KR800001195B1 - Epoxy resin composition cored by reaction product of phenol carboxylic acids with polyamino compounds - Google Patents

Abstract

Chelate forming coating compns. contained epoxy resin(contg. >=2 epoxy group), active H-contg. amino type hardener (contg. >=2 N), 5-30 wt.% phenolcarboxylic acid and org. sol. vent. Thus, 100 parts bisphenol type epoxy resin(epoxy equiv. 450-500) was dissolved in 100 parts BuOCH2CH2OH(I) and mixed with 50 parts red iron oxide, 100 parts talc, 50 parts BaSO4 and 100 parts I to give the main compn. 100 parts polyamide (amine value 300±20) and 15 parts gallic acid, were heated at 140-150≰Cn and thinned with I to give 50% hardener soln. which was mixed in 100:18 solid ratio with the main compn.

Description

Epoxy Resin Compositions with Chelated Performance

The present invention relates in particular to epoxy resin compositions having chelate type performance useful as anticorrosive coatings.

BACKGROUND ART Vehicles conventionally used for coatings are used for various kinds of resins such as unsaturated fatty acids, alkyds, olefins, dienes, acrylics, polyesters, epoxys, urethanes, or copolymerized resins thereof. have. Among them, the demand for epoxy resins is increasing due to its excellent physical properties (adhesiveness, hardness) and chemical resistance (chemical resistance).

In recent years, there has been a great demand for paints that have no danger, for example, low flammability or no toxicity to humans.

As one of them, a so-called water-based paint has been developed which is used by dispersing, emulsifying or dissolving epoxy resin in water.

As a known example of such an aqueous epoxy resin coating composition, for example, US Patent No. 2811495, No. 2899397, No. 3324041 No. 3355409, No. 349281, No. 3640926 and the like are already known.

Although various other things have been researched and developed, it is still not enough in terms of moisture resistance, corrosion resistance, physical properties, etc. compared with a solvent type composition.

In order to improve their corrosion resistance, for example, anti-corrosive pigments such as cyanamide lead, nitrous oxide, basic chromate, podium, strontium chromate, zinc chromate and zinc chromate have been proposed. In view of the above, it is not preferable.

Moreover, it was not necessarily satisfied with various physical properties including moisture resistance and corrosion resistance.

On the other hand, compounds having chelate-binding properties, such as polyhydric phenols such as pyrogolols, phenolcarboxylic acids, chromium complex salts, phthalocyanines, pyridines, and derivatives thereof, are blended into the coating material and then applied to the paint. Attempts have been made to perform chelation reactions with iron surface of c) and to improve its coating performance.

In the past, solvent-based paints simply added tanning to linseed oil-based resins or dry oils are known (British patents 826564 and 826566).

Then, RN Faulkner et al. Covalently bond catechol, pyrogarol, molar or molar asset esters to vegetable oils, fatty acid esters, alkyd resins, plant rheological epoxy ester resins or plant rheological polyamide resins using a catalyst such as metal alkoxide. Solvent-based one-component paints have been developed.

For example, British Patent No. 1045118, US Pat. No. 3,304,276 and No. 3,320,320 and Journal of the Oil and Color Chemists' Association, Volume 50, page 524 (1967). In addition, British Patent No. 1114400 discloses a composition obtained by reacting a styrene aryl alcohol hole copolymer with a molar ester.

Moreover, the composition which has the chelate type performance using an epoxy resin is also known. For example, a chelate-forming resin in which a part of an epoxy group is modified into a monobasic fatty acid in an epoxy resin, the remaining epoxy group has two or more adjacent phenolic hydroxyl groups having a chelate-forming ability, and is reacted with a fatty acid derivative having one free carboxyl group. So 48-24389), a composition consisting of an epoxy polyamide resin having a chelating ability and a phosphoric acid compound obtained by reacting a polyamide resin having an amine value of 10 or less with a residual epoxy group of a reaction product of an epoxy resin (method 48-17443). One-component or two-component (amine) diluted with an organic solvent formed by adding epoxy resin, vinyl resin, fluorine resin, etc. to a partial ester compound obtained by reacting a part of epoxy group in epoxy resin with salicylic acid, a molar asset or ester compound thereof. Use of hardening agent) Paint (Special Public Service No. 49-4811, It places a call deulsu the 48-56227, No. 48-56228 Patent places, particularly places No. 49-122538, and No. 49-122597 Patent places).

