer having a C-C main chain and having an amine terminal group. A mixture containing about 1 to about 2000 parts by weight of either type is applied to the surface of the object to be coated, and the mixture is cured in water. Hereinafter, the composition used in the present invention will be explained in detail.

Liquid polymer having amine terminal groups The liquid polymer having amine terminal groups used in the present invention is represented by the following formula.

where Y is a monovalent radical obtained by removing hydrogen from the amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine containing at least two primary and/or secondary amines, B is a polymer backbone with carbon-carbon bonds.

Generally, carbon-to-carbon bonds account for at least about 90%, preferably about 95% by weight of the total weight of the polymer backbone.
The amine-terminated polymer has an average b per molecule of about 1.7 to
It contains about 3, preferably about 1.7 to about 2.3 primary and/or secondary amines. In addition, polymers with amine terminal groups have approximately 500 cps to 2,500,000 CPS1
Preferably, it can have a Bruckfield viscosity (measured at 27°C using a Bruckfield RVT viscometer) of about 500 cps to about 500,000 cps. Noamine-terminated liquid polymers are defined as liquid polymers having a carbon-carbon backbone with carboxyl- or ethyl-terminated groups containing at least two primary and/or secondary amine groups. It can be easily prepared by reacting with one aliphatic, alicyclic or heterocyclic amine.

Amine-terminated liquid polymers also include acid chloride-terminated liquid polymers with a carbon-carbon backbone containing at least one amine group containing at least two primary and/or secondary amine groups. It can also be easily produced by reacting with aliphatic, alicyclic, heterocyclic or aromatic amines. The carboxyl-terminated liquid polymer has a polymer backbone consisting of carbon-to-carbon bonds, and has a polymer chain of about 500 cps to about 500,000 cps.
ps, and more preferably has a Brookfield viscosity of about 500 cps to about 250,000 cps.

The carboxyl functional groups are located at least at both ends of the polymer molecule, but there may be some suspended in the middle of the polymer main chain. The average number of total carboxyl groups per molecule is approximately 1.7
to about 3, preferably about 1.7 to 2.3. Polymers having a carbon-carbon main chain and a carboxyl terminal group are as follows (a), (b). It may contain at least one polymerized unit of vinylidene monomer selected from the group consisting of (c), (d) and (e) with at least one terminal CH2=C group.

(a) Monoolefins having 2 to 14 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 1-benzene, 1-hexene, 1-dodecene and the like. (b) Number of carbon atoms: 4 to 10, preferably 4 to 8
dienes such as butadiene, isobrene, 2-isopropyl-1,3-butadiene, chloroprene, etc. (c)
Vinyl and allyl esters of carboxylic acids having 2 to 8 carbon atoms, such as vinyl acetate, vinyl propionate, allyl acetate, and the like. (d) Vinyl and allyl ethers of alkyl radicals having 1 to 8 carbon atoms, such as vinyl methyl ether, allyl methyl ether, etc. (e) Acrylic acids and acrylates represented by the following formula. In the above formula, R
is hydrogen or an alkyl radical having 1 to 3 carbon atoms; R1 is hydrogen or an alkyl radical having 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms;
8 alkyl radicals or alkoxyalkyl, alkylthioalkyl or cyanoalkyl radicals having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms.

More preferably R1 is hydrogen or an alkyl radical having 1 to 8 carbon atoms. Suitable acrylates include, for example, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, hexylthioethyl acrylate, Examples include β-cyanoethyl acrylate, cyanooctyl acrylate, methyl methacrylate, ethyl methacrylate, and octyl methacrylate. Two or more types of these polymerizable monomer units may be contained in the polymer main chain. Among the above-mentioned polymers, more preferred liquid polymers are a). Contains at least one polymerized unit of vinylidene monomer selected from the group consisting of (b) and (e) and having at least one terminal CH2=C group.

(a) Monoolefin having 2 to 14 carbon atoms, preferably 2 to 8 carbon atoms; (b) Monoolefin having 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms;
8, and (e) acrylic acids and acrylates represented by the following formula. In the formula, R is hydrogen or an alkyl radical having 1 to 3 carbon atoms. R1 is hydrogen, an alkyl radical having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms.

More preferably R1 is hydrogen or an alkyl radical having 1 to 3 carbon atoms. Excellent results can also be obtained using dienes having 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms. The vinylidene monomers described above may contain up to about 50% by weight of O, preferably up to 35% by weight of O, as shown in (f), (g) below.
, (h), (1). (J) and at least one comonomer selected from the group consisting of ω.

