CN115702224B - Electrodeposition coating composition - Google Patents

Electrodeposition coating composition Download PDF

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CN115702224B
CN115702224B CN202180029788.7A CN202180029788A CN115702224B CN 115702224 B CN115702224 B CN 115702224B CN 202180029788 A CN202180029788 A CN 202180029788A CN 115702224 B CN115702224 B CN 115702224B
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epoxy resin
weight
epoxy
composition
parts
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CN115702224A (en
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李奎相
金孝浄
道京海
崔在一
金性民
金健泰
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KCC Corp
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KCC Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to an electrodeposition coating composition comprising a resin, a curing agent and a cationic water-dispersible additive prepared from an additive composition comprising a first epoxy resin, a second epoxy resin and an amine group-containing alkoxysilane, and comprising the above-mentioned first epoxy resin and second epoxy resin in a weight ratio of 1:1 to 5:1.

Description

Electrodeposition coating composition
Technical Field
The present invention relates to an electrodeposition coating composition excellent in storage stability and filterability and capable of forming a coating film excellent in weather resistance and excellent in rust resistance of an edge (edge).
Background
In general, after the body of an automobile is completed, multilayer coating is generally performed to prevent corrosion of the surface of the body and to improve a sound insulation function and to make the appearance elegant. Generally, the above-mentioned multilayer coating is formed by subjecting a vehicle body subjected to a pretreatment step to electrodeposition coating, intermediate coating, top coating, and clear coating.
The electrodeposition coating is a coating method in which an object to be coated is immersed in an electrodeposition coating liquid, and electricity is supplied between the object to be coated and a counter electrode to electrically deposit a coating film on the surface of the object to be coated, and is also called as electrodeposition coating, or ED coating. As the paint used for such electrodeposition coating, epoxy type and acrylic type are mainly used, and epoxy type paint is mainly used in the coating specification requiring high corrosion resistance, and acrylic type paint is mainly used in the coating specification requiring weather resistance and appearance characteristics.
As an example, a cathode electric coating composition is disclosed in korean patent No. 713732 (patent document 1), which comprises: polyoxyalkylene amine; glycidoxy alkyl alkoxy silane; and a sealant as an additive comprising a reaction product of a glycidyl compound. However, the composition of patent document 1 is excellent in edge coating rate but insufficient in storage stability and insufficient in filterability.
Therefore, in practice, there is a need for research and development of an electrodeposition coating composition excellent in storage stability and filterability, which is capable of forming a coating film excellent in weather resistance and excellent in rust resistance of edges (edge).
Prior art literature: korean patent No. 713732 (publication day: 4/26/2002).
Disclosure of Invention
(problem to be solved by the invention)
The present invention aims to provide an electrodeposition coating composition which is excellent in storage stability and filterability and can form a coating film excellent in weather resistance and excellent in rust resistance of an edge (edge).
(measures taken to solve the problems)
The invention provides an electrodeposition coating composition comprising a resin, a curing agent, and a cationic water-dispersing additive,
the cationic water-dispersible additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane,
and comprises the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1.
(effects of the invention)
The electrodeposition coating composition of the present invention is excellent in storage stability and filterability and can form a coating film excellent in weather resistance and excellent in rust inhibitive performance of edges (edge).
Detailed Description
The present invention is described in detail below.
In the present invention, the basic value of the action such as the "unreacted NCO content (NCO%)" can be determined by a method known in the art, and for example, it can be a value determined by a titration method (titration) or the like.
The electrodeposition coating composition according to the present invention comprises a resin, a curing agent, and a cationic water-dispersing additive.
Resin composition
The resin is a main agent of the electrodeposition coating composition, and plays a role in adjusting the characteristics of the prepared coating film.
The resin is not particularly limited as long as it is a resin that can be generally used as a main agent of an electrodeposition coating material, and may include, for example, an epoxy resin. The resin may be a bisphenol type epoxy resin, and the bisphenol type epoxy resin may be a bisphenol a type epoxy resin, for example.
