CN1249764A - Amino-based curing agent, curable resin composition containing said curing agent, and anticorrosion coating composition containing said curing agent - Google Patents

Abstract

The present invention relates to an amine-based curing agent prepared by reacting a condensation reaction product of a mixture of xylylenediamine and an aliphatic polyamine, (b) a mixture of at least one selected from bisphenol A, bisphenol F and phenol and an alkylphenol having 9 or more carbon atoms in the alkyl chain, and (c) formaldehyde with (d) an epoxy resin having at least two epoxy groups in one molecule, a curable resin composition containing the same, and an anticorrosive coating composition containing the same.

Description

Amine-based curing agent, curable resin composition containing said curing agent, and anti-corrosion coating composition containing said curing agent

The invention relates to an amine-based curing agent used as an epoxy resin curing agent, which has good curing performance especially at low temperatures, and has good compatibility with widely used petroleum resins in anticorrosion coating compositions; the present invention It also relates to a curable resin composition containing the curing agent and an anti-corrosion coating composition containing the curing agent and having good low-temperature curing performance, and especially relates to a tar-free anti-corrosion coating composition for internal coating of ships such as ballast tanks.

Amine-based curing agents are well known in the art as curing agents for epoxy resins. The resin composition containing the above-mentioned curing agent and epoxy resin can be cured at room temperature, so it can be widely used in heavy-duty anti-corrosion coating compositions for ships, steel structures and the like. However, the above-mentioned resin composition has poor curing performance at low temperature such as winter, so that it cannot exhibit the original performance of epoxy resin.

In order to improve the low-temperature curing performance of the resin composition, the following methods (1) to (4) have been proposed in the art, that is, (1) use a curing accelerator, (2) use a mercaptan-based curing agent, (3) Use an acrylate-containing resin, and (4) use an epoxy-polyurethane curing system.

The above-mentioned method (1) has the disadvantage that, as used in curing accelerators, the low-temperature acceleration effect obtained by using catalysts such as tertiary amines, phenols, etc. for the ring-opening of epoxy groups is not satisfactory, and the curing The residual catalyst in the final film leads to poor water resistance and film performance of the cured film.

The above-mentioned method (2) has the disadvantage that the use of the curing agent makes the composition exhibit good low-temperature curing performance, but the cured film has poor water resistance and chemical resistance, and produces bad odor.

The above-mentioned method (3) has the disadvantage that the Michael addition reaction of the acrylate group and the amine improves the low-temperature curing performance of the composition, but many ester connections remain in the cured film to make the water resistance and alkali resistance of the cured film Poor sex.

The method (4) above uses a curing system composed of a combination of epoxy resin (as epoxy polyol) and isocyanate (as curing agent), thus obtaining good low-temperature curing performance during actual use. However, the disadvantages of the above-mentioned curing systems are that the isocyanate swells under high humidity, so that the long-term corrosion resistance of the coating is not satisfactory, and the above-mentioned curing systems are compatible with petroleum resins used in anti-corrosion coating compositions. Poor compatibility makes it difficult to use in heavy duty coating compositions.

Tar-epoxy coating compositions have been used in the art as anticorrosion coating compositions for marine and steel structures. The above-mentioned coating composition has good corrosion resistance, water resistance, chemical resistance, etc., but its disadvantage is that due to containing tar, the composition is still worrying from the perspective of safety and health, and the black color of the tar makes the coating composition After coating, it is difficult to maintain and control, and produces a closed space black, which makes the operation dangerous.

By using petroleum resins instead of tar, various methods of preparing coating compositions capable of giving light-colored finishes and useful for coating interiors of ships such as ballast tanks have been proposed. The present applicant has also proposed an anti-corrosion coating composition containing a petroleum resin having specific properties (see Japanese Patent Application Laid-Open Nos. 263713/97 and 302276/97). The above-mentioned anti-corrosion coating composition contains a petroleum resin with relatively good compatibility with the amine-based curing agent, and can form a light-colored coating film with good anti-corrosion, water resistance, and adhesion properties. However, since an amine-based curing agent is used therein, the curing performance of the coating film at low temperature is not satisfactory, so that a coating film having good film properties cannot be obtained as the case may be.