However, these are all modified from the epoxy resin of the subject with a chelate-forming compound.

In short, it is a one-component or two-component composition in which all or part of the epoxy groups in the epoxy resin are reacted with a compound having a chelate-forming ability, thereby significantly reducing the properties of the epoxy resin.

The present inventors have improved these points, and have an aqueous epoxy resin composition having a chelate-type performance consisting of an epoxy resin emulsion and a curing composition that has already been "bonded" with protocadic acid and / or a molar asset, or an ester amino curing agent thereof. Suggested.

In addition, a two-component composition containing i) an epoxy resin, ii) a chelating agent having a chelate-forming ability, and iii) an organic solvent capable of dissolving the epoxy resin and the curing agent was studied. Even now, it has been found that an epoxy resin rust preventive paint capable of forming a coating film having excellent corrosion resistance and moisture resistance can be produced.

That is, the present invention,

i) an epoxy resin having at least two epoxy groups in one molecule,

ii) obtained by condensation of an amino-based curing agent having at least two or more nitrogen atoms and active hydrogens bound thereto in one molecule with 5-30% by weight of phenolcarboxylic acid and / or esters thereof based on the curing agent; Reaction product, and

iii) The present invention relates to an epoxy resin composition having a chelate type performance mainly comprising an organic solvent capable of dissolving the epoxy resin and the reaction product.

Examples of the "epoxy resin having at least two epoxy groups in one molecule" used as the subject of the present invention are exemplified below.

Trade names Epicote 828, East 834, East 836, East 1001, East 1004, East 1007 manufactured by Shell Chemical Co., Ltd., commercially available as bisphenol-type epoxy resins; The brand name Ararudite GY 252, copper GY 250, copper GY 260, copper GY 280, copper 6071, copper 6084, copper 6097 by Chiba Co., Ltd .; Dow Chemical Co., Ltd. brand names DER 330, 331, 337, 661, 664; Epikron 800, Copper 1010, Copper 3010 manufactured by Nippon Ink Chemical Co., Ltd .; As a phenol novolak-type epoxy resin, For example, the brand name Epicoat 152,154 of the shell chemical company make; Dow Chemical Co., Ltd. brand names DEN 431, East 438, East 439: The trade name EPN 1138 by Chiba Co., Ltd .; The trade name Epiclon N-565 and N-577 manufactured by Dainippon Ink and Chemicals Co., Ltd .; As a polyglycol type epoxy resin, For example, the brand name Ararudite CT-508 by Chiba Co., Ltd .; Dow Chemical Co., Ltd. brand names DER-732, 736, 741; As an ester type epoxy resin, For example, the product name of the Dai Nippon Ink Chemical Co., Ltd. make is a Pylon 200, copper 400, copper 1400; As epoxidized polybutadiene, Brand name BF-1000 by Soda Japan Co., Ltd .; Trade name sumikaoil # 50 manufactured by Sumidomo Chemical Co., Ltd .; As epoxidized oil, brand name Adeka Saiza-0-180 of the Adeka Agas Chemical Co., Ltd., 9-130P; Etc. can be mentioned.

It should also be noted that the epoxy-based compounds and derivatives of the epoxy resins easily inferred from these compositions are included within the scope of the present invention.

For example, polyol type epoxy resin, alicyclic epoxy resin, halogen containing epoxy resin, silicone modified epoxy resin, etc. are contained.

Although the said epoxy resin is a liquid thing and a solid thing at normal temperature, either can be used favorably by addition of the solvent which can melt | dissolve these.

Moreover, even if it uses a liquid epoxy resin and a solid epoxy resin at normal temperature, it does not interfere at all.

Moreover, in this invention, the monoepoxy compound which has one epoxy group in a molecule | numerator can be used up to 20 weight with respect to the said epoxy resin in order to improve the workability, coating-film performance, and coating state of the said epoxy resin.

Examples of the monoepoxy compound include arylglycidyl ether, 2-ethylated sillycidyl ether, methylglycidyl ether, butylglycidyl ether, phenylglycidyl ether, styrene oxide, cyclohexene oxide and epi And crothydrin or a compound having one epoxy group modified by fatty acid or the like with an epoxy resin having two or more epoxy groups in the molecule.