(f) a vinyl aromatic daughter compound represented by the following formula, where R
2 is selected from the group consisting of hydrogen,...rogen, and alkyl radicals having 1 to 4 carbon atoms, such as styrene, α
-Methylstyrene, chlorostyrene, vinyltoluene, etc. (g) Vinyl nitriles represented by the following formula, where R3 is hydrogen or an alkyl radical having 1 to 3 carbon atoms, such as acrylonitrile, methacrylonitrile, etc.

(h)...Vinyl rogenide, such as vinyl bromide, vinyl chloride, etc. (1) Divinyl and diacrylates, such as divinylbenzene, divinyl ether, diethylene glycol diacrylate, and the like. (j) Number of carbon atoms: 2-8
amides of D,β-olefinic unsaturated carboxylic acids, such as acrylamide. ω Allyl alcohol etc. A liquid polymer comprising a polymerized unit consisting of a dominant amount of at least one vinylidene monomer selected from (a) to (e) and a minor amount of at least one comonomer selected from (f) to ω. It falls within the scope of the present invention. More preferred comonomers are selected from the group consisting of (f) and @ below.

(f) A vinyl aromatic compound represented by the following formula, selected from 1 to 4 alkyl radicals.

(g) Vinyl nitrile acid represented by the following formula, R3 in the above formula
is hydrogen or an alkyl radical having 1 to 3 carbon atoms.

In particular, excellent results were obtained with styrene and acrylonitrile. Useful liquid polymer backbones containing carbon-to-carbon bonds include, for example, polyethylene, polyisoptylene, polyisobrene, polybutadiene, poly(vinylethyl ether), polyethyl acrylate and polybutyl acrylate, and butadiene and acrylonitrile,
Butadiene and styrene, vinyl acetate and isoprene, vinyl acetate and chloroprene, vinyl ethyl ether and diallyl ether, vinyl ethyl ether and α-methylstyrene, vinyl ethyl ether and vinyl bromide, methyl acrylate and butadiene, methyl acrylate and acrylic acid Ethyl, methyl acrylate and butyl acrylate, methyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and ethylene, ethyl acrylate and isobutylene, ethyl acrylate and isoprene, ethyl acrylate and butadiene, ethyl acrylate and vinyl acetate , ethyl acrylate and styrene, ethyl acrylate and chlorstyrene,
Ethyl acrylate and styrene and butadiene, ethyl acrylate and n-butyl acrylate, ethyl acrylate and n-butyl acrylate and 2-ethylhexyl acrylate,
Ethyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and vinyl bromide, ethyl acrylate and acrylic acid, ethyl acrylate and acrylamide, ethyl acrylate and allyl alcohol, butyl acrylate and styrene and isobrene, butyl acrylate and There are copolymers of styrene, butyl acrylate and acrylonitrile, and butyl acrylate and vinyl chloride. Liquid polymers with carboxyl end groups can be prepared by free radical polymerization using carboxyl-containing initiators and/or modifiers as disclosed in U.S. Pat. Patent No. 3135
No. 716 and No. 3,431,235, it can be produced by solution polymerization using metallic lithium or an organometallic compound and post-treatment of the polymer to generate carboxyl groups.

This polymer can also be obtained by reacting a polymer having a terminal group other than a carboxyl terminal group with a carboxyl group-forming compound. For example, liquid polymers with carboxyl end groups can be obtained by reacting liquid polymers with hydroxyl end groups with dicarboxyl compounds or anhydrides. ... Carboxyl groups can also be produced by reacting a liquid polymer with rogene end groups with an unsaturated anhydride in the presence of a Lewis acid. In any event, it will be understood that the method of preparing the liquid polymer having carboxyl end groups is not critical to the invention. The essential characteristics of a polymer are that it has at least a carboxyl terminal group and a polymer main chain of carbon-carbon bonds.
Suitable examples of liquid polymers with carboxyl end groups include polyethylene with carboxyl end groups, polyisobutylene with carboxyl end groups, polybutadiene with carboxyl end groups, polyisoprene with carboxyl end groups, polyethylene with carboxyl end groups. There are ethyl acrylates and copolymers of butadiene and acrylonitrile and of butadiene and styrene with carboxyl end groups.

Copolymers of butadiene with carboxyl end groups and acrylonitrile or styrene have been found to be particularly useful. These polymers may contain from about 50 to about 99.6 weight percent butadiene, from about 0 to about 40 weight percent acrylonitrile or styrene, and from about 0.4 to about 10 weight percent carboxyl. Liquid polymers having carboxyl end groups can be esterified with aliphatic monohydric alcohols to form liquid polymers having ester end groups by well known methods.