In order to solve the above problems, the inventors have carried out in-depth research and found that an amine-based curing agent can be prepared by modifying the Michael addition product with a specific composition with an epoxy resin; the curing agent has good low-temperature curing performance, and is compatible with corrosion Petroleum resins widely used in coating compositions have good compatibility; the use of amine-based curing agents can obtain tar-free anti-corrosion coating compositions with good low-temperature curing performance, and can form anti-corrosion, water resistance, adhesion, etc. The light-colored coating film; Above-mentioned research result obtains the present invention.

In a first embodiment, the present invention provides an amine-based curing agent obtained by combining the condensation reaction product of (a) amine, (b) phenol and (c) formaldehyde with (d) one molecule containing at least two The epoxy resin of two epoxy groups is prepared by reacting, the amine (a) is a mixture of xylylene diamine and aliphatic polyamine, and the phenol (b) is selected from bisphenol A, bisphenol F and phenol Mixtures of at least one alkylphenol with an alkyl chain having 9 or more carbon atoms.

In a second embodiment, the present invention provides a curable resin composition comprising (A) an epoxy resin and (B) an amine-based curing agent, the amine-based curing agent being obtained by combining (a) xylylenediamine with an aliphatic polyamine (b) a mixture of at least one selected from bisphenol A, bisphenol F and phenol and an alkylphenol having an alkyl chain of 9 or more carbon atoms and (c) a condensation reaction product of formaldehyde with ( d) The epoxy resin containing at least two epoxy groups in one molecule is prepared by reacting.

In a third embodiment, the present invention provides an anti-corrosion coating composition containing (A) epoxy resin, (B) amine-based curing agent and (C) petroleum resin, and the amine-based curing agent is obtained by adding (a) xylene A mixture of diamine and aliphatic polyamine, (b) a mixture of at least one selected from bisphenol A, bisphenol F, and phenol and an alkylphenol having an alkyl chain of 9 or more carbon atoms, and (c) The condensation reaction product of formaldehyde is reacted with (d) an epoxy resin containing at least two epoxy groups in one molecule, and for every 100 parts by weight of curable resin solids, the content of the petroleum resin (C) is 20 to 150 parts by weight.

The amine-based curing agent in the first embodiment of the present invention or the amine-based curing agent (B) in the second and third embodiments of the present invention (hereinafter referred to as the amine-based curing agent of the present invention) is obtained by adding (a) amine, (b) a curing agent prepared by reacting a condensation reaction product of phenol and (c) formaldehyde with (d) an epoxy resin containing at least two epoxy groups in one molecule.

The amine (a) in the present invention is a mixture of xylylenediamine and aliphatic polyamine. Preferable examples of the aliphatic polyamine include diethylenetriamine, triethylenetetramine, and the like.

The preferred mixing ratio of xylylenediamine to aliphatic polyamine is 2:1 to 1:2 by weight. Too much xylylenediamine exceeding the above ratio will result in poor adhesion of the coating film. On the other hand, too much aliphatic polyamine will lead to poor low-temperature curing performance of the coating and poor compatibility with petroleum resins.

The phenol (b) in the present invention is a mixture of at least one selected from bisphenol A, bisphenol F and phenol and an alkylphenol having an alkyl chain of 9 or more carbon atoms. Alkylphenols have an alkyl chain of 9 or more carbon atoms. The use of alkyl chains having less than 9 carbon atoms undesirably reduces compatibility with petroleum resins. Examples of alkylphenols include nonylphenol, dodecylphenol, cardanol, and the like.

A preferable mixing ratio of at least one selected from bisphenol A, bisphenol F and phenol to alkylphenol in phenol (b) is 2:1 to 1:2 by weight. Too much amount of at least one phenol selected from bisphenol A, bisphenol F, and phenol reduces compatibility with petroleum resins. On the other hand, too much amount of alkylphenol undesirably reduces low-temperature curing properties and water resistance of the paint.

The epoxy resin (d) used in the present invention includes an epoxy resin containing at least two epoxy groups in one molecule, preferably an epoxy resin with an epoxy equivalent of 150 to 600. Especially preferred epoxy resins are bisphenol type epoxy resins in view of water resistance and low-temperature curing properties.