In addition, in this invention, 20 weight% or less of other resin can be used together with preferable thing with respect to the said epoxy resin. Although the combined resin does not need to react especially with the epoxy group in epoxy group-containing resin, the amino group in a later-hardening | curing agent, etc., it can add and use together for the improvement of the coating workability of a composition, coating-film performance, the surface state of a coating film, etc.

Examples thereof include amino resins, phenol resins, alkyd resins, polyester resins, urethane-ized oils, coals, asphalt, xylene resins, polyvinyl formal, polyvinyl acetal, and the like.

On the other hand, "amino-based curing agent having at least two or more nitrogen atoms in one molecule and active hydrogen bonded thereto" used in the present invention is amino such as amine adducts, polyamides, polyamines, etc. which are usually used as curing agents for epoxy resins. System compound.

The polyamide resin includes dimer acid (a general industrial product contains about 3% of monomeric acid, about 85% of dimer acid, and about 12% of trimeric acid), and ethylenediamine, diethylenetriamine, or metaphenyrenidiamine. Condensation product with polyamines. For example, Fuji-Hwa Kogyo Co., Ltd. brand name Tomide Y-25, copper 210, copper 215, copper 215-X copper 225-X, copper 235S, copper 235, A, copper 245, copper 2400, Copper 2500; First General Co., Ltd. product name Genamide 2000, Baasamide 115, Copper 125, Copper 100, Copper 140, Copper 230, Copper 280, Copper 400, Copper 401, Copper 415, DSX-1280; Sanwa Chemical Co., Ltd. tradename Sanamide 320, Copper 330; Shell Chemical Co., Ltd. brand name Epicure 4255 etc. are mentioned.

Moreover, the said amine duct resin is an addition product of said epoxy resin, such as bisphenol-type epoxy resin, and polyamines, such as ethylenediamine, diethylenetriamine, or metaphenylenediamine. For example, Fuji Kasei Kogyo Co., Ltd. brand name Tomide 238, Fuji Cure (202, East 110; Asahi Telephone Co., Ltd. brand name Adeka Haadner EH-531, East 101, East 532, East 551, and the like.

Moreover, as said amine adduct, it is an addition product with a butylglycidyl ether, a glycidyl ester of baasatic acid, a bisfenyu type epoxy resin, etc., for example, the heterocyclic diamine represented by following Formula.

For example, Ajinomodo Co., Ltd. brand name Efomate B-002, copper B-001, copper C-002, copper S 005, copper S002, copper LX-1, copper RX-2, copper Rx- 3, copper N-001; There is something like These hardeners are used as 1 type, or 2 or more types of mixtures according to the objective.

In order to perform crosslinking reaction with an epoxy resin, the said hardening | curing agent needs to have at least 2 or more nitrogen atoms in 1 molecule, and the active hydrogen couple | bonded with this. Although there is no restriction | limiting in particular about this hardening | curing agent, It is preferable that it is 50 or more as an amine number. However, when the amine value of the curing agent is extremely large, a limitation arises that the usable time after mixing with the epoxy resin as the main ingredient becomes short.

In the present invention, the reaction product must have a compound having a chelate type performance, that is, phenolcarboxylic acid and / or esters thereof, bound to the amino-based curing agent.

As said phenolic carboxylic acid, for example, a protocatecuic acid, a molar asset, etc. are mentioned. Moreover, as ester of a phenol carboxylic acid, ester, such as a molar asset of 1-12 carbon atoms of an alkyl group, protocatecuic acid, is mentioned. For example, methyl methyl acetate, ethyl ethyl acetate, propyl propyl, sodium amyl, lysyl sulfuryl, ethyl protocatesilicate, propyl protocatecuic acid, etc. are mentioned.

The phenolcarboxylic acid and / or esters thereof are used in an amount of 5-30% by weight, preferably 10-25% by weight based on the amino-based curing agent solid component.

When the compound having the chelate type performance in the above ratio is 5% by weight or less, the effect of the present invention is not very expected, while when it is 30% by weight or more, it is not easily dispersed, and more than required chelate is formed. The resulting coating film becomes hard and brittle, and the moisture resistance is also lowered and uneconomical.

Reaction of the phenolcarboxylic acid and / or these esters in this invention with the said hardening | curing agent is performed as follows.