For example, polymers with carboxyl end groups and aliphatic 1
The altar can be reacted in the presence of small amounts of acid catalysts under reflux or in a distillation column. Suitable acid catalysts include organic acids having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms;
For example, monoesters and diesters of orthophosphoric acid, propionic acid, benbroic acid, alkaryl sulfonic acids such as p-toluenesulfonic acid, inorganic acids such as boric acid, hydrochloric acid, phosphoric acid, sulfuric acid, etc. Lewis acids such as tetraisopropyl titanate. The amount of acid catalyst used may be as little as about 0.01 to about 5% by weight, based on the total weight of all reaction components. Suitable aliphatic monohydric alcohols used in this esterification reaction contain from 1 to 12, preferably from 1 to 6 carbon atoms, and below about 150°C.
Preferably it has a boiling point below about 100°C. Primary aliphatic monohydric alcohols are preferred. Suitable aliphatic monohydric alcohols include, for example, alkanols having 1 to 6 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-hexanol, 3-hexanol. Other suitable aliphatic monohydric alcohols include 2-methoxyethanol, 2-ethoxyethanol, and the like. In particular, ethanol, 1-propanol or 1-
Excellent results are obtained with butanol. Liquid polymers having carboxyl end groups can be acylated by well known methods to form acid chloride terminated liquid polymers. For example, a polymer having carboxyl end groups can be reacted with thionyl chloride to form an acid chloride terminated polymer. Although HCI and SO2 are primarily evolved as gases, they are easily separated from the acid chloride-terminated polymer, and excess thionyl chloride can be removed by vacuum distillation or washing with a solvent such as methanol. It can be easily removed by Other suitable acylating agents, although less preferred than thionyl chloride, include phosphorus trichloride and phosphorus pentachloride. Amines that react well with the above-mentioned polymers having carboxyl, ester and acyl end groups include those having at least two, preferably two primary and/or secondary amine groups and having 1 carbon atom. There are ˜20, preferably 1 to 12 aliphatic amines. Also suitable are cycloaliphatic amines having at least two, preferably two primary and/or secondary amine groups and containing from 4 to 201, preferably from 4 to 12 carbon atoms. L having at least two, preferably two primary and/or secondary amine groups
/． It is also possible to use polycyclic amines containing 2 to 20, preferably 2 to 12 carbon atoms. Suitable examples of such amines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 2-methyl-1,2-propanediamine,
Aliphatic amines such as 1,5-pentanediamine, 1,6-hexanediamine, 1,7-hebutanediamine, 1,8-octanediamine, 1.10-decanediamine, 1,12-dodecanediamine; diethylenetriamine, Aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, bis(hexamethylene)triamine, and 3,3'iminobispropylamine; alicyclic polyamines such as 1,2-diaminocyclohexane and 1,8-p-tantanediamine Diamines and polyamines; and 4-(aminomethyl)piperidine, piperazine and N-(
Heterocyclic diamines and polyamines such as (aminoalkyl)piperazine (e.g., N-(2-aminoethyl)piperazine, N-(3-aminopropyl)piperazine, N-N'-bis(3-aminopropyl)piperazine, etc.) There is. More preferred amines contain at least two primary and/or secondary amine groups with different reactivities.

When amine groups with different reactivities are present, termination reaction by amines is more likely to occur than coupling between liquid polymers, and the amount of excess amine may be smaller to avoid coupling. Preferred amines include, for example, 1,8-p-
Certain cycloaliphatic amines such as tantanediamine, 4-(aminomethyl)piperidine and N-(aminoalkyl)piperazines having 1 to 12, preferably 1 to 6 carbon atoms in the alkyl group, such as N-( There are certain heterocyclic amines such as 2-aminoethyl)piperazine, N-(3-aminopropyl)piperazine, etc.). Particularly good results were obtained using N-(2-aminoethyl)biperazine. Aromatic diamines and polyamines can also be used to make amine-terminated polymers.

However, the reaction of polymers with carboxyl end groups with aromatic amines must be at high temperatures. Therefore,
This is less preferred since depolymerization of the reactants and products occurs. However, aromatic amines react well with the aforementioned polymers having acyl end groups. Suitable aromatic amines contain at least two primary and/or secondary amine groups directly bonded to at least one aromatic interlock. Suitable aromatic amines include 4,5-acenaphthylenediamine,
3,5-diaminoacridine, 1,4-diaminoanthraquinone, 3.5-diaminobenzoic acid, 2.7-fluorenediamine, 1,5-naphthalenediamine, 1.8-
naphthalenediamine, 2,4-toluenediamine, 2,
6-toluenediamine, o-phenylenediamine, m-
Examples include phenylene diamine and p-phenylene diamine. A solvent is not essential to the amine termination reaction, but may be used.

Mixtures of solvents can also be used. Suitable solvents include
Aliphatic and cycloaliphatic ethers having 3 to 101 carbon atoms, preferably 3 to 6 carbon atoms, such as tetrahydrofuran, diethyl ether, etc.; mono-logenated aliphatic hydrocarbons having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, e.g. Chloroform, carbon tetrachloride, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, etc.; and carbon atoms with 3 to 3 carbon atoms
101 Preferably 3 to 6 esters, such as ethyl acetate, n-butyl acetate, hexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, and the like. More preferred are aromatic compound solvents having the following general formula. In the above formula, R4 is hydrogen, monologen, or an alkyl radical having 1 to 3 carbon atoms, and at least two of 1R4 are hydrogen.