The amine-based curing agent of the present invention is prepared by a conventional method comprising mixing the above-mentioned components (a), (b) and (c), followed by heating and dehydration at a temperature of 50 to 180° C. to obtain a Michael reaction condensation product, Component (d) is added, and the amino group and epoxy group in the condensation product are reacted by heating at a temperature of 20 to 200°C.

The mixing molar ratio of the above-mentioned components (a), (b), (c) and (d) is such that, for 1 mol of component (a), the amount of component (b) is 0.7-1.3 moles, and the component (c) is 0.7 -1.3 mol, component (d) is 0.2-0.5 mol. When the amount of the component (a) is higher than the range of the above-mentioned molar ratio, low-temperature curability decreases, and unreacted products bleed out from the surface of the coating film. On the other hand, when the amount of the component (a) is lower than the range of the above molar ratio, the curing performance is reduced, and the unreacted component (b) will remain in the coating film, reducing the water resistance of the coating.

The amine-based curing agent of the present invention obtained by the above method is useful as a curing agent for epoxy resins, exhibits good low-temperature curing properties, and can shorten the drying and curing time at room temperature.

The epoxy resins (A) used in the second and third embodiments of the present invention include epoxy resins containing at least two epoxy groups in one molecule, preferably rings having an epoxy equivalent weight of 150 to 600, preferably 180 to 300 oxygen resin. Examples of the epoxy resin (A) include epoxy resins such as bisphenol-type epoxy resins, aliphatic epoxy resins, glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, novolac-type epoxy resins, and cresol-type epoxy resins. Oxygen resin, dimer acid modified epoxy resin, etc. These resins may be used alone or in combination.

In the second and third embodiments of the present invention, the mixing ratio of component (A) to component (B) can be freely changed depending on the kinds of component (A) and component (B) used, but preferably component (B) The equivalent ratio of the active hydrogen equivalents in the component (A) to the epoxy equivalents in the component (A) is in the range of 0.5 to 1.0.

The curable resin composition in the second embodiment of the present invention optionally includes petroleum resins, other liquid modifiers and active or inactive diluents; pigments, such as extender pigments, anti-corrosion pigments, coloring pigments, etc.; and known additives, Such as organic solvents, anti-sedimentation agents, anti-sagging agents, wetting agents, reaction accelerators, adhesion-giving agents, dehydrating agents, etc.

The petroleum resin (C) in the third embodiment of the present invention preferably includes a petroleum resin that is solid at normal temperature and has a softening point of 50 to 150°C, preferably 80 to 100°C. Examples of the above-mentioned petroleum resins include aromatic-based petroleum resins obtained by polymerizing _C9 fractions such as styrene derivatives, indene, etc. (obtained from heavy oil produced in the cracking process of petroleum naphtha); the above-mentioned _C5 fractions and _C9 fractions are copolymerized The obtained copolymer petroleum resin; the aliphatic-based petroleum resin obtained by partially cyclic polymerization of conjugated dienes in the _C5 fraction such as cyclopentadiene and 1,3-pentadiene; the hydrogenation of the aromatic-based petroleum resin Resins; alicyclic petroleum resins obtained by polymerizing cyclopentadiene and the like.

When the softening point of the petroleum resin (C) is lower than 50° C., the water resistance of the coating film decreases, and the component (C) penetrates to the surface of the coating film to maintain adhesion. On the other hand, when the softening point of the petroleum resin (C) is higher than 150° C., the viscosity of the coating composition increases, degrading the applicability and physical properties of the coating film.

In particular, the petroleum resin (C) preferably includes a hydroxyl-containing petroleum resin having a softening point of 50 to 150° C., wherein the content of the hydroxyl group in one molecule is 0.5 to 1.5 mol. Hydroxyl-containing petroleum resins can be produced by introducing hydroxyl groups into the above-mentioned petroleum resins. Among these resins, hydroxyl group-containing aromatic-based petroleum resins are preferable from the standpoint of water resistance and compatibility with components (A) and (B).