Phenolcarboxylic acid and / or esters thereof and the curing agent at an arbitrary temperature up to 100-240 ° C until a predetermined condensation water or alcohol is obtained (usually 3-10 hours), and inert gas such as nitrogen gas. Heat and stir in the presence. By doing so, the reaction product into which phenolcarboxylic acid and / or these esters were introduce | transduced in the hardening | curing agent by covalent bond is obtained.

The reaction product of the present invention as described above has the performance of performing crosslinking reaction with epoxy resin, that is, acting as a curing agent, and also chelation reaction with the iron surface of the workpiece.

That is, when coated on the iron surface as a coating composition, the reaction product enables chelation reaction with the base iron surface, regardless of the degree of possession of the iron surface and the degree of rust generation, and especially without adding an rust preventive pigment or the like. Significantly improves coating performance such as moisture resistance and corrosion resistance.

The reaction product is preferably solid in terms of coating performance, but a liquid may be used at room temperature.

Usually the reaction product is used in 10-100% by weight of solids.

In addition, in the present invention, 2-30% by weight of tanning may be mixed with the reaction product to increase chelating ability.

In addition, as an organic solvent used for this invention, if it is a solvent common to the said two components, there will be no restriction | limiting in particular, For example, Ketones, such as methyl ethyl ketone and a methyl isobutyl ketone; Alcohols such as methanol, ethanol and n-butanol; Ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; Aromatic hydrocarbons such as toluene, xylene and aromatic petroleum naphtha; Acetate esters, such as methyl acetate, ethyl acetate, and a butyl acetate, are mentioned.

However, there is no problem even if other solvents are added unless separated.

Therefore, in a single solvent, the solubility of either component may decrease in either of the two components. In that case, a mixed solvent using 2-3 kinds of the solvents or other soluble solvents in combination is used. Is also ok. Although the usage-amount differs also by a coating method and a coating condition, it is 5 weight% or more with respect to normal coating.

The composition of the present invention is based on the epoxy resin (topic), the reaction product (curing agent) having a chelate type performance, and an organic solvent as the main components, but the subject matter, such as talc, precipitated barium sulfate, calcium carbonate, etc. Sulfur lead, carbon black, titanium oxide, zinc oxide, red iron oxide, flaky iron oxide, aluminum powder, cordierite, phthalocyanine blue, iron black and other pigments, glass fiber, glass flake, mica powder, synthetic silica , Reinforcing pigments such as asbestos, other thickeners, anti-rusting or pollution-free anti-rusting pigments, antifoaming agents, wetting agents, precipitation inhibitors, curing accelerators, chelating reaction accelerators, and the like.

Examples of the rust preventive agent or pollution-free rust pigment include conventionally known sodium pentoxide phosphate, ammonium phosphate, zinc phosphate, lead molybdate, barium metaborate, and iron.

Examples of the curing accelerators include phenol, cresol, nonylphenol, bisphenol A, saritylic acid, resorucine, hexmethylenetetramine, 2,4,6-tris (dimethylaminomethyl) phenol, triethylenediamine, and the like.

Especially when tertiary amine is used, it is effective in low temperature hardenability.

Examples of the chelation reaction accelerator include organic acids such as ferrous chloride, ferric chloride, and acetic acid, and inorganic acids such as hydrochloric acid.

In the present invention, the reaction product (curing agent composition) in which the main component containing the epoxy resin as a main component and the compound having the chelate-forming ability are introduced can not achieve the object of the present invention alone. That is, it needs to be mixed before use. Thereafter, the coating is applied to the coated object by a general method such as brush painting, air display coating, roll coater coating, flow coater coating, and the like, and the coating is formed by normal temperature drying or heat drying.

面), 습윤면, 용접면 등에 도포할 수가 있다. 또 아연도금판, 주석도금판이나 알루미늄판, 동판 등의 비철재료 및 샵프라이머(예컨대 워슈프라이머, 아연리치프라이머등)나 각종 하도(下塗)도막상에 도포할 수도 있다.As the material to be coated, steel materials such as mild steel and hard steel are preferred, and cotton wool, chemically treated cotton and green cotton (

Surface), wet surface, weld surface and the like. It can also be applied to non-ferrous materials such as galvanized plate, tin plate, aluminum plate, copper plate, shop primers (for example, wash primers, zinc rich primers, etc.) or various undercoats.