In the above formula, a more preferable fushun is 1R4 in which R4 is hydrogen, chlorine, or an alkyl radical having 1 to 2 carbon atoms.
At least three of them are hydrogen. Suitable aromatic daughter solvents include benzene, chlorobenzene, toluene, om- and p-xylene, o-, m- and p-diethylbenzene, kyumene, mesitylene, and the like. molecule per b approximately 1.7
A sufficient amount of at least one amine described above is added to a carboxyl end group, an ester end group, as described above, to produce an amine terminated liquid polymer containing ~3 primary and/or secondary amine groups. Alternatively, it may be reacted with a polymer having an acid chloride end group.

Typically, the average total number of J-nocarboxyl, ester, or acid chloride groups in the liquid polymer before reaction is about 1.7 to about 3, preferably about 1.7 to about 2.3 molecular weights. Dew.

In such normal cases, b about 1.2 to
About 6 molar equivalents, preferably about 1,2 to about 3 molar equivalents of at least one of the aforementioned amines can be used. However, when the carboxylated, esterified, or acylated liquid polymer contains polymerized units of acrylic acid, acrylate, etc. in an amount of kana b, the amount of amine used is such that the amine-terminated liquid polymer Must be limited to not containing more than about 1.7 to about 3 primary and/or secondary amine groups. No catalyst is required for the amine termination reaction, and many types of mixing equipment can be used. For example, simple mixers such as turbine agitators and propeller mixers can be used. The reactants can be combined in any order. The reaction mixture may be heated at about 80° C. to about 150° C., usually for about 1 to 6 hours (if a solvent is used, in a far current). The amine-terminated liquid polymer may be purified by vacuum distillation or washing with a solvent such as a benzene-methanol mixture and then dried. The amine content of amine-terminated liquid polymers can be qualitatively analyzed by infrared spectroscopy. The amine content can also be determined by Sigia, “Quantitative Organic Analysis Based on Functional Groups,” pp. 452-456 (N.Y.Wis.
yanbS0ns, Ine. It can be quantitatively analyzed according to the method described in 1963 (published in 1963). Underwater curing of amine-terminated liquid polymer and non-alicyclic epoxy resin The composition used in the method of the present invention comprises (A) at least one of the non-alicyclic epoxy resins mentioned above, 100 parts by weight, and 8 parts by weight of the above-mentioned amine. From about 1 to about 2000 parts by weight of at least one terminal liquid polymer.

The properties of this composition vary greatly depending on the amount of liquid polymer with amine end groups. Although not essential components, a chain-extending crosslinking agent and a curing agent can be incorporated into the composition as necessary, as described below. Non-alicyclic epoxy resins suitable for use with the amine-terminated liquid polymers in this invention have an average D per molecule of at least about 1.
It contains 7 epoxy groups, preferably an average of about 1.7 to about 3.0, more preferably an average of about 1.7 to about 2.3.
The non-alicyclic epoxy resin can be a liquid or a low melting point solid,
Preferably, the liquid has a viscosity of cps (measured at 25° C. using a Bruckfield RVT viscometer). The preferred epoxy resin has an epoxy equivalent weight (weight) (v gram molecules per epoxy group) of from about 70 to about 6,000, preferably from about 70 to about 2,000. Suitable non-alicyclic epoxy resins include epoxidized cyclic silanes, epoxidized soybean oil,
Polyglycidyl esters of polycarboxylic acids, epoxidized polyolefins and glycidyl ether resins,
Among these, glycidyl ether resin is preferred. Suitable polycarboxylic acid polyglycidyl esters include, for example, diglycidyl ester of linoleic dimer acid, triglycidyl ester of linoleic trimer acid, and the like. Suitable glycidyl ether resins include polyallyl glycidyl ether, diglycidyl ether of chlorendiol, diglycidyl ether of dioxanediol,
Examples include endomethylene cyclohexane diol diglycidyl ether, epoxy novolac resin, alkanediol diglycidyl ether, alkanetriol triglycidyl ether, and the like. More preferred glycidyl ether resins include alkanediol diglycidyl ethers represented by the following formula. (In the formula, x is the number of carbon atoms 1 to 10
, preferably an alkylene or alkylidene group having 2 to 6 carbon atoms, n is 1 to 20, preferably 1 to 15.

