JPH08198943A - Epoxy resin composition for execution on wet face or in water - Google Patents

Abstract

PURPOSE: To obtain a composition having excellent coating performances, trowel spreadability and adhesiveness to a base even in execution on a wet face or in water, providing a coating film and an adhesive bond not peeling and having excellent corrosion resistance for a long period of time and slightly contaminating the circumference of an execution site and water quality of operation environment. CONSTITUTION: This epoxy resin composition for execution on a wet face or in water comprises (A) an epoxy resin, (B) an amine-based epoxy resin curing agent, (C) an anionic surfactant containing an anionic hydrophilic group bonded directly or indirectly through a short-chain aliphatic group to a secondary carbon atom and/or nitrogen atom of a hydrophobic part and (D) an inorganic filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for application on a wet surface or underwater, and more particularly to an epoxy resin composition for application as a paint or adhesive on a wet surface or underwater. Is.

[0002]

2. Description of the Related Art Conventionally, paints and sealants have been applied to water or wet surfaces for the purpose of preventing permeation of water into the base material and rust prevention for structures, ships, etc. that are frequently in contact with water. In many cases. In particular, epoxy resin-based paints and sealers are highly demanded for construction due to their anticorrosive performance and adhesive performance, and for that purpose, epoxy resin compositions for wet surface or underwater construction have been developed.

[0003]

However, the epoxy resin composition for wet surface or underwater application which has been developed hitherto has been difficult to apply to a wet surface or when it is applied in water, the coating property to the base material and the iron. There are problems such as poor spreadability, shrinkage of the formed coating film, and insufficient adhesion to the substrate.

Therefore, an object of the present invention is that even when applied on a wet surface or in water, it has good coatability to the substrate, spreadability of the iron, and adhesiveness, does not peel off for a long period of time, and is anticorrosive. Provides a good coating and adhesive layer with excellent properties,
Another object of the present invention is to provide a wet surface or underwater epoxy resin composition which does not pollute the water quality around the construction site or the working environment.

[0005]

In order to solve the above-mentioned problems, the present invention provides an epoxy resin (A), an amine-based epoxy resin curing agent (B), a secondary carbon atom of a hydrophobic portion, and And / or an anionic surfactant (C) in which an anionic hydrophilic group is bonded directly to a nitrogen atom or indirectly via a short-chain aliphatic group, and an inorganic filler (D)
And an epoxy resin composition for construction on a wet surface or underwater.

The present invention will be specifically described below. Examples of the above-mentioned epoxy resin (A) used in the present invention include various epoxy resins that can be used in paints, adhesives, sealing materials and the like. Such epoxy resin is
General formula:

Embedded image (In the formula, Z represents a hydrogen atom, a methyl group, an ethyl group or the like.) An epoxy resin having an average of more than one substituted or unsubstituted glycidyl group in the molecule, such as a glycidyl ether group and a glycidyl group. Epoxy resins having an average of more than one ester group, glycidylamine group and glycidylimine group in the molecule can be mentioned.