When the amount of hydroxyl groups contained in one molecule of the hydroxyl-containing petroleum resin is less than 0.5 moles, the compatibility with the amine-based curing agent is reduced, which adversely affects the performance of the coating film. When the amount of hydroxyl groups contained in one molecule of the hydroxyl-containing petroleum resin exceeds 1.5 moles, the water resistance of the coating film decreases.

In the anticorrosive coating composition in the third embodiment of the present invention, the petroleum resin (C) is contained in an amount of 20 to 150 parts by weight, preferably 50 to 150 parts by weight, per 100 parts by weight of cured resin solids. When the above content is less than 20 parts by weight, satisfactory water resistance cannot be obtained. On the other hand, when the above content is more than 150 parts by weight, the resulting brittle coating film may not have good physical properties, and the low-temperature curing performance is severely reduced.

The anti-corrosion coating composition in the third embodiment of the present invention may optionally contain other liquid modifiers or diluents; pigments, such as extender pigments, anti-corrosion pigments, coloring pigments, etc.; reactive diluents; and additives commonly used in the composition , such as organic solvents, anti-sedimentation agents, anti-sagging agents, wetting agents, reaction accelerators, adhesion-giving agents, dehydrating agents, etc.

The anti-corrosion coating composition in the third embodiment of the present invention is a two-component type coating composition, including the base material (base material) containing epoxy resin (A) and petroleum resin (C), and amine-based curing agent (B ), usually applied to a primer anti-corrosion coating such as zinc primer. The above-mentioned coating composition can be coated by coating methods known in the art, such as air spray coating, airless spray coating, brush coating, roller coating, etc., and the thickness of the dry film is 150 to 500 μm.

Example

The present invention is explained in more detail by the following examples, wherein "parts" and "%" mean "parts by weight" and "% by weight".

Preparation of amine-based curing agent

Example 1

Into a reactor equipped with a stirrer and a thermometer, 68 g (0.5 mol) of xylylenediamine, 52 g (0.5 mol) of diethylenetriamine, 114 g (0.5 mol) of bisphenol A and 110 g (0.5 mol) of nonyl Phenol, then stir completely, add 81g (1 mole) 37% formaldehyde water to react, be heated to 100 ℃ of reaction 2 hours, dehydration obtains condensation reaction product, add 95g (0.25 mole) Epon #828 (trade name, epoxy Resin, epoxy equivalent: 190, sold by Yuka Shell Epoxy Co.Ltd.), was reacted at 80° C. for 2 hours, diluted with a mixed solvent of toluene: isopropanol = 1: 1 to obtain a non-volatile matter content of 60%. Amine-based curing agent (B-1). The viscosity of the curing agent solution is 900cps (measured with a B-type viscometer at 25°C/60 r.p.m).

Embodiment 2-4 and comparative example 1-6

Repeat Example 1, except that various components are listed in Table 1, to obtain various amine-based curing agents (B-2) to (B-9). The viscosity of Comparative Example 6 was so high that it was impossible to prepare a curing agent. In Table 1, the components are expressed by molar ratio, (Note 1) and (Note 2) are explained below.

(Note 1) Epon #1001: epoxy resin, epoxy equivalent: 475, sold by Yuka Shell Epoxy Co. Ltd., trade name.

(Note 2) Epiclon #520: trade name, monoepoxide, sold by Dainippon Inkand Chemicals, Inc.

Table 1 Example comparative example 1 2 3 4 1 2 3 4 5 6 Amine based curing agent B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 - Element a Methylxylenediamine 0.5 0.6 0.5 0.5 1.0 - 0.5 0.5 0.5 0.5 Diethylenetriamine 0.5 0.6 0.5 0.5 - 1.0 0.5 0.5 0.5 0.5 b Bisphenol A 0.5 0.5 0.6 0.5 0.5 0.5 - 0.5 0.5 1.0 Nonylphenol 0.5 0.5 0.6 0.5 0.5 0.5 1.0 0.5 0.5 - c formaldehyde 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 d Epon #828 0.25 0.25 0.25 0.25 0.25 0.25 - 0.25 Epon #1001 (Note 1) 0.25 Epiclon #520 (Note 2) 0.25 Non-volatile content 60 60 60 60 60 60 60 60 60 - Viscosity (cps/25℃) 900 400 400 2000 600 1000 400 400 700 - Active hydrogen equivalent 150 122 165 198 187 124 149 102 127 -