) Suitable alkanediol diglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, and the like. Other more preferred glycidyl ether resins include *2 to 10 carbon atoms) especially 3 to 1 carbon atoms;
There are alkanetriol triglycidyl ethers having 0 alkane groups, such as glyceryl triglycidyl ether and trimethylolpropane triglycidyl ether.

Yet another more preferred glycidyl ether resin is a di- and polyglycidyl ether of birophenol represented by the following formula. (wherein R5 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, More preferably, it is an alkylene or alkylidene group having N1 to N6 carbon atoms.) Suitable bisphenols include methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octyl bisphenol, bisphenol sulfide, These include bisphenol sulfone, bisphenol ether, and bisphenolamine.
In particular, excellent results were obtained using isopropylidene bisphenol (bisphenol A). Suitable di- and polyglycidyl ethers include isopropylidene bisphenol di- and polyglycidyl ethers of the formula: (where n is about 0 to about 20, preferably about 0 to about 2.

) Alicyclic epoxy resins are not preferred in the present invention.

This is because a mixture of this and a liquid polymer with amine end groups is substantially non-curable at room temperature. Here, the alicyclic epoxy resin means one in which the epoxy group itself forms a part of the alicyclic grooved ring. Such cycloaliphatic epoxy resins include bir(2,3-epoxycyclobentyl) ether, synclopentane edge oxide, bis(epoxydicyclopentyl) ether of ethylene glycol, 3,4-epoxycyclohexylmethyl-(3
．． 4-epoxy)-cyclohexane carboxylate,
Bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate and the like. Other alicyclic resins are described in Epoxy Resin Handbook, co-authored by Lee et al., Kugrow Building Co., N. Y. It is described in Chapter 4 of 1967flk. In the composition of the amine-terminated liquid polymer and epoxy resin used in the present invention, there is no need to incorporate other reactive auxiliaries.

However, chain extenders and/or crosslinkers can be used. The amount of chain extender and/or crosslinker used will vary widely depending on the relative weights of the epoxy resin and amine terminated liquid polymer and the number of reactive functional groups. The amount of chain extender and/or crosslinker also depends on the desired properties of the composition. Generally, the amount of chain extender and/or crosslinking agent used can vary from about 0 to about 60 parts by weight, preferably from about 0 to about 35 parts by weight, based on 100 parts by weight of epoxy resin. Suitable chain extenders and/or crosslinkers may be any difunctional materials known in the art to be reactive with epoxy resins.

Such substances include dibasic acids such as azelaic acid, phthalic acid, and dimercaptans such as 1,6-hexanedithiol, 1,8-octanedithiol. Furthermore, acid anhydrides such as left maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 4,4'-dicyclobentyl methylene diisocyanate, 4,4'-diphenylmethylene diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,)
Diisocyanates such as 4-phenylene diisocyanate; for the production of liquid polymers with amiso end groups, including diamines obtained by the reaction of linoleic acid dimer with diamines, ethylenediamine, N-(2-aminoethyl)piperazine, etc. Di- and polyamines detailed above in connection; and 1,4-dibromobutane, 1,3-dipromoptane, 1,4-dichlorobutane, 1,2-dichloroethane, 1,4-diiodobutane, 1 .6-dichlorohexane and the like having from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, preferably aliphatic dibromides and/or dichlorides.

Other suitable chain extenders and/or crosslinking agents, more preferably 6 to 24 carbon atoms.
, especially dihydroxy aromatic compounds having 6 to 18 carbon atoms.

Such dihydroxy aromatic compounds include catechol, resorcinol, 3-hydroxybenzyl alcohol, 4
-Hydroxybenzyl alcohol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1.
Among them are 7-dihydroxynaphthalene and the like, and preferred ones for the 1st layer include bisphenol represented by the following formula. (In the formula, R5 is an alkylene or alkylidene group having 1 to 8 atoms selected from C, O, S and N, more preferably an alkylene or alkylidene group having 1 to 6 carbon atoms.

) Suitable bisphenols include, for example, methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, bisphenol amine, and the like. Particularly excellent results were obtained using isopropylidene bisphenol (bisphenol A). A curing agent may be used to promote and/or assist the reaction between the epoxy resin and the amine-terminated liquid polymer, but is not essential.

Suitable curing agents include BF3-amine complex, hexahydrophthalic anhydride, dicyandiamide, 2-ethyl-4-
Examples include imidazoles such as methyl-imidazole, triethylenetetramine, and the like. In addition to both the essential components of the amine-terminated liquid polymer and the epoxy resin, and both the optional components of the chain extender and curing agent, various formulation ingredients can be included in the compositions employing this invention.