The epoxy resin (A-1) having an average of more than one glycidyl ether group in the molecule includes (1) polyvalent resins such as ethylene glycol, propylene glycol, butanediol, glycerin and trimethylolpropane. Polyglycidyl ether of alcohol (A-1-1), (2) For example resorcinol, hydroquinone, pyrocatechol, phloroglicinol,
Polyglycidyl ethers of mononuclear polyhydric phenols such as 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene (A-1-
2), (3) For example, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4'-dihydroxydiphenylmethane, bis- (2-hydroxyphenyl) -methane, bis- (4-hydroxyphenyl)-. Methane, bis- (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl) -ethane, 1,2-bis- (4-hydroxyphenyl) -Ethane, 1,1-bis- (4-hydroxy-2-chlorophenyl) -ethane, 1,1-bis-
(3,5-Dimethyl-4-hydroxyphenyl) -ethane, 1,3-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxy) Phenyl) -propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-isopropyl-4-hydroxyphenyl) -propane, 2,2-bis- ( 2-isopropyl-4-hydroxyphenyl) -propane, 2,2
-Bis- (4-hydroxynaphthyl) -propane, 2,
2-bis- (4-hydroxyphenyl) -pentane,
3,3-bis- (4-hydroxyphenyl) -pentane, 2,2-bis- (4-hydroxyphenyl) -heptane, bis- (4-hydroxyphenyl) -methane,
1,2-bis- (4-hydroxyphenyl) -1,2-
Bis- (phenyl) -propane, 2,2-bis- (4-
Bis- (hydroxyphenyl) -alkane such as hydroxyphenyl) -1-phenyl-propane or dihydroxybiphenyl such as 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl or Bis- (4-
Hydroxyphenyl) -sulfone, 2,4'-dihydroxydiphenylsulfone, chloro-2,4-dihydroxydiphenylsulfone, 5-chloro-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-Chloro-4,4 '
-Di- (hydroxyphenyl) -sulfone- or bis- (4-hydroxyphenyl) -ether, such as dihydroxydiphenyl sulfone, 4,3 '-(or 4,2'- or 2,2'-) dihydroxy-diphenyl -Ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl-ether, bis- (4-hydroxy-
3-isopropylphenyl) -ether, bis- (4-
Hydroxy-3-chlorophenyl) -ether, bis-
(4-hydroxy-3-fluorophenyl) -ether, bis- (4-hydroxy-3-bromophenyl)-
Ether, bis- (4-hydroxynaphthyl) -ether, bis- (4-hydroxy-3-chloronaphthyl)-
Ether, bis- (2-hydroxybiphenyl) -ether, 4,4'-dihydroxy-2,6-dimethoxydiphenyl-ether, 4,4'-dihydroxy-2,5
Di- (hydroxyphenyl) -ethers such as diethoxydiphenyl-ether, or 1,1-bis-
(4-hydroxyphenyl) -2-phenylethane,
1,3,3-Trimethyl-1- (4-hydroxyphenyl) -6-hydroxyindane, 2,4-bis- (4-
Polyglycidyl ethers of polynuclear dihydric phenols such as hydroxyphenyl) -4-methylpentane (A-1-
3), (4) For example, 1,4-bis- (4-hydroxybenzyl) -benzene, 1,4-bis- (4-hydroxybenzyl) -tetramethylbenzene, 1,4-bis-
(4-hydroxybenzyl) -tetraethylbenzene,
Polyglycidyl ethers of other polynuclear dihydric phenols such as 1,4-bis- (4-hydroxychromyl) -tetraethylbenzene (A-1-4), (5) For example, initial condensation products of phenols and carbonyl compounds ( For example, phenol resin initial condensation product, phenol-acrolein condensation reaction product, phenol-glyoxal condensation reaction product, phenol-pentanediallyl condensation reaction product, resorcinol-acetone condensation reaction product, xylene-phenol-formalin initial condensation product), Polyglycidyl ethers of polynuclear polyhydric phenols such as condensation products of phenols and polychloromethylated aromatic compounds (A-1-
5), (6) For example, the polyhydric alcohols, mononuclear polyhydric phenols, polynuclear dihydric phenols, polynuclear polyhydric phenols and the like exemplified in (1) to (5) above include, for example, ethylene oxide, propylene oxide, butylene oxide. Polyglycidyl ether (A-1-6) obtained by adding an alkylene oxide such as the above and converting the hydroxyl group to glycidyl ether (A-1-6).

The epoxy resin (A-2) having an average of more than one glycidyl ester group in the molecule is, for example, polyglycidyl ester of aliphatic polycarboxylic acid, aromatic carboxylic acid, glycidyl ester of acrylic acid. And homopolymers or copolymers thereof.
Further, an epoxy resin (A having an average of more than one glycidylamino group or glycidylimino group in the molecule (A
-3) include, for example, aniline or an aromatic amine such as aniline having an alkyl substituent in the benzene nucleus, an initial condensation product of the aromatic amine with an aldehyde such as formaldehyde, the aromatic amine, the aldehyde and a phenol. The polyglycidyl compound etc. which converted the amine group of the initial condensate of these to the glycidyl amino group or the glycidyl imino group etc. are mentioned.

Among the above epoxy resins, a preferred group is the polyglycidyl ether of polynuclear dihydric phenol (A-1-3) exemplified in (3) above and (3) above.
Polyglycidyl ether (A-1-6) obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the polynuclear dihydric phenol exemplified in, and converting the hydroxyl group into glycidyl ether (A-1-6), A particularly preferred group of the group (1) is the polyglycidyl ether of polynuclear dihydric phenol (A-1-3) exemplified in (3) above.
Is a polyglycidyl ether of bis- (hydroxyphenyl) -alkane.