Moreover, you may perform normal top coat on the coating film obtained by the composition of this invention for the purpose of plastering.

Examples of this top coat include vinyl resin paint, chlorinated rubber paint, urethane resin paint, silicone resin paint, acrylic resin paint, fluorine resin paint, alkyd resin paint, epoxy resin paint, and the like. Top coat needs to be selected.

The composition of the present invention can again be utilized for its characteristics and can be used for adhesives and the like.

In the present invention, the crosslinking reaction of the main agent and the curing agent occurs in the drying and film formation process.

Therefore, an appropriate mixing ratio is required between the reaction product (curing agent) in which the compound having the chelate binding ability is introduced. Usually, 1 / 2-2 / 1 is preferable as (epoxy group in the subject) / (active hydrogen group bonded to the nitrogen atom in the hardener).

However, it may be beyond the range of this ratio.

Since the resin composition of this invention mixed at the time of use reacts when left for a long time, and becomes gel, it is preferable to apply | coat within 8 hours immediately after mixing. The coating film thus obtained has very excellent properties in the properties such as surface dryness, moisture resistance, and corrosion resistance after dry curing.

The composition of the present invention can obtain a coating film which is excellent in coating performance obtained in the conventional anticorrosive coating composition and has no inferiority even without using an anti-corrosive pigment.

鋼板)위에 도포한 경우 충분한 도막성능을 발휘할 수 없다고 하는 결점이 있지만, 본 발명 조성물은 청면상(

面上)에 도포해도 우수한 성능을 발휘한다.In addition, ordinary epoxy resin paint is generally steel sheet (

Iii) there is a drawback that sufficient coating performance cannot be exhibited when applied over the present invention.

Excellent performance is achieved even when applied to the surface.

In addition, the composition of the present invention also has a feature that, after formation of the coating film, the chelation reaction with the iron surface proceeds further due to the penetration of a small amount of moisture such as air, resulting in a stronger coating film.

Hereinafter, the details of the present invention will be described according to the examples.

"Part" or "%" shall be expressed as "parts by weight" or "% by weight".

Example 1

100 parts of bisphenol-type epoxy resins (trade name Epicorth 1001, Epoxy equivalent 450-500) manufactured by Shell Chemicals Co., Ltd. were dissolved in 100 parts of ethylene glycol monobutyl ether to obtain a resin solution adjusted to 50% nonvolatile matter.

50 parts of red shell, 100 parts of talc, 50 parts of precipitated barium sulfate, and 100 parts of ethylene glycol monobutyl ether were added to the said resin solution, and it combined with the roller and made it the main subject.

On the other hand, 100 parts of polyamide resin (trade name Tomide 225 made by Fuji Chemical Industry Co., Ltd .: 300 ± 20) and 15 parts of molar assets were reacted in the presence of an inert gas until a predetermined amount of water was obtained at a temperature of 140-150 ° C. A reaction product (curing agent) having a chelate type performance was obtained.

100 parts of the obtained chelate-forming hardeners were dissolved in ethylene glycol monobutyl ether to obtain a solution adjusted to a nonvolatile content of 50%.

The epoxy resin composition having the chelate-forming ability of the present invention was obtained by mixing the main agent and the curing agent solution having the chelate-forming ability at a ratio of 100/18 (weight ratio).

The composition was viscosity-composed with ethylene glycol monobutyl ether so as to be 10-20 poise with a Leon viscometer (rotor No. 1), and then dried film thickness on a blue steel plate (about 1.6 × 50 × 150 mm) rubbed with send paper (# 80). The test was performed using an air spray to 100 microns, followed by naturally drying in a constant temperature room (20 ° C., 75% RH) for 7 days.

The coating performance test results were summarized in Table 1 in accordance with the examples described later.

The result was very excellent in the salt spray test, the moisture resistance test, the salt immersion test and the water resistance test as compared with the comparative examples described later.

Example 2

100 parts of bisphenol-type epoxy resin [the same as Example 1] were melt | dissolved in 100 parts of ethylene glycol monoethyl ether, and the resin solution adjusted to 50% of non volatile matter was obtained.

To the resin solution, 150 parts of talc, 75 parts of precipitated barium sulfate, and 100 parts of ethylene glycol monoethyl ether were added to form a roller.