The above resin may be contained in the composition in a content of 5 to 30 parts by weight or 10 to 25 parts by weight for 5 to 30 parts by weight of the curing agent. When the content of the resin is less than the above content, the rust inhibitive performance of the composition is insufficient, and when the content exceeds the above content, the impact resistance of the produced coating film is insufficient.
Curing agent
The curing agent reacts with the resin in a crosslinking manner to effect the curing of the composition.
The curing agent may be an isocyanate resin, and the isocyanate resin is not particularly limited as long as it is a curing agent generally used for a paint. For example, the isocyanate resin may be an aromatic isocyanate and a cycloaliphatic isocyanate, and the aromatic isocyanate may be a cycloaliphatic isocyanate because the aromatic isocyanate is exposed to UV to decompose an aromatic ring by double bonds, thereby reducing weather resistance.
The above alicyclic isocyanate may include, for example, one selected from the group consisting of 1-isocyanato (isocyanato) -3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4-diisocyanato-3, 5-trimethylcyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclohexane, 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4 '-or 4,4' -diisocyanato-dicyclohexylmethane, 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane, 4 '-diisocyanato-3, 3' -dimethyldicyclohexylmethane, 4 '-diisocyanato-3, 3',5,5 '-tetramethyl dicyclohexylmethane, 4' -diisocyanato-1, 1 '-bicyclohexane (dicyclohexyl), 4' -diisocyanato-3, 3 '-dimethyl-1, 1' -bicyclohexane, and 4,4 '-diisocyanato-2, 2',5 '-tetramethyl-1, 1' -bicyclohexane.
The isocyanate resin may be blocked at the end thereof with a blocking agent. The blocking agent stabilizes the terminal isocyanate group to a specific temperature, and when the temperature is equal to or higher than the specific temperature, the blocking agent dissociates from the isocyanate group to regulate the reactivity. The blocking agent may be, for example, an oxime compound such as diethyl malonate, dimethylpyrazole, cyclohexanone oxime, or methylethyl ketoxime, a lactam compound such as epsilon-caprolactam, or gamma-butyrolactam, or an alcohol compound such as methanol or ethanol.
The above-mentioned curing agent may be contained in the composition in a content of 5 to 30 parts by weight or 10 to 20 parts by weight with respect to 5 to 30 parts by weight of the resin. When the content of the curing agent is less than the above content, the composition has poor curability, and when the content exceeds the above content, the coating film prepared has poor rust inhibitive performance.
Cationic water-dispersible additives
The cationic water-dispersible additive controls the fluidity of the composition at the edge (edge) when forming a coating film, and plays a role in improving the coating rate at the edge and the thickening property of the coating film.
The cationic water-dispersible additive described above is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane. The above-described additive composition may include the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1 or a weight ratio of 2:1 to 4:1. The edge (edge) coating film thickening property of the composition is insufficient in the case where the weight ratio of the first epoxy resin to the second epoxy resin is less than 1:1, i.e., the content of the first epoxy resin is less than the second epoxy resin, and the resin synthesis stability is insufficient in the case where the weight ratio exceeds 5:1, i.e., the second epoxy resin is contained in excess.
The epoxy resin (the total amount of the first epoxy resin and the second epoxy resin) and the amine group-containing alkoxysilane may be contained in a weight ratio of 5:1 to 1:1 or a weight ratio of 3:1 to 1:1. In the case where the weight ratio of the epoxy resin to the amine group-containing alkoxysilane is smaller than the above range, i.e., the content of the epoxy resin is smaller than the amine group-containing alkoxysilane, there is a problem that the electrodeposition coating film is redissolved due to an excessive amount of unreacted amine, and in the case where the epoxy resin is contained in excess beyond the above range, the storage stability of the additive is insufficient due to an increase in the molecular weight of the prepared cationic water-dispersible additive.