These epoxy resins may be used alone or in combination of two or more.
You may use together with the other resin compatible with the said epoxy resin. Examples of such resins include thermosetting resins such as phosphoric acid-modified epoxy resins, epoxy resins having chelating ability, unsaturated polyester resins, phenoxy resins, phenol resins, xylene resins, and polyester resins, ethylene-vinyl acetate copolymers. Coalescing, thiocol resin, coal
Examples thereof include petroleum resin, modified butadiene-acrylonitrile resin, vinyl acetate resin and the like.

Further, in the present invention, examples of the diluent for the epoxy resin include olefin oxide, glycidyl methacrylate, octylene oxide, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, vinylcyclohexene monooxide, styrene oxide, phenyl. Glycidyl ether, p-sec. A monoepoxy compound such as butyl phenyl glycidyl ether, cresyl glycidyl ether, α-pinene oxide; for example, butadiene oxide, dimethylpentane dioxide, diglycidyl ether, butanediol diglycidyl ether, ethylene glycol diglycidyl ether, di- or poly -Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, di- or poly-propylene glycol diglycidyl ether, vinyl cyclohexene dioxide, neopentyl glycol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, glycerine triglycidyl Ether, limonene dioxide, resorcin diglycidyl ether, 2,6-jig Reactive diluents such as di- or poly-epoxy compounds such as sidyl phenyl glycidyl ether and 2-diglycidyl phenyl glycidyl ether, such as non-reactive diluents such as dibutyl phthalate, glycol ether-ester, styrene and phenols. Can be used.

Next, as the amine type epoxy resin curing agent (B) used in the present invention, for example, an amine compound (B-1) such as an aliphatic amine, an alicyclic amine or an aromatic amine,
Alternatively, a modified product of the amine compound (B-1) (B-
2), and specific examples of the amine compound (B-1) include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine. , undecamethylenediamine, _{2-methyl-2,4-diaminopentane, H 2 n (CH 2)} n -CH (CH 3) NH
₂ (n: an integer of 1 to 8) and other aliphatic diamines, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethyleneheptamine, di (hexamethylene) triamine, tri (hexamethylene) tetramine, tetra (hexa) Methylene) pentamine, tripropylenetetramine, tetrapropylenepentamine, iminobispropylamine, methyliminobispropylamine, tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, triethylene-bis (trimethylene) hexamine Alkylene polyamines or polyalkylene polyamines such as 1,3-diaminomethylnaphthalene, 1,4-diaminomethylnaphthalene, 4,4′-diaminomethylbiphenyl, ortho-, meta- or Para - xylylenediamine (omega, omega .'- diamino xylene) aliphatic diamine having an aromatic ring structure such as, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,2
-Diaminocyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine), 1,8-diamino-8-menthane, bis- (4-aminocyclohexyl) methane, 2,2 ' −
Bis- (4-aminocyclohexyl) propane, 1,3
Aliphatic amines containing alicyclic structures such as -bis- (aminomethyl) cyclohexane, 1,2-bis- (aminomethyl) cyclohexane, bis- (4-amino-3-methylcyclohexyl) methane, for example N- Aminoethylpiperazine, 1,4-bis- (3-aminopropyl) piperazine, 3,9-bis- (3-aminopropyl) -2,
Aliphatic amines containing a heterocyclic structure such as 4,8,10-tetraoxaspiro (5,5) undecane, such as metaphenylenediamine, orthophenylenediamine, 2,4
-Toluenediamine, 4-chloro-orthophenylenediamine, metaaminobenzylamine, 4-methoxy-6
-Methyl-metaphenylenediamine, benzidine, 4,
4'-diaminodiphenylmethane, 2,4,6-tri (dimethylaminomethyl) phenol, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, Bis (3,4-diaminophenyl) sulfone,
Diaminoditolyl sulfone, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenyl , 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, and other aromatic amines, and the modified products (B
As a specific example of -2), the modification method shown in the following (1) to (5) of the amine compound (B-1) shown as the above specific example: (1) A compound having a phenol and a carbonyl group (2) Epoxy compound addition modification method in which an epoxy compound is reacted (3) Michael addition modification method in which a substituted or unsubstituted acrylic compound is reacted (4) Polyamidation modification method in which a polycarboxylic acid is reacted ( 5) Examples include modified products modified by a ketimine modification method of reacting a ketone compound or a mixture thereof.

