CN101595148A - Cathode electrodeposition paint composition with improved curing and anticorrosion patience - Google Patents

Cathode electrodeposition paint composition with improved curing and anticorrosion patience Download PDF

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Publication number
CN101595148A
CN101595148A CNA2007800489266A CN200780048926A CN101595148A CN 101595148 A CN101595148 A CN 101595148A CN A2007800489266 A CNA2007800489266 A CN A2007800489266A CN 200780048926 A CN200780048926 A CN 200780048926A CN 101595148 A CN101595148 A CN 101595148A
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compound
resin
amine
glycidyl ether
composition
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CN101595148B (en
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宋胤锡
吴溢锡
郑夏泽
金载孝
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KCC Corp
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KCC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates

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  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to the cationic electrodeposition resin combination, it comprises the cross-linking agent resin that the 20-70 weight part contains the reaction product of glycidyl ether-amine deutero-polyol compound and blocked polyisocyanates compound; 30-80 weight part base resin; With the metallic curing catalysts resin of 0.1-10 weight part, wherein said glycidyl ether-amine deutero-polyol compound is derived from the Mannich reaction products of phenolic compound, amine compound and formalin, and described composition shows good preservative property and curing performance when time on the parts that are applied to automobile frame and various steel construction.

Description

Cathode electrodeposition paint composition with improved curing and anticorrosion patience
Technical field
The present invention relates to the cationic electrodeposition resin combination, it comprises the cross-linking agent resin that the 20-70 weight part contains the reaction product of glycidyl ether-amine deutero-polyol compound and blocked polyisocyanates compound; 30-80 weight part base resin; With the metallic curing catalysts resin of 0.1-10 weight part, wherein said glycidyl ether-amine deutero-polyol compound is derived from the Mannich reaction products of phenolic compound, amine compound and formalin.
Background technology
Galvanic deposit lacquer was introduced and as the antifouling paste based on the various industry of automotive industry in the seventies in 20th century, and because their validity, homogeneity and environment friendly have been widely used for various parts and automobile frame.Electrodeposition resin (it is the main ingredient of galvanic deposit lacquer) is the most important component of decision lacquer overall performance.Electrodeposition resin comprises base resin and cross-linking agent resin usually, and can comprise curing catalysts.
Resins, epoxy is the representative that is used for the base resin of cationic electrodeposition.As cross-linking agent resin, mainly use blocked polyisocyanates.More particularly, prepare conventional cationic electrodeposition resin according to the method for following steps: will have 180-10,000 normal Resins, epoxy by based on the amount of solids content 10-90% and bisphenol-A and its derivative or softening agent for example modified polyether mix; Make the reaction in the presence of excessive solvent under 70-170 ℃ of amine and glycol; At high temperature remove the organic solvent that is included in this reaction mixture by the vacuum removal process; Cross-linking agent resin is mixed in this mixture of having removed solvent; For example formic acid, lactic acid or acetate neutralize this mixture fully with organic acid; With by adding deionized water 4-12 hour this mixture is dispersed in the water.
Japan special permission publication number H4-91170 and H5-155980 (KANSAI) use polyamide resin as erosion resistance and the curing performance of base resin with the raising edge, worsen and shortage flexible problem but have such as outward appearance, reason is that this polyamide resin increases the cross-linked speed during coating forms.The common softening agent that uses is solving this kind problem, but softening agent causes another problem water-fast and that corrodibility reduces.
Japan special permission publication number H2-219870 (KANSAI) has described plumbous oxide and has improved the adhesion property of this type of conventional cationic electrodeposition resin, crosslinked and solidification rate.Yet plumbous comprising runs counter to the international trend of heavy metal being implemented restriction.
Summary of the invention
The inventor has developed the cationic electrodeposition resin combination, and it contains the reaction product of glycidyl ether-amine deutero-polyol compound and blocked polyisocyanates as linked; With barium as improving the solidified curing catalysts.Can improve erosion resistance and curing performance and keep the outward appearance of equivalent level and flexible simultaneously by using conventional production unit (non-specially designed equipment) preparation and comparing according to cationic electrodeposition resin combination of the present invention with those of routine.
Therefore, the purpose of this invention is to provide high functionality cationic electrodeposition resin combination with improved erosion resistance and curing performance.
Detailed Description Of The Invention
The present invention relates to the cationic electrodeposition resin combination, it comprises the cross-linking agent resin that the 20-70 weight part contains the reaction product of glycidyl ether-amine deutero-polyol compound and blocked polyisocyanates compound; 30-80 weight part base resin; With the metallic curing catalysts resin of 0.1-10 weight part, wherein said glycidyl ether-amine deutero-polyol compound is derived from the Mannich reaction products of phenolic compound, amine compound and formalin.
To describe the present invention below in detail.
Cross-linking agent resin
Electrodeposition resin comprises base resin and cross-linking agent resin usually, and can comprise curing catalysts.Cross-linking agent resin and base resin reaction also form final coating.More particularly, the isocyanate group that is included in the cross-linking agent resin forms stable coating with the hydroxyl that is included in the base resin giving reaction under fixed temperature or the higher temperature.For wherein with cross-linking agent resin and base resin blended composition, in order to prevent that isocyanate group and the hydroxyl in the base resin in the cross-linking agent resin from reacting under than the described temperature low to fixed temperature, use has the cross-linking agent resin of blocked isocyanate system and the component in base resin is passed through to provide the function such as good curing performance, erosion resistance, water tolerance etc. forming coating for the urethane reaction under the high temperature of fixed temperature than described.
Be used for the reaction product that cross-linking agent resin of the present invention contains glycidyl ether-amine deutero-polyol compound and blocked polyisocyanates compound; 30-80 weight part base resin, and described glycidyl ether-amine deutero-polyol compound is derived from the Mannich reaction products of phenolic compound, amine compound and formalin.
Mannich reaction is the reaction that contains between aldehyde compound, uncle or secondary amine compound and the phenolic compound.As everyone knows, comprise amine compound is