< first epoxy resin >
The first epoxy resin has a low epoxy group content (Epoxy Group Content) and a high viscosity at 25 ℃ as compared to the second epoxy resin. For example, the epoxy group content may be 300 to 2,000mmol/kg or 500 to 1,100mmol/kg lower with respect to the above-described first epoxy resin, and the viscosity at 25 ℃ may be 40 to 75mpa·s or 50 to 70mpa·s higher than the second epoxy resin.
The epoxy group content of the above first epoxy resin may be 2,500 to 3,500mmol/kg or 2,900 to 3,300mmol/kg. When the epoxy group content of the first epoxy resin is less than the above range, the gloss of the coating film is reduced, and when the epoxy group content exceeds the above range, the problem of insufficient edge coverage of the composition occurs.
The viscosity of the first epoxy resin at 25 ℃ may be 50 to 80mpa·s or 55 to 70mpa·s. When the viscosity of the first epoxy resin at 25 ℃ is less than the above range, the edge coverage of the composition is reduced, and when the viscosity exceeds the above range, the gloss of the coating film is reduced.
The epoxy equivalent of the first epoxy resin may be 250 to 400g/eq or 300 to 350g/eq. When the epoxy equivalent of the first epoxy resin is less than the above range, the gloss of the coating film is lowered, and when the epoxy equivalent exceeds the above range, the edge coverage of the composition is lowered.
< second epoxy resin >
The epoxy group content of the above second epoxy resin may be 3,800 to 4,500mmol/kg or 4,000 to 4,300mmol/kg. In the case where the epoxy group content of the second epoxy resin is less than the above range, the synthetic stability of the additive may be problematic, and in the case where it exceeds the above range, the edge coverage of the composition may be lowered.
The viscosity of the second epoxy resin at 25℃may be 3 to 15 mPas or 5 to 10 mPas. The gloss of the coating film prepared in the case where the viscosity of the second epoxy resin at 25 ℃ is less than the above range may be reduced, and in the case where it exceeds the above range, the edge coverage of the electrodeposition coating composition may be reduced.
The epoxy equivalent of the second epoxy resin may be 200 to 280g/eq or 220 to 260g/eq. When the epoxy equivalent of the second epoxy resin is less than the above range, the reaction rate of the composition increases, resulting in insufficient workability of the composition, and when the epoxy equivalent exceeds the above range, the purity is lowered.
< amino group-containing alkoxysilane >
The amine group-containing alkoxysilane reacts with an epoxy group of the epoxy resin to form a cationic resin and silanol is formed in the resin, and when the viscosity is lowered by drying after electrodeposition coating, the viscosity of the composition is raised by a siloxane reaction, thereby controlling the fluidity of the edge portion.
The amine group-containing alkoxysilane may be represented by the following chemical formula 1.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
R 1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
For example, R 1 May be a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, R 2 Can be a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms.
The above alkylene and alkoxy groups may be linear or branched. The alkylene group refers to a branched or straight-chain or cyclic divalent radical derived by removing 1 hydrogen atom from a carbon atom of an alkyl group. For example, the alkylene group may be methylene (-CH) 2 (-), 1-ethylene (-CH (CH) 3 ) (-), 1, 2-ethylene (-CH) 2 CH 2 (-), 1-propylene (-CH (CH) 2 CH 3 ) (-), 1, 2-propylene (-CH) 2 CH(CH 3 ) (-), 1, 3-propylene (-CH) 2 CH 2 CH 2 (-), 1, 4-butylene (-CH) 2 CH 2 CH 2 CH 2 (-), 2, 4-butylene (-CH) 2 (CH 3 )CH 2 CH 2 (-) and the like, but is not limited thereto.
The cationic water-dispersing additive may be a silanol group-containing silane-modified epoxy resin. For example, with respect to the above cationic water-dispersing additive, the solids content may be 20 to 30 wt% or 23 to 27 wt%, the degree of neutralization may be 10 to 40mmol/100g or 15 to 35mmol/100g, and the viscosity at 25 ℃ may be 10 to 100cps or 30 to 80cps.