These formulation ingredients are those commonly used in rubber and/or epoxy formulations. These ingredients are used in standard amounts well known in the art. For example, reinforcing fillers and other components that thicken liquid compositions are generally a mixture of an epoxy resin and an amine-terminated liquid polymer at room temperature.
They can be incorporated at levels up to about 250 parts by weight to 0 parts by weight or more. Ingredients include, for example,
carbon black, carbonaceous and silicic acid metal salts, glass,
Reinforcing fillers such as aspest and fibers; non-reinforcing fillers such as titanium oxide and silica; inorganic and organic colorants such as metal oxides and metal sulfides; petroleum, castor oil, glycerin, silicone, lubricants and plasticizers such as aromatic and paraffinic oils and alkyl and aromatic esters such as phthalic acid, sepacic acid, trimellitic acid; and phenyl-β-naphthylamine,
2.6-di-t-butyl para-cresol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol)
, 2,2'-thiobis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(6-t-butyl-m-cresol), tris(3,5-di-t-butyl- 4-Hydroxybenzyl)isocyanurate, hexahythro1.3.5-tris-β-(3,5-di-t)
-butyl-4-hydroxyphenyl)propionyl ● triazine, tetrakis-methylene-3(3'.5'-di-t-butyl-4'-hydroxyphenyl) propionate ● methane, distearyl ● thiodipropionate,
There are antioxidants and stabilizers such as tri(nonylated phenyl) phosphite. The epoxy resin composition used in the present invention includes (4) 100 parts by weight of the above-mentioned non-alicyclic epoxy resin;
from about 1 to about 2,000 liquid polymers having amine end groups as described above;
parts by weight, preferably about 300 to about 1500 parts by weight, (C
) Chain extenders and/or crosslinking agents as desired components
．． 9. A curing agent as a desired component, and 9. A curing agent as a desired component, and other compounding components as described above.
The mixture can be mixed using a Banbury mixer or the like.

Mixing can be done using standard techniques. When a curing agent is used, it is desirable to first mix it with the amine-terminated liquid polymer. The pot life after mixing of this underwater curable composition is usually about 2 to about 4 hours. Mixture about 100
Heating to temperatures of 0.degree. C. or lower makes it easier to achieve melting and uniform dispersion of the materials, while significantly speeding up curing. The underwater curable materials described above can be applied to various surface materials by coating, puttying, pasting, etc.

Such surface materials include natural rubber, cis-polyisoprene, cis-polyptadiene (Q3) (acrylonitrile-butadiene-styrene copolymer CABS), butadiene-
Acrylonitrile rubber (NBR), isoprene-acrylonitrile rubber, butadiene-styrene rubber (SBR)
, isoprene-styrene copolymer, polychloroprene, etc. Other suitable surface materials include isoprene-
Isobutylene (butyl) rubber, copolymers of conjugated dienes with lower alkyl and gylkoxy acrylates, ethylene-propylene-diene polymers (EPOM), SchO
These include polyurethanes such as those disclosed in U.S. Pat. Nos. 2,871,218 and 2,899,411 to Illenberger. Further suitable surface materials include wood,
concrete, stainless steel, glass, ceramic tile,
There are tin and antifouling coatings such as those disclosed in US Pat. No. 3,426,473.

It is desirable that the underwater surface or substrate that is brought into contact with the composition described above be pre-cleaned prior to contact in order to promote adhesion of the composition to the surface or substrate.

Rust, dirt, oil, etc. should be removed as completely as possible.
Cleaning may be performed by known methods such as sand blasting, wire brushing, water blasting, and manual wiping. When applying to a damaged coating, it is desirable to clean the soiled surface about 0.5 to 1 inch wider than the area to be applied and thoroughly coat the coating. This pretreatment makes it possible to achieve a good adhesive bond in the overlaps of the patch material. Application of the above compositions can be carried out by methods well known in the art. For example, a viscous composition can be scooped with wet hands or gloves and applied by hand to a cleaned substrate. By strongly pressing the spherical composition against the base material by hand and gently squeezing the composition from the center toward the outer periphery, water is removed to reduce the amount of water to about 1/2.
A coating layer 8 to 1/4 inch thick may be formed. Then, the peripheral edges of the coating may be smoothed. Alternatively, the underwater curable compositions of the present invention may be applied by brush or roll using a pressure delivery system. Yet another method of application is to place the box face down on the structure to be coated and firmly adhere it. Water is removed by pumping out the air between the box and the surface to be coated to create a coating, and the coating is applied while damp. The box can be removed immediately after coat and
Alternatively, the composition may be left as is until curing is completed. The adhesive coat thickness of the underwater curable compositions described above can vary over a wide range, usually from about 0.01 to about 0.250 inch, preferably from about 0.005 inch to about 0.10 inch.

When used as a repair putty, its thickness can vary widely, up to several inches, to seal cracks and holes. The curing temperature of the composition is from about 351=' to about 100'F or higher, with the curing time decreasing with each increase in temperature. Underwater curing times generally range from about 1 hour to about 20 hours, more usually from about 3 to 1 hour.
It is 2 hours. The compositions described above can be applied to dry or wet surfaces or submerged surfaces and cured dry, wet or underwater.