Preparation of Curable Resin Composition

Embodiment 5-8 and comparative example 7-12

In a 1-liter reactor, 100 parts of Epon #828 and various amine-based curing agents obtained above according to the formula in Table 2 were charged, followed by mixing and stirring to obtain various curable resin compositions. Various compositions were subjected to the following performance tests. The test results are listed in Table 2. In Table 2, (Note 3) represents the following meanings.

(Note 3) Versamin F20: trade name, Michael-modified o-xylylenediamine, active hydrogen equivalent: 80, sold by Henkel Japan Ltd., non-volatile matter content: 100%, viscosity: 3000 cps.

Performance Testing

(*1) Compatibility:

Immediately after mixing, each sample was coated on a glass plate with a film applicator to obtain a dry film thickness of 250 μm, followed by drying at 5°C and 65% RH for 24 hours, and visually evaluated the appearance of the coating film according to the following criteria .

3: no change; 2: turbidity; 1: separation.

(*2)Low temperature curing properties:

Immediately after mixing, each sample was coated on a degreased polished mild steel plate (0.8×70×150 mm) with a dry film thickness of about 250 μm, followed by drying at 5°C and 65% RH After 16 hours, press the surface of the coating film with fingers, and visually evaluate the appearance of the coating film according to the following criteria.

3: Heavy pressure with fingers, the coating film does not slip;

2: Press heavily with your fingers, and the coating film will slip;

1: Press lightly with your fingers, and the coating film will slip;

(*3) Adhesive properties:

Immediately after mixing, each sample was coated on a shot-peened steel plate (2×70×150 mm) with a film applicator to obtain a film thickness of about 250 μm, followed by drying at 5°C and 65% RH After 7 days, various coating test panels were obtained, and the cross-hatch adhesion test was carried out on the test panels, followed by sticking adhesive cellophane strips on it, separating the paper strips, and visually evaluating the appearance of the coating film according to the following standards.

3: Good;

2: Partial peeling occurs;

1: Peeling occurs on the entire surface.

Table 2 Example comparative example 5 6 7 8 7 8 9 10 11 12 Epon #828 100 100 100 100 100 100 100 100 100 100 Amine based curing agent (B-1) 100 (B-2) 100 (B-3) 100 (B-4) 100 (B-5) 100 (B-6) 100 (B-7) 100 (B-8) 100 (B-9) 100 Amine-based curing agent for comparison (Note 3) 40 performance compatibility 3 3 3 3 3 3 3 3 3 3 low temperature curability 3 3 3 3 3 2 2 2 2 3 Adhesiveness 3 3 3 3 3 3 3 2 3 2

Preparation of anti-corrosion coating composition

Example 9

100 parts of Epon #828, 70 parts of titanium dioxide, 100 parts of talcum powder, 100 parts of hydroxyl-containing petroleum resin (note 4), 10 parts of anti-sagging agent (note 5) and 10 parts of Xylene, then mixed and stirred in a disperser to form a dispersion as a base material, just before coating, add 100 parts of amine-based curing agent (B-1) to the base material, mix and stir to obtain an anti-corrosion coating combination thing.

Examples 10-14 and Comparative Examples 13-21

Repeat Example 9, the difference is to use the ingredients and formulations shown in Table 3 to obtain various anti-corrosion coating compositions. In Table 3, (Note 4), (Note 5) and (Note 6) are explained as follows.

(Note 4) Neopolymer K-2: Trade name, divinyltoluene-indene copolymer, containing 1 to 1.1 moles of hydroxyl groups in one molecule, softening point: 100°C, sold by Nippon Petrochemicals Co., Ltd.

(Note 5) Disparion A630-20XN: trade name, polyamide wax, sold by Kusumoto Chemicals Ltd.

(Note 6) Coronate L: trade name, isocyanate curing agent, tolylene diisocyanate modified product, NCO content: 13%, sold by Nippon Polyurethane IndustryCo.Ltd.