When the solid content of the cationic water-dispersible additive is less than the above range, the edge coverage of the composition is reduced, and when the solid content exceeds the above range, the viscosity of the composition is increased and the storage property is lowered. In addition, when the neutralization degree of the cationic water-dispersible additive is less than the above range, the storage property of the composition may be insufficient, and when the neutralization degree exceeds the above range, the storage property of the composition may be insufficient. In addition, when the viscosity of the cationic water-dispersible additive is less than the above range, the edge coverage of the composition is reduced, and when the viscosity exceeds the above range, the storage stability of the composition is insufficient.
The above cationic water-dispersing additive may be contained in the composition in a content of 3 to 15 parts by weight or 5 to 10 parts by weight with respect to 5 to 30 parts by weight of the resin. When the content of the cationic water-dispersible additive is less than the above content, the edge coverage of the composition may be reduced, and when the content exceeds the above content, the appearance characteristics and gloss of the coating film prepared may be reduced.
Additive agent
The electrodeposition coating composition may further contain 1 or more additives selected from the group consisting of amine compounds, solvents, neutralizing agents, defoamers, degreasing agents, and fluidity regulators.
The additives are not particularly limited as long as they can be generally used in the electrodeposition coating composition.
The electrodeposition coating composition according to the present invention as described above is excellent in storage stability and filterability and can form a coating film excellent in weather resistance and excellent in rust inhibitive performance of edges (edge).
The present invention will be described in more detail with reference to examples. However, these examples are merely for aiding in understanding the present invention, and the scope of the present invention is not limited to these examples in any way.
Modes for carrying out the invention
Synthesis example 1: curing agent-1 (blocked cycloaliphatic isocyanate)
To a four-necked flask equipped with a thermometer and a cooler, 40 parts by weight of methyl isobutyl ketone, 400 parts by weight of isophorone diisocyanate, and 0.27 parts by weight of dibutyltin laurate were added and the temperature was raised to 30℃under a nitrogen atmosphere. Thereafter, the temperature was adjusted to not more than 60℃while adding 360 parts by weight of 2- (2-butoxyethoxy) ethanol, and then left at 60℃for 90 minutes. Thereafter, 120 parts by weight of methyl ethyl ketoxime was added, and then the temperature was raised to 80℃and kept for 3 hours until the unreacted NCO% became 0.02% by weight or less, and then methyl isobutyl ketone was added to adjust the solid content to 80% by weight, to prepare a blocked alicyclic isocyanate.
Synthesis example 2: curing agent-2 (blocked aromatic isocyanate)
To a four-necked flask equipped with a thermometer and a cooler, 1,800 parts by weight of 2- (2-butoxyethoxy) ethanol, 106.6 parts by weight of methyl isobutyl ketone and 0.2 part by weight of dibutyltin laurate were charged and heated to 30℃under a nitrogen atmosphere. Thereafter, while adding 2,028.6 parts by weight of an aromatic isocyanate (manufacturer: dow chemical Co., ltd. (DOW CHEMICAL COMPANY), product name: PAPI PB 7519), the temperature was adjusted to not more than 60℃and left at 60℃for 90 minutes. Thereafter, 0.1 part by weight of dibutyltin laurate and 200 parts by weight of trimethylolpropane were added, and then the temperature was raised to 80℃and kept for 3 hours until the unreacted NCO% became 0.02% by weight or less, and then methyl isobutyl ketone was added to adjust the solid content to 80% by weight, to prepare a blocked aromatic isocyanate.