Typical examples of the phenols used in the above-mentioned Mannich modification method include phenol, alkyl-substituted phenol, cresol, halogen-substituted phenol, anisole, bisphenol-A, bisphenol-F, and mixtures thereof. Further, as the compound having a carbonyl group used in the above-mentioned Mannich modification method, for example, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, acetone and a mixture thereof and the like are mentioned as typical examples, and other phenols and Other carbonyl compounds can also be used.

Examples of the epoxy compound used in the above-mentioned epoxy compound addition modification method include various epoxy resins exemplified as the epoxy resin (A) and reactive diluents for the epoxy resin. Examples of various epoxy compounds and the like, the substituted or unsubstituted acrylic compound that can be used in the Michael addition modification method, for example, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, acrylic ester,
Methacrylic acid ester and the like can be mentioned as a typical example, and other epoxy compounds and other substituted or unsubstituted acrylic compounds can be used for each.

Further, examples of the polycarboxylic acid used in the above-mentioned polyamidization modification method include a monomer acid,
Dimer acid, trimer acid, tall oil fatty acid, phthalic acid,
Maleic acid and the like can be mentioned as a typical example, other polycarboxylic acids can also be used, and examples of the ketone compound used in the above-mentioned ketimine modification method include acetone, methyl ethyl ketone, diisopropyl ketone, methyl isopropyl ketone, and methyl isobutyl. Representative examples are ketones and the like, and other ketone compounds can also be used.

The above-mentioned amine type epoxy resin curing agent (B)
Preferred among these are, for example, m-xylenediamine,
One or more amine compounds selected from the group consisting of cyclohexanediamine, bis- (aminomethyl) cyclohexane, methylenedi (cyclohexylamine), diaminodiphenylmethane, metaphenylenediamine, norbonenediamine and isophoronediamine, or those Is a modified product or a mixture thereof in which the amine compound of (1) to (5) is modified by one or more modification methods selected from the group consisting of (1) to (5), and among them, particularly preferred are: It is a modified product obtained by modifying the above specific amine compound by the above specific modification method or a mixture thereof.

The above amine type epoxy resin curing agent (B)
The amount of active hydrogen contained in the epoxy resin curing agent (B) is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the epoxy groups contained in the epoxy resin (A), In particular, the amount is preferably 0.7 to 1.5 equivalents. If the compounding amount is too small, the curing will be delayed, and if it is too large, the physical properties of the cured product will be deteriorated, which is not preferable.

The anionic surfactant (C) used in the present invention is directly attached to the secondary carbon atom and / or nitrogen atom of the hydrophobic portion or via a short-chain aliphatic group. An anionic hydrophilic group is indirectly bound,
For example, a sulfuric acid esterified product or sulfonated product of a hydrophobic organic compound having a double bond inside the molecule or a water-soluble salt thereof; a hydrophobic organic compound having a secondary hydroxyl group inside the molecule or an alkylene oxide at the hydroxyl group. Sulfated or phosphoric acid ester of the hydroxyl group of the derivative obtained by adding a few moles of the above or a water-soluble salt thereof; represented by the -NH- of the hydrophobic organic compound having a bond represented by -NH- in the molecule. A sulfonated compound or a water-soluble salt thereof; a hydrophobic organic compound having a bond represented by -NH- in the molecule, and a derivative obtained by adding a few moles of alkylene oxide to the group represented by -NH-. Hydroxyl ester of sulfuric acid or phosphoric acid or its water-soluble salt; higher fatty acid chloride and N-
N-alkanoyl or alkenoyl-N-alkylaminoalkyl sulfonic acids obtained by reaction with alkylaminoalkyl sulfonic acids or water-soluble salts thereof; N
-N obtained by reaction of alkylaminoalkylcarboxylic acid or water-soluble salt thereof with higher fatty acid chloride
-Alkanoyl or alkenoyl-N-alkylaminoalkylcarboxylic acid or a water-soluble salt thereof and the like.