On the other hand, polyamide resin [trade name Baasamide 115 made by First General Corporation; 100 parts of the amine titer and 15 parts of the molar asset n-propyl ester were reacted at a temperature of 150-160 ° C. in the presence of an inert gas until a predetermined alcohol was obtained to obtain a reaction product (curing agent) having a chelate-forming ability. 100 parts of obtained chelate-forming hardeners were melt | dissolved in ethylene glycol monoethyl ether, and the solution adjusted to 50% of non volatile matter was obtained.

The epoxy resin composition having the chelate-forming ability of the present invention was obtained by mixing the above-mentioned main agent and the curing agent solution having the chelate-forming ability at a ratio of 100/20 (weight ratio). Table 1 shows the test results of the coating film performance obtained in the same manner as in Example 1 using this composition.

Example 3

100 parts of bisphenol-type epoxy resins (trade name Epicoate 1004, Epoxy equivalent 900-1,000) manufactured by Shell Chemicals Co., Ltd. are dissolved in a mixed solvent of xylene / methyl isobutyl ketone = 1: 1 (weight ratio) to obtain a nonvolatile content of 50%. The adjusted resin solution was obtained.

To the resin solution, 50 parts of red shell, 100 parts of talc, 50 parts of precipitated barium sulfate, 50 parts of xylene, and 50 parts of methyl isobutyl ketone were added to form a roller.

On the other hand, 100 parts of polyamide resin (trade name Tomide 210 made by Fuji Chemical Industry Co., Ltd .: 100 ± 5) and 15 parts of protocatecuic acid were present at an inert gas until a predetermined amount of water was obtained at a temperature of 170-175 ° C. Reaction was carried out to obtain a reaction product (curing agent) having a chelate type performance. 100 parts of obtained chelate-forming hardening | curing agents were melt | dissolved in the mixed solvent of xylene / methyl isobutyl ketone / ethylene glycol monoethyl ether = 1: 1: 1 (weight ratio), and the solution adjusted to 50% of non volatile matter was obtained.

The composition of this invention was obtained by mixing the said main material and the hardening | curing agent solution which has chelate formation ability in the ratio of 100/21 (weight ratio). The composition was viscosity-adjusted with a dilute solvent (xylene / methyl isobutyl ketone ethylene glycol monoethyl ether = 1: 1: 1) until it became 10-20 poise with a Leon viscometer (rotor No. 1), and sandpaper (# 80). It was applied by air spray to a dry film thickness of 100 microns on a clean steel sheet (approximately 0.8 x 70 x 150 mm) rubbed with).

After naturally drying for about 20 minutes, the resultant was heat-dried for 60 minutes with a hot stove at 80 ° C. to perform a performance test.

Coating performance test results are shown in Table 1.

Example 4

100 parts of bisphenol-type epoxy resin [the same as Example 1], 5 parts of urea resin (60% non-volatile content) dissolved in a mixed solution of xylene (methyl isobutyl ketone 1: 1 (weight ratio) and adjusted to 50% of non-volatile content) One resin solution was obtained.

To the resin solution were added 10 parts of glass flakes, 40 parts of red shell, 100 parts of talc, 50 parts of precipitated barium sulfate, 50 parts of xylene, 30 parts of methyl isobutyl ketone and 20 parts of isobutanol, and combined with a roller to make the subject.

On the other hand, the same as 70 parts of polyamide resin Example 1, amine adduct resin manufactured by Fuji Kasei Kogyo Co., Ltd. product name Fujicure 202: 120 parts of active hydrogen equivalent weight 120 parts, 10 parts of moles, 5 parts of protocatecuic acid 130-140 ℃ The reaction product (curing agent) having a chelate-forming ability was obtained by reacting in the presence of an inert gas until the desired product water was obtained at a temperature.

100 parts of the obtained chelate type hardening | curing agents were melt | dissolved in the mixed solvent of xylene / methyl isobutyl ketone / ethylene glycol monoethyl ether = 1: 1: 1 (weight ratio), and the solution of 50% of non volatile matter was obtained.

The composition of this invention was obtained by mixing the said hardening | curing agent solution which has a chelate type performance in the ratio of 100/16 (weight ratio). Viscosity of the composition was adjusted with diluent solvent (xylene / methyl isobutyl ketone / ethylene glycol monoethyl ether = 1: 1: 1) to obtain 20-30 poises using a Leon viscometer (rotor No. 1), followed by polishing with a disk On one blue steel sheet (about 2 grains) (approximately 1.6 x 50 x 150 mm), it was applied using a brush to have a dry film thickness of 100 microns. Next, it dried under the same conditions as in Example 1.