Synthesis example 3: preparation of cationic Water-dispersing additive-1
112 parts by weight of a first epoxy resin (manufacturer: dow chemical Co., product name: DER 732, epoxy group content: 3,130mmol/kg, viscosity at 25 ℃ C.: 65.+ -. 5 mPa.s, epoxy equivalent: 320 g/eq), 36 parts by weight of a second epoxy resin (manufacturer: hexion, product name: cardura E-10P, epoxy group content: 4,170mmol/kg, viscosity at 25 ℃ C.: 7 mPa.s, epoxy equivalent: 240 g/eq), 110 parts by weight of an amino-containing alkoxysilane (manufacturer: momentive, product name: silquest A-1100, gamma-aminopropyl triethoxysilane (gamma-aminopropyltriethoxy silane)) and 120 parts by weight of isopropanol were charged into the reaction vessel. Thereafter, the reaction was performed by heating to 110℃under an anhydrous nitrogen atmosphere until the Gardner-Holdt viscosity became T to W. Thereafter, 600 parts by weight of deionized water and 22 parts by weight of lactic acid (aqueous solution having a concentration of 50% by volume) were added and dispersed in an aqueous medium to prepare a cationic water-dispersible additive-1 having a solids content of 25% by weight, a neutralization degree of 25mmol/100g and a viscosity of 45cps at 25 ℃.
Synthesis examples 4 to 8: preparation of cationic Water-dispersing additives-2 to-6
Cationic water-dispersible additives were prepared in the same manner as in Synthesis example 3, except that the contents of the respective components were adjusted as in Table 1 below.
Synthesis example 9: preparation of cationic Water-dispersing additive-7
24 parts by weight of a third epoxy resin (manufacturer: national chemical, product name: YD-011, epoxy equivalent: 450 to 490 g/eq) and 52 parts by weight of BUTYL CELLOSOLVE (BUTYL CELLOLVE) were added to the reaction vessel, followed by heat thawing. Thereafter, 276 parts by weight of polyoxypropylene diamine (manufacturer: huntsman, product name: jeffamine D2000, number average molecular weight: 2,000mol/g, amine equivalent: 996.5 g/eq) and 29 parts by weight of a second epoxy resin (manufacturer: hexion, product name: cardura E-10P, epoxy group content: 4,170mmol/kg, viscosity at 25 ℃ C.: 7mPa.s, epoxy equivalent: 240 g/eq) were added for reaction. When the epoxy equivalent was 1,000g/eq or more, 24 parts by weight of a fourth epoxy resin (manufacturer: national chemistry, product name: YD-128, epoxy equivalent: 180 to 190 g/eq) was added to react the epoxy resin, 19 parts by weight of lactic acid (aqueous solution having a concentration of 50 vol%) was added to neutralize the epoxy resin, and 576 parts by weight of ionized water was slowly dropped to disperse the mixture in water, thereby preparing cationic water-dispersible additive-7 having a solid content of 35 wt% and a neutralization degree (MEQACID) of 25mmol/100 g.
TABLE 1
Synthesis example 10: preparation of silane-modified epoxy amine compounds
Into the reaction vessel were charged 1,000 parts by weight of polyoxypropylene diamine (manufacturer: huntsman, product name: jeffamine D2000, number average molecular weight: 2,000mol/g, amine equivalent: 996.5 g/eq), 100 parts by weight of a second epoxy resin (manufacturer: hexion, product name: cardura E-10P, epoxy group content: 4,170mmol/kg, viscosity at 25 ℃ C.: 7 mPa.s, epoxy equivalent: 240 g/eq), 141.6 parts by weight of glycidoxypropyl trimethoxysilane (manufacturer: momentive, product name: silquest A-187), and 130 parts by weight of 2-ethylhexanol. Thereafter, the reaction was performed by heating to 110℃under an anhydrous nitrogen atmosphere until the Gardner-Holdt viscosity became S-T. Thereafter, 4049.6 parts by weight of deionized water and 66.3 parts by weight of lactic acid (aqueous solution having a concentration of 50% by volume) were added and dispersed in an aqueous medium to prepare a silane-modified epoxy amine compound having a solids content of 22% by weight.