Specific examples of the anionic surfactant include, for example, a fatty acid having a double bond or a glyceride thereof, an alkyl ester, an amide, an alkylamide or a hydrocarbon having a double bond having 10 to 24 carbon atoms. Sulfated ester compound, sulfonated compound or water-soluble salt of heavy bond; fatty acid of secondary higher alcohol or fatty acid having secondary hydroxyl group, glyceride, alkyl ester, amide, alkylamide or ethylene oxide of the secondary hydroxyl group , Propylene oxide average 4
Sulfate ester or phosphate ester derivative or water-soluble salt thereof obtained by adding a mole or less; dialkylsulfosuccinate ester or water-soluble salt thereof; sulfonated amide compound of fatty acid and aliphatic monoamine or aliphatic diamine Alternatively, a sulfuric acid esterified product or phosphoric acid esterified product of the hydroxyl group of a derivative obtained by adding 4 mol or less of ethylene oxide or propylene oxide to the amide bond of the amide compound; or a water-soluble salt thereof; a higher fatty acid chloride and N-alkyl taurine or N-alkanoyl or alkenoyl-N-alkyltaurine or water-soluble salt thereof obtained by reaction with water-soluble salt thereof; N-alkanoyl obtained by reaction of higher fatty acid chloride with N-alkylaminoacetic acid or water-soluble salt thereof Others include alkenoyl -N- alkylamino acid or its water-soluble salts and the like. Examples of the water-soluble salt include sodium salt, potassium salt, ammonium salt and the like.

Among the above anionic surfactants (C), preferred ones are those whose anionic hydrophilic group is a sulfate ester group, a sulfonic acid group and its water-soluble base, and among them, particularly preferred ones are, for example, Secondary higher alcohols or fatty acids containing secondary hydroxyl groups, glycerides, alkyl esters, amides, alkylamides thereof or sulfuric acid esters of the hydroxyl groups of derivatives obtained by adding ethylene oxide or propylene oxide on average to 4 mol or less to the hydroxyl groups. Or a water-soluble salt thereof; a fatty acid containing a double bond or a glyceride thereof, an alkyl ester, an amide,
And a sulfated compound, a sulfonated compound, or a water-soluble salt of the double bond of an alkylamide; a dialkylsulfosuccinic acid ester or a water-soluble salt thereof.

The content of the above-mentioned surfactant (C) is preferably 0.1 to 4% by weight, particularly preferably 0.3 to 2% by weight, based on the whole epoxy resin composition. If this blending amount is too small, the effect of the present invention is not sufficiently exhibited, and conversely, if the blending amount is too large, when the epoxy resin composition of the present invention is applied, the composition is partially in water or contact water. It is undesirable as it dissolves and contaminates them.

As the inorganic filler (D) of the present invention, for example, a filler that can be used in epoxy resin-based paints, adhesives, sealing materials and the like can be used. Examples of the inorganic filler (D) include dioxide. Examples thereof include inorganic oxides such as titanium, magnesium oxide, zirconium oxide and aluminum oxide, inorganic sulfates such as barium sulfate, calcium carbonate, silica, clay and talc. Particularly for an epoxy resin composition for construction in water, it is preferable to use an inorganic filler having a specific gravity of 3.0 or more because the coating material needs to be settled in order to prevent contamination in water.

The content of the inorganic filler (D) in the epoxy resin composition of the present invention is preferably 10 to 70% by weight based on the whole amount. If the workability is lowered, and if it is less than the above range, the coating property with the base material in water is poor, and the coating film is easily peeled off due to buoyancy of water, water flow, etc. even when applied to the base material, which is not preferable. .

Further, the epoxy resin composition of the present invention preferably has an initial viscosity of 10 to 5,000 poise at 25 ° C. If it is out of this range, workability may be impaired. To adjust the viscosity, various reactive or non-reactive epoxy diluents can be used, the amount of which is 30% by weight.
If it is less, there is no loss in performance.

It is also possible to use an auxiliary agent such as a surfactant for improving the pigment dispersibility or an antifoaming agent for the purpose of defoaming. If the amount used is small, the epoxy resin of the present invention can be used. The intended performance of the resin composition is not impaired.