Performance Testing

Various anticorrosion coating compositions obtained above were subjected to the following performance tests. The results are listed in Table 4.

(*4) Compatibility

The above (*1) was repeated except that the anti-corrosion coating composition was used instead of the resin composition in the above (*1).

(*5)Low temperature curing properties

The above (*2) was repeated except that the anti-corrosion coating composition was used instead of the resin composition in the above (*2).

(*6) Flexibility

Each anti-corrosion coating composition is coated on the degreasing polished low-carbon steel plate (150 × 70 × 0.8mm) by airless spraying method, and the dry film thickness obtained is about 250 μm, then under the conditions of 20 ℃ and 65% RH environment After drying for 7 days, test samples for each coating were obtained. The test sample of each coating is folded outward at a temperature of 20°C at a folding angle of 90°, and the cracks appearing on the folded part of the coating film are visually evaluated according to the following standards. 3: No cracks appear; 2: Few cracks appear; 1: Many cracks appear

(*7) Water resistance to temperature difference water

Each anticorrosion coating composition obtained above is applied to the steel plate (300 * 100 * 3.2mm) after shot blasting by airless spraying, that is, on the test sample I, and is coated on the test sample II, and the obtained dry The film thickness is about 250 μm, and then dried for 7 days under the conditions of 20° C. and 65% RH environment to obtain various coating test panels. The test sample II is prepared by coating SDZinc 1000 HA (trade name, sold by Kansai Paint Co., Ltd., zinc silicate primer) on the above-mentioned steel plate to obtain a dry film with a thickness of about 25 μm, followed by drying for one day .

Each coating test panel was immersed for 14 days in such an immersion container that the coated surface of the coating test panel was in contact with hot water at 40°C, and the back of the coating test panel was in contact with water at 20°C, and then according to the following standard Visually assess the coating surface condition.

3: No abnormality; 2: A small amount of blistering and rusting occurred; 1: Blistering and rusting were clearly observed.

(*8) Seawater resistance

Each coating test specimen obtained in the same manner as above (*7) was immersed in seawater at 50°C for 3 months, followed by visual evaluation of the coating surface condition according to the following criteria.

3: no abnormality; 2: a small amount of foaming occurs; 1: obvious foaming occurs.

table 3 Example comparative example 9 10 11 12 13 14 13 14 15 16 17 18 19 20 twenty one Binder Epon #828 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Epon #1001 100 Titanium dioxide 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 talcum powder 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Hydroxyl-containing petroleum resin (Note 4) 100 100 100 100 50 100 100 100 100 100 100 100 100 200 Anti-sagging agent (Note 5) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Xylene 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Hardener Amine based curing agent (B-1) 100 100 100 100 100 (B-2) 100 (B-3) 100 (B-4) 100 (B-5) 100 (B-6) 100 (B-7) 100 (B-8) 100 (B-9) 100 Amine-based curing agent for comparison (Note 3) 40 Isocyanate curing agent (Note 6) 50

Table 4 Example comparative example 9 10 1 1 12 13 14 13 14 15 6 17 18 19 20 twenty one compatibility 3 3 3 3 3 3 3 2 3 3 3 2 1 3 3 Low temperature curing properties 3 3 3 3 3 3 3 2 1 2 2 1 3 1 3 flexibility 3 3 3 3 3 3 3 3 3 3 3 2 2 3 1 Water resistance to temperature difference water Test sample I 3 3 3 3 3 3 2 3 1 3 2 2 2 2 1 Test sample II 3 3 3 3 3 3 2 3 1 3 2 2 2 2 1 Sea water resistance Test sample I 3 3 3 3 3 3 3 3 2 3 2 2 2 2 2 Test sample II 3 3 3 3 3 3 3 3 2 3 2 2 2 2 2

The invention provides an amine-based curing agent, which is prepared by modifying a Michael reaction product with a specific composition with an epoxy resin, has good low-temperature curing performance, and has good compatibility with petroleum resins. The invention also provides A curable resin composition containing the amine-based curing agent is provided, which has good low-temperature curing performance and can form a coating film with good corrosion resistance and adhesion.