Examples 1 to 5 and comparative examples 1 to 6: preparation of electrodeposition coating composition
The raw materials of the portions (part) 1 to 4 described in tables 2 and 3 were charged into a separate reactor equipped with a stirrer, a cooler, a heater and a thermometer and heated to 125 ℃, and then the portion 5 was charged and the temperature was kept 145 ℃ while measuring the epoxy equivalent until 1,110g/eq was reached. Thereafter, the temperature was adjusted to 110 ℃, part 6 and part 7 were added in this order and the reaction was performed at 125 ℃ for 90 minutes. Thereafter, the temperature was adjusted to 100 ℃ and cooled to 70 ℃ after adding part 8 to part 10. Thereafter, part 11 was followed by part 12 and the reaction was carried out at 100℃for 1 hour. Thereafter, the solvent was recovered in a vacuum to a content corresponding to the portion 13 to obtain a resin reactant. Thereafter, 1 water dispersion was performed while adding the above resin reactant to the dispersion tank containing the portions 14 to 16, and after stirring for 1 hour, the portion 17 was added to adjust the viscosity. Thereafter, the temperature was adjusted to 45 ℃ or lower and the part 18 was added to prepare an electrodeposition coating composition.
TABLE 2
TABLE 3
The product names of the respective components used in the comparative examples and examples are shown in table 4 below.
TABLE 4
Composition of the components Product name
Resin-1 KOREMUL-BSA-60A (manufacturer: korean agriculture chemical Co., ltd.)
Resin-2 BISPHENOL A (manufacturer: jinhu P)&B chemistry)
Resin-3 EPOXY YD-128 (manufacturer: national institute chemical)
Organic solvents DOWANOL PM (manufacturer: dow chemical Co.)
Crosslinking agent AMICURE KT-22 (manufacturer: win-win)
Defoaming agent SN DEFOAMER-180 (manufacturer: SAN NOPCO)
Test example: evaluation of physical Properties
The electrodeposition coating compositions prepared in the above examples and comparative examples were subjected to electrodeposition coating at 240V for 3 minutes using a rectifier on a test piece pretreated with zinc phosphate (chromate treated aluminum test piece, transverse width×vertical length×thickness=150 mm×70mm×0.8 mm) to form a coating film. The physical properties of the prepared coating film were measured by the following methods and the results are shown in tables 5 and 6.
(1) Gloss of the product
The 60 ° gloss of the coating film was measured vertically and horizontally. At this time, it is determined that the higher the gloss value is, the higher the gloss is.
(2) Curability of
Cotton sufficiently wetted with methyl isobutyl ketone (Methyl isobutyl ketone, MIBK) solvent was used to move on the coating film, and the number of movements until defects occurred in the coating film were measured at 170 ℃ and 175 ℃.
(3) Impact resistance
When 1kg of dropping weight was dropped onto the final coating film while changing the dropping height of the dropping weight from 20cm to 50cm, the appearance of the coating film was observed and the maximum dropping height at which cracking and peeling phenomenon did not occur in the coating film was measured to evaluate impact resistance.
(4) Hardness of
Hardness was measured using Mitsubishi pencils for coating film according to MS652-05 and ISO 15184.
Specifically, the maximum hardness (3B, 2B, B, HB, F, H, 2H, 3H: poor) that did not damage the final coating film was measured using the pencils of 3B, 2B, B, HB, F, H, 2H and 3HExcellent).
(5) Weather resistance-1: Q-UVA
According to ISO 11507, gloss change was confirmed on a Q-UVA Type 21 day basis. The initial coating film before weather resistance test was evaluated on the basis of 60 ° gloss as follows: the gloss change rate is excellent when less than 10%; the gloss change rate is generally 10% or more and less than 30%; when the gloss change rate is 30% or more, the effect is poor.
(6) Weather resistance-2: outdoor exposure
Test pieces were prepared and exposed outdoors for 21 days, and gloss change was confirmed on the basis of 60 ° gloss of the initial coating film before the test. The evaluation was as follows: the gloss change rate is excellent when less than 10%; the gloss change rate is generally 10% or more and less than 30%; when the gloss change rate is 30% or more, the effect is poor.