Further, other additives may be used in the epoxy resin composition of the present invention. Examples of such additives include coloring such as red iron oxide, yellow lead, yellow iron oxide, titanium white, phthalocyanine blue and phthalocyanine green. Pigment; for example, chromic acid type, molybdic acid type, phosphoric acid type, boric acid type,
Anticorrosion pigments such as ferrite and lead acid pigments; for example, flaky pigments such as glass flakes, stainless flakes, aluminum flakes; fibrous substances such as asbestos, vegetable fibers, glass fibers, carbon fibers, synthetic fibers; Antifouling agents such as copper, triphenyltin hydroxide, bis-tributyltin-α, α'-dibromosuccinate, and other organic antifouling agents; chelating agents such as ethylenediaminetetraacetic acid; copper powder, copper alloys Metal powder such as powder, zinc powder, aluminum powder, iron powder;
For example, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldialkoxysilane, vinyltriacetoxysilane, vinyltrialkoxysilane, vinyltris (β
-Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldialkoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-amino Propylmethyldimethoxysilane, γ- (polyethyleneamino) propyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane,
silane coupling agents such as γ-ureidopropyltriethoxysilane, methylaminoethoxypropyldialkoxysilane, N′-vinylbenzyl-N-trimethoxysilylpropylethylenediamine salt; other additives as sedimentation / anti-sagging agents, thickening agents Agents, antibacterial / mildewproofing agents, conductive agents, flame retardants, plasticizers, stabilizers and the like.

In the epoxy resin composition of the present invention, the epoxy resin (A), the surfactant (C), the inorganic filler (D) and, if necessary, other components are preliminarily placed in a dispersing machine such as a sand mill or a triple roll mill. An epoxy resin mixture is prepared by mixing and uniformly dispersing the filler, and separately from this, an epoxy resin curing agent (B) and, if necessary, other components are uniformly mixed to prepare an epoxy resin curing agent mixture. Then, the above-mentioned epoxy resin mixture and the above-mentioned epoxy resin curing agent mixture are mixed in a mixer and used at the time of execution.

When the epoxy resin composition of the present invention is applied in water, the surface of the base material is subjected to general pretreatment such as sandblasting, then applied with a brush, a spatula or a roller and applied to the wet surface. In this case, it is effective to use a two-liquid type spray gun or the like to improve work efficiency.

[0029]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. In addition, a part shows a weight part. Examples 1 to 3 and Comparative Examples 1 and 2 Bisphenol-A type epoxy resin (E produced by Asahi Denka Co., Ltd.
P-4100) 55 parts, butyl glycidyl ether (reactive diluent) 5 parts, titanium oxide 10 parts, barium sulfate 3
0 parts of each of the surfactants of the types and amounts shown in Table 1 below were mixed with a triple roll to obtain an epoxy resin mixture. Separately, 78 parts of crude DDM (diaminodiphenylmethane) and 18 parts of benzyl alcohol were mixed. Parts and 0.4 parts of silane coupling agent were uniformly mixed to obtain an epoxy resin curing agent mixture. Then, 20 parts of the above epoxy resin curing agent mixture was mixed with 100 parts of the above epoxy resin mixture with a mixer to obtain an epoxy resin composition of the present invention and an epoxy resin composition for comparison.

These epoxy resin compositions were applied on a steel plate of 500 × 500 × 1 mm immersed in water by using a brush or a trowel in water to obtain coatability in water, spreadability of trowel, shrinkage of coating film. The stain resistance and adhesive strength were evaluated, and the results shown in Table 1 below were obtained. The surfactant used and the evaluation method are as follows.

(1) Surfactant used Surfactant I: Secondary higher alcohol sulfate ester
Sodium salt (Nippon Yushi Co., Ltd. "Syntrekkus EH-
R ”) Surfactant II: sulfosuccinic acid di (2-ethylhexyl) ester sodium salt (“ Adeka Call EC4500 ”manufactured by Asahi Denka Co., Ltd.) Surfactant III: Sulfated oleic acid butyl ester sodium salt Surfactant IV: Higher alcohol sulfate ester / sodium salt (Adeka Hope DS25 manufactured by Asahi Denka Co., Ltd.) Surfactant V: Higher alkyl polyethylene glycol ether sulfate ester sodium salt (Adeka Hope DES3025 manufactured by Asahi Denka Co., Ltd.)

(2) Evaluation method The applicability in water is, when applied on the steel plate in water using a brush or a trowel, ○ when easily applied, Δ when slightly applied, and considerably difficult. The case was evaluated as x.