A wet surface here means a surface to which water is attached or absorbed. 38. While the composition described above excludes water on wet or submerged surfaces. It was completely surprising and unexpected that it cured quickly, bonded strongly to the surface being treated, and exhibited excellent adhesion and flexibility. It is believed that water is somewhat reactive to the compositions described above and acts as an accelerator. Examples will be described in more detail below.

General Mixing and Sample Preparation Method The underwater curable composition was prepared according to the following general formula.

If a filler was used, it was mixed with the epoxy resin in an ink mill. If additional fillers were used, they were mixed with the amine-terminated liquid polymer in an ink mill. The two mixtures were stirred in a beaker using a spatula and the final mixture was used within about 2 hours after mixing was complete.

The components of System X were stirred and mixed in a beaker at room temperature. Samples were prepared as follows. Approximately 25mm x 20 including antifouling agent
0mm x 2.21! I! neoprene rubber compound strips were prepared from the following formulation. Each rubber strip was suspended in 29 gallons of synthetic ocean water aged at 70-80'F for at least 24 hours, then removed from the tank, wiped clean, and immediately placed back into the tank. The underwater curable composition was applied underwater to a 25 mm x 200 mm side of the strip. This application was done by hand or with a putty knife.
The thickness of the applied composition was approximately 0.25 inches. Immediately thereafter, the wiped surface of the second strip was pressed against the application surface under water to form a sandwich. Both strips were squeezed together to eliminate water between them and cured in water.

Composition Materials The liquid polymers with amine end groups used in the following examples are:
It was easily prepared as detailed above using N-(2-aminoethyl)piperazine in the amine termination reaction.

A liquid polymer with amine end groups, abbreviated as ATBN, is
Refers to an amine-terminated (butadiene/acrylonitrile) copolymer with an acrylonitrile content of approximately 9.5% by weight;
The viscosity of TBN polymer at 27°C is approximately 90,000 cp
s, and the molecular weight was approximately 3,600. The most frequently used non-alicyclic epoxy resins have an epoxy equivalent (weight) of about 185-192 and a viscosity of about 10,000 at 25°C.
It was liquid bisphenol A diglycidyl ether (hereinafter abbreviated as DGEBA) with a concentration of ~16,000 cps.

DGEBA resin is commercially available from Ciel Chemical under the trade name EpOn 828. The other non-alicyclic epoxy resins used had an epoxy equivalent (weight) of about 140 to 1.
A triglycidyl ether of glycerol having a viscosity of about 100 to 170 cps at 60.25°C,
This resin is commercially available from Ciel Chemical under the trade name Kohon 812. Yet another cycloaliphatic epoxy resin is liquid diglycidyl ether of bisphenol A (DGEBA) having an epoxy equivalent weight (weight) of about 10,000 to 16,000 cps at 180.25°C; It is commercially available under the trade name Epirets 510 from the company. The polyamide resin used to prepare the underwater curable composition used in the method of the present invention and the composition used for comparison was Versamid 1
15 and Versamide 140, commercially available from General Mill Company.

Versamide 115 is a reaction product of dimer [Ramaki ■_] and polyamine, and has an amine value of about 238 and a reaction equivalent of about 23.
It was 6. Versamide 140 is a reaction product of dimanitic acid and polyamine, and has an amine value of about 385.
The reaction equivalent was approximately 146. Here, amine number is defined as the millif number of potassium hydroxide equal to the amine alkalinity present in 1 ft of polyamide resin sample. The reaction equivalent is 56100 (milliequivalent of potassium hydroxide)
divided by the amine value of the polyamide resin sample. For comparative purposes, an underwater curing system (hereinafter referred to as system X), which is commercially available as a two-part system, was used.

Part 1 contained liquid pisphenol A diglycidyl ether (DGEBA) and approximately 52% by weight silica filler. Part 2 contained a polyamide resin believed to be Versamide 115, described above. Both parts were thoroughly mixed immediately before being used for testing. Except for the amine-terminated liquid polymer described above, the non-alicyclic epoxy resin, polyamide resin, and other materials used in Example Z4 below are all readily available from Ichihaka.

Test method Peel adhesion strength was measured according to ASTM D-903, and flexibility (softness) was evaluated by bending to 3603 and stretching by hand.

Examples 1-3 Water-curable compositions were prepared according to the general mixing and sample preparation methods described above.

Testing was performed after approximately 48 hours in water at 23°C.

The test results are shown in Table 1. The samples of Examples 1 and 2 cured rapidly and exhibited excellent peel adhesion strength and flexibility, and exhibited no sagility.