The present invention can provide a tar-free anti-corrosion coating composition with good low-temperature curing performance without safety and health problems by using an amine-based curing agent prepared by modifying a Michael reaction product with a specific composition with an epoxy resin , and has good compatibility with petroleum resins. The anticorrosion coating composition of the invention can form a light-colored coating film, and has good anticorrosion, water resistance and adhesion.

The anticorrosion coating composition of the present invention is very useful as a heavy anticorrosion coating composition for ships and steel structures.

Claims (11)

1, a kind of amido solidifying agent, by being reacted, (a) amine, (b) phenol and the Resins, epoxy that (c) contains at least two epoxy group(ing) in condensation reaction products and (d) molecule of formaldehyde makes, described amine (a) is the mixture of dimethylphenylene diamine and aliphatic polyamine, and described phenol (b) is the mixture that at least a and alkyl chain that is selected from dihydroxyphenyl propane, Bisphenol F and phenol has the alkylphenol of 9 or more carbon atoms.

2, the amido solidifying agent of claim 1, wherein the ratio of mixture of dimethylphenylene diamine and aliphatic polyamine is weight ratio 2: 1 to 1: 2 in the amine (a).

3, the amido solidifying agent of claim 1, the ratio of mixture that wherein is selected from least a and alkylphenol of dihydroxyphenyl propane, Bisphenol F and phenol in the phenol (b) is weight ratio 2: 1 to 1: 2.

4, the amido solidifying agent of claim 1, employed composition (a) and (b), (c) and mol ratio (d) are like this, and promptly for 1 mole composition (a), the amount of composition (b) is the 0.7-1.3 mole, composition (c) is the 0.7-1.3 mole, and composition (d) is the 0.2-0.5 mole.

5, a kind of curable resin composition, contain (A) Resins, epoxy and (B) amido solidifying agent, the mixture of the alkylphenol of described amido solidifying agent by the mixture of (a) dimethylphenylene diamine and aliphatic polyamine, at least a and alkyl chain that (b) is selected from dihydroxyphenyl propane, Bisphenol F and phenol being had 9 or more carbon atoms and (c) condensation reaction products of formaldehyde and the Resins, epoxy that (d) contains at least two epoxy group(ing) in molecule react and makes.

6, the curable resin composition of claim 5, wherein Resins, epoxy (A) contains at least two epoxy group(ing) in a molecule, and epoxy equivalent (weight) is 150 to 600.

7, the curable resin composition of claim 5, wherein composition (A) is such with the ratio of mixture of composition (B), promptly the equivalence ratio of middle reactive hydrogen equivalent of composition (B) and the middle epoxy equivalent (weight) of composition (A) is in 0.5 to 1.0 scope.

8, a kind of anticorrosive paint composition, contain (A) Resins, epoxy, (B) amido solidifying agent and (C) petroleum resin, described amido solidifying agent is by the mixture with (a) dimethylphenylene diamine and aliphatic polyamine, (b) be selected from dihydroxyphenyl propane, at least a and the alkyl chain of Bisphenol F and phenol has the mixture of alkylphenol of 9 or more carbon atoms and the Resins, epoxy that (c) contains at least two epoxy group(ing) in condensation reaction products and (d) molecule of formaldehyde and reacts and make, for the solidified resin solid thing of per 100 weight parts, the amount of contained petroleum resin (C) is 20 to 150 weight parts.

9, the anticorrosive paint composition of claim 8, wherein Resins, epoxy (A) contains at least two epoxy group(ing) in a molecule, and epoxy equivalent (weight) is 150 to 600.

10, the anticorrosive paint composition of claim 8, wherein petroleum resin (C) are that hydroxyl, softening temperature are 50 to 150 ℃ petroleum resin, the content of hydroxyl is the 0.5-1.5 mole in molecule.

11, the anticorrosive paint composition of claim 8, wherein composition (A) is such with the ratio of mixture of composition (B), promptly the equivalence ratio of middle reactive hydrogen equivalent of composition (B) and the middle epoxy equivalent (weight) of composition (A) is in 0.5 to 1.0 scope.