The trowel spreadability was evaluated as ◯ when the composition had good trowel spreadability when coated in water using a trowel on the steel plate, Δ when the composition was slightly poor, and X when it was poor. .

The shrinkage of the coating film is observed when the coating film after coating is not observed to be shrunk when coated in water using a brush or a trowel on the steel sheet, and when it is observed a little, it is considerably observed. The case was evaluated as x.

Contamination is evaluated as follows: ○ When no floating substance in the water, floating substance on the surface or turbidity of water is observed when it is applied on the steel plate in water using a brush or a trowel, and when it is observed a little. The evaluation was made as Δ, and the case of being considerably observed was evaluated as ×.

The adhesive strength was evaluated by coating the steel sheet in water with a brush or a trowel, curing the steel sheet at room temperature for 1 week, pulling up the steel sheet from the water, and measuring the adhesive force of the coating film by an adhesion tester. .

[0037]

[Table 1]

Examples 4 to 6 and Comparative Example 3 Bisphenol-A type epoxy resin (E manufactured by Asahi Denka Kogyo KK
P-4100) 55 parts, butyl glycidyl ether (reactive diluent) 5 parts, titanium oxide 10 parts, barium sulfate 3
0 parts of the secondary higher alcohol sulfate ester sodium salt having the compounding amounts shown in Table 2 below was mixed with a triple roll to obtain an epoxy resin mixture. Separately from this, crude DDM (diaminodiphenylmethane) 78 was added. Parts, 18 parts of benzyl alcohol and 0.4 parts of a silane coupling agent were uniformly mixed to obtain an epoxy resin curing agent mixture. Then, 20 parts of the above epoxy resin curing agent mixture was mixed with 100 parts of the above epoxy resin mixture with a mixer to obtain an epoxy resin composition of the present invention and an epoxy resin composition for comparison.

These epoxy resin compositions were applied on a 500 × 500 × 1 mm steel plate immersed in water using a brush or a trowel in water to obtain coatability in water, spreadability of the trowel, and shrinkage of the coating film. The stain resistance and adhesiveness were evaluated, and the results shown in Table 2 below were obtained. The evaluation method is as described above.

[0040]

[Table 2]

[0041]

As described above, according to the present invention, even when applied on a wet surface or in water, the coating property on the substrate,
Good iron spreadability and adhesiveness, does not peel off over a long period of time, and provides a good coating and adhesive layer with excellent anticorrosion properties, and further contaminates the water quality around the construction site and work environment It was possible to provide an epoxy resin composition for wet surface or underwater construction, which is rare.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hisashi Murase 7-35 Higashiohisa Arakawa-ku Tokyo 2-35 Asahi Denka Kogyo Co., Ltd.

Claims (9)