(7) Coating film thickening-1: blade
The electrodeposition coating composition was applied to the edge portion of the blade (blade) as described above, and the thickness of the coating film at the edge portion of the blade (blade) was measured by an electron microscope.
(8) Thickening of coating filmSex-2: punching hole
The electrodeposition coating composition was applied to a punched test piece (manufacturer: ever Steel) at 240V for 3 minutes, and the thickness of the coating film at the edge portion of the punched test piece was measured by an electron microscope.
(9) Filterability
The degree of passage of the electrodeposition coating compositions prepared in examples and comparative examples was grasped by using a nylon mesh screen (sieve) of 100 mesh (mesh), and filterability was evaluated with o (good), Δ (general), and X (bad).
In addition, the filterability was evaluated in the same manner as described above after storing the above composition at 40℃for 7 days.
(10) Screen residue (sieve residue)
The amount of residue remaining on the mesh screen was measured after 500g of the electrodeposition coating composition prepared in examples and comparative examples was filtered with a 100 mesh nylon mesh screen (sieve).
In addition, after the above composition was stored at 40℃for 7 days, the screen residue was measured in the same manner as in the above method.
TABLE 5
TABLE 6
As shown in table 5, the compositions of examples 1 to 5 were excellent in filterability and small in screen size even after storage at 40 ℃ for 7 days, and the coating films prepared therefrom were also excellent in thickening property.
In contrast, comparative example 1 using the cationic water-dispersible additive containing no cationic water-dispersible additive and comparative example 6 using the cationic water-dispersible additive containing no amino group-containing alkoxysilane of synthetic example 9 were insufficient in curability, insufficient in coating film thickening property, and insufficient in weather resistance. In addition, comparative example 2 using the cationic water-dispersible additive of synthetic example 6 containing no second epoxy resin and comparative example 3 using the cationic water-dispersible additive of synthetic example 7 containing no first epoxy resin were insufficient in filterability after storage at 40 ℃ and also insufficient in weather resistance. Further, comparative example 4 using the cationic water-dispersible additive of Synthesis example 8 in which the weight ratio of the first epoxy resin to the second epoxy resin was 0.32:1 was insufficient in weather resistance.
On the other hand, comparative example 5 using a silane-modified epoxy amine compound instead of the cationic water-dispersible additive was insufficient in weather resistance.
(industrial applicability)
The electrodeposition coating composition according to the present invention is excellent in storage stability and filterability, and can form a coating film excellent in weather resistance and excellent in rust inhibitive performance of edges (edge).

Claims (2)

1. An electrodeposition coating composition comprising an epoxy resin, a curing agent which is a blocked isocyanate resin of a blocking agent, and a cationic water-dispersing additive,
the cationic water-dispersible additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane,
the first epoxy resin has an epoxy group content of 2,500 to 3,500mmol/kg, a viscosity of 50 to 80 mPas at 25 ℃ and an epoxy equivalent of 250 to 400g/eq,
the second epoxy resin has an epoxy group content of 3,800 to 4,500mmol/kg, a viscosity of 3 to 15 mPas at 25 ℃ and an epoxy equivalent of 200 to 280g/eq,
the electrodeposition coating composition contains the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1,
the cationic water-dispersible additive has a solids content of 20 to 30 wt%, a degree of neutralization of 10 to 40mmol/100g, a viscosity of 10 to 100cps at 25 ℃,
in the above composition, 5 to 30 parts by weight of the above curing agent and 3 to 15 parts by weight of the above cationic water-dispersing additive are contained with respect to 5 to 30 parts by weight of the above epoxy resin.
2. The electrodeposition coating composition according to claim 1, wherein,
the above-mentioned amine group-containing alkoxysilane is represented by the following chemical formula 1,
[ chemical formula 1]
In the above-mentioned chemical formula 1,
R 1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
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