In contrast, the known composition of Example 3 was slow to odorize and had poor adhesive strength and flexibility. Examples 4-8 Underwater curable compositions were prepared according to the general mixing and sample preparation methods described above.

Testing was carried out after approximately 72 hours in water at 25°C.

Claims (1)

Claims: 1. A water-curable composition comprising both components (A) and (B) listed below is applied to a dry or wet surface or a surface to be immersed in water; An underwater curing method consisting of curing on an underwater surface. (A) 100 parts by weight of at least one non-alicyclic epoxy resin containing an average of at least about 1.7 epoxy groups per molecule and having an epoxy equivalent (weight) of about 70 to 6,000; At least about 1 type of liquid polymer having an amine-terminated group having an average of about 1.7 to about 3 amine groups per molecule consisting of 1, 2, or a mixture thereof, and represented by the following formula: ~ Approximately 2000 parts by weight, ▲ Numerical formulas, chemical formulas, tables, etc. ▼ In the above formula, Y represents at least two amine groups consisting of primary, secondary, or a mixture thereof, and 2-20 carbon atoms. A monovalent radical obtained by removing hydrogen from an aliphatic, alicyclic, heterocyclic, or aromatic amine group, and B is the following (a), (b), (c), (d) and At least one terminal selected from the group consisting of (e) ▲ mathematical formula, chemical formula,
There are tables etc. ▼ A polymeric backbone consisting of carbon-carbon bonds containing at least one vinylidene monomer weight unit with groups. (a) Monoolefins having 2 to 14 carbon atoms; (b) dienes having 4 to 10 carbon atoms; (c) vinyl and allyl esters of carboxylic acids having 2 to 8 carbon atoms; (d) 1 carbon atom. -8 vinyl and allyl ethers of alkyl radicals, and (e) acrylic acids and acrylates represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R is hydrogen or an alkyl group having 1 to 3 carbon atoms, and R^1 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 2 to 3 carbon atoms. 12 alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical. 2 the carbon-carbon bonds account for at least 90% by weight of the total weight of the polymer backbone, and the vinylidene monomer is
2. The method according to claim 1, wherein the method is selected from the group consisting of: ), (b) and (e). (a) Monoolefin having 2 to 8 carbon atoms, (b) diene having 4 to 8 carbon atoms, and (e) acrylic acids and acrylates represented by the following formula. ▲Mathematical formulas, chemical formulas,
There are tables etc. ▼ In the formula, R is hydrogen or an alkyl group having 1 to 3 carbon atoms, and R^1 is hydrogen, an alkyl group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms, It is an alkylthioalkyl or cyanoalkyl radical. 3 The epoxy equivalent (weight) of the epoxy resin is about 70 to
3. The method of claim 2, wherein the number of cells is about 2,000. 4. The method according to claim 3, wherein the epoxy resin is a glycidyl ether resin. 5 The epoxy resin is the following (1), (2), and (3)
) The method according to claim 4, wherein the method is selected from the group consisting of: (1) Alkanediol diglycidyl ether represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is an alkylene or alkylidene group having 1 to 10 carbon atoms, and n is 0 to 20. ) (2) Di- and poly-glycidyl ethers of bisphenol represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R^5 is selected from the group consisting of C, O, S and N. It is a divalent radical containing 1 to 8 atoms of at least one kind of atom.) (3) Alkantriol triglycidyl ether having an alkane group having 2 to 10 carbon atoms. 6 Up to about 50% by weight of polymer units copolymerized with the vinylidene monomer in addition to the following (f), (g), (h):
, (i), (j) and (k). (f) Vinyl aromatic compound represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^2 is hydrogen, halogen, or has 1 to 1 carbon atoms
4 alkyl radical. ), (g) Vinyl nitriles represented by the following formula ▲ Formula,
There are chemical formulas, tables, etc. ▼ (In the formula, R^3 is hydrogen or an alkyl radical having 1 to 3 carbon atoms.), (h) Vinyl halide, (i) Divinyl and diacrylates, (j) Amides of α,β-olefinically unsaturated carboxylic acids having 2 to 8 carbon atoms, and (k) allyl alcohol. 7. The method of claim 6, wherein the amine groups in the amine have different reactivities and the comonomer is selected from the group consisting of (f) the vinyl aromatic compound and (g) vinyl nitriles. 8 The epoxy resin is diglycidyl ether of isopropylidene bisphenol, the amine is at least one type of N-(aminoalkyl)piperazine having 1 to 12 carbon atoms in the aminoalkyl group, and the vinylidene monomer is 8. The method of claim 7, wherein the comonomer is at least one of the dienes and the comonomer is at least one of the vinyl nitriles. 9. The method of claim 8, wherein the diene is butadiene, the vinyl nitrile is acrylonitrile, and the amine is N-(2-aminoethyl)piperazine.