[Claims] 1. An epoxy resin (A), an amine-based epoxy resin curing agent (B), a secondary carbon atom and / or a nitrogen atom of a hydrophobic portion, directly or with a short-chain aliphatic group. An epoxy resin composition for application on a wet surface or underwater, which comprises an anionic surfactant (C) in which an anionic hydrophilic group is indirectly bonded via an inorganic filler (D). 2. The epoxy resin (A) is selected from the group consisting of polyglycidyl ethers of polynuclear dihydric phenols and polyglycidyl ethers obtained by adding alkylene oxides to polynuclear dihydric phenols and converting their hydroxyl groups into glycidyl ethers. The epoxy resin composition according to claim 1, which is at least one kind. 3. The epoxy resin composition for wet surface or underwater application according to claim 2, wherein the epoxy resin (A) is a polyglycidyl ether of a polynuclear dihydric phenol. 4. The epoxy resin composition for wet surface or underwater application according to claim 3, wherein the epoxy resin (A) is a polyglycidyl ether of bis- (hydroxyphenyl) alkane. 5. Anionic surfactant (C) is a hydrophobic organic compound having a double bond inside the molecule, wherein said double bond is a sulfate ester or sulfonate or a water-soluble salt thereof; A hydrophobic organic compound having a primary hydroxyl group or a derivative obtained by adding a few moles of alkylene oxide to the hydroxyl group, a sulfuric acid esterified product or phosphoric acid esterified product of the hydroxyl group or a water-soluble salt thereof;
A hydrophobic organic compound having a bond represented by NH-
Sulfonated product of a group represented by NH- or a water-soluble salt thereof; obtained by adding a few moles of alkylene oxide to the group represented by -NH- of a hydrophobic organic compound having a bond represented by -NH- in the molecule. Sulfate or phosphate ester of the hydroxyl group of the derivative obtained or a water-soluble salt thereof; N-alkanoyl or alkenoyl-N-obtained by reacting a higher fatty acid chloride with N-alkylaminoalkylsulfonic acid or a water-soluble salt thereof Alkylaminoalkylsulfonic acid; or N-alkanoyl or alkenoyl-N-alkylaminoalkylcarboxylic acid or a water-soluble salt thereof obtained by reacting N-alkylaminoalkylcarboxylic acid or a water-soluble salt thereof with a higher fatty acid chloride. Any one of items 1 to 4 Wet surface or underwater construction epoxy resin composition of the mounting. 6. A fatty acid having an anionic surfactant (C) having a double bond or a glyceride thereof, an alkyl ester, an amide, an alkyl amide or a carbon number of 10 to 2
A sulfate esterified product, a sulfonated product, or a water-soluble salt of a hydrocarbon having a double bond of 4; a secondary higher alcohol or a fatty acid having a secondary hydroxyl group, a glyceride thereof, an alkyl ester, an amide, an alkyl Amide or the ethylene oxide in the secondary hydroxyl group,
Sulfonic acid ester or phosphoric acid ester of a derivative obtained by adding 4 mol or less of propylene oxide on average or a water-soluble salt thereof; a dialkylsulfosuccinic acid ester or a water-soluble salt thereof; an amide of a fatty acid and an aliphatic monoamine or an aliphatic diamine. A sulfonated compound or a amide bond of the amide compound, and a sulfuric acid esterified product or phosphoric acid esterified product of the hydroxyl group of a derivative obtained by adding ethylene oxide or propylene oxide on average 4 mol or less; or a water-soluble salt thereof; higher fatty acid chloride and N -N-alkanoyl or alkenoyl-N obtained by reaction with alkyl taurine or its water-soluble salts
Alkyl-taurine or a water-soluble salt thereof; or N-alkanoyl or alkenoyl-N-alkylaminoacetic acid or a water-soluble salt thereof, which is obtained by reacting a higher fatty acid chloride with N-alkylaminoacetic acid or a water-soluble salt thereof. 5. The epoxy resin composition for wet surface or underwater construction according to 5. 7. The epoxy resin composition for wet surface or underwater application according to claim 6, wherein the anionic hydrophilic group of the anionic surfactant (C) is a sulfuric acid ester group, a sulfonic acid group or a water-soluble salt thereof. . 8. A fatty acid in which the anionic surfactant (C) contains a secondary higher alcohol or a secondary hydroxyl group, a glyceride, an alkyl ester, an amide, an alkylamide thereof, or an ethylene oxide or propylene oxide average 4 group in the hydroxyl group. A sulfuric acid esterified product of the hydroxyl group or a water-soluble salt of the derivative obtained by adding not more than mol; a fatty acid having a double bond or a glyceride thereof, an alkyl ester, an amide, a sulfuric esterified product of the double bond of an alkylamide, The epoxy resin composition for wet surface or underwater application according to claim 7, which is a sulfonated compound or a water-soluble salt thereof, or a dialkylsulfosuccinic acid ester or a water-soluble salt thereof. 9. The epoxy resin curing agent (B) is m-xylenediamine, cyclohexanediamine, bis- (aminomethyl) cyclohexane, methylenedi (cyclohexylamine), diaminodiphenylmethane, metaphenylenediamine, norbonenediamine, isophoronediamine. Mannich for reacting one or more amine compounds selected from the group consisting of or a group consisting of the following (1) to (5): (1) phenols and a compound having a carbonyl group Modification method (2) Epoxy compound addition modification method of reacting epoxy compound (3) Michael addition modification method of reacting substituted or unsubstituted acrylic compound (4) Polyamidation modification method of reacting polycarboxylic acid (5) Ketone compound Or a ketimine modification method A modified product or a mixture thereof modified by one or more modification methods selected from the group consisting of:
8. An epoxy resin composition for wet surface or underwater construction according to claim 8.