Example 5

90 parts of bisphenol-type epoxy resin [brand name Epicoat 834, epoxy equivalent 230-270] made by Shell Chemical Co., Ltd., polyglycol type epoxy resin [product name of Dow Chemical Co., Ltd. brand name DER-741: epoxy equivalent 364-385 ] 10 parts was dissolved in a mixed solvent of xylene / methyl isobutyl ketone / isobutanol = 5: 4: 1 (weight ratio) to obtain a resin solution adjusted to a nonvolatile content of 50%.

To the resin solution, 45 parts of red shell, 5 parts of zinc phosphate, 100 parts of talc, 50 parts of precipitated barium sulfate, 50 parts of xylene, 30 parts of methyl isobutyl ketone, and 20 parts of isobutanol were added together to form a roller.

On the other hand, 100 parts of the amine adduct resin (same as Example 4) and 10 parts of the molar asset were reacted in the presence of an inert gas until a predetermined amount of water was obtained at a temperature of 130-150 ° C., thus having a chelate type reaction product (curing agent). Got. 100 parts of the obtained chelating type curing agent was dissolved in ethylene glycol monobutyl ether, and adjusted to 50% of nonvolatile content to obtain a solution.

The composition of this invention was obtained by mixing the said hardening | curing agent solution which has the said chelate type performance in the ratio of 100/23 (weight ratio).

After adjusting the composition with a dilution solvent (xylene / methyl isobutyl ketone / ethylene glycol monoethyl ether = 1: 1: 1) to 10-20 poise with a Leon viscometer (Roller No. 1), use a disk thunder The coated steel sheet (about 2 grains) (about 1.6 x 70 x 150 mm) was applied using an air spray so as to have a dry film thickness of 100 microns, and dried under the same conditions as in Example 1.

The performance test results of the coating film thus obtained are shown in Table 1.

Comparative Example 1

The subject constructed in the same manner as in Example 1 was used. The hardening | curing agent was used unmodified polyamide resin (same as Example 1) by 50% of non volatile matter. The master and curing agent solutions were mixed at a ratio of 100/17 (weight ratios). The test results of the coating film performance obtained in the same manner as in Example 1 using this mixture are shown in Table 1.

Comparative Example 2

The subject constructed in the same manner as in Example 2 was used.

The hardening | curing agent was used unmodified polyamide resin (the same as Example 2) by 50% of non volatile matter. The main solution and the stabilizer solution were mixed at a ratio of 100/19 (weight ratio).

The coating film performance test results obtained in the same manner as in Example 1 using this mixture are shown in Table 1.

Comparative Example 3

The subject constructed in the same manner as in Example 3 was used. The curing agent was uniformly mixed with 70 parts of unmodified polyamide resin (same as Example 1) and 30 parts of amine adduct resin (same as Example 4), and was adjusted to a nonvolatile content of 50%. The main ingredient and the curing agent solution were mixed at a ratio of 100/15 (weight ratio). The coating film performance test results obtained in the same manner as in Example 4 using this mixture are shown in Table 1.

The subject constructed in the same manner as in Example 5 was used.

The curing agent was used by adjusting the unmodified amine adduct resin (same as in Example 4) with a nonvolatile content of 50%. The main ingredient and the curing agent solution were mixed at a ratio of 100/22 (weight ratio).

The coating film performance test results obtained in the same manner as in Example 5 using this mixture are shown in Table 1.

TABLE 1

As is apparent from the above comparative test results, the composition of the present invention can provide a coating film having excellent water resistance, moisture resistance, or corrosion resistance even without adding an anticorrosive pigment, and exhibits excellent effects even when applied to a steel sheet.

Claims (1)

An amino-based curing agent having an epoxy resin having at least two epoxy groups in one molecule and at least two nitrogen atoms in one molecule and active hydrogens bonded thereto, 5-30% by weight of phenolcarboxylic acid, And / or an epoxy resin composition having a chelate type performance comprising a reaction product obtained by condensation reaction of these esters with an organic solvent capable of dissolving the epoxy resin and the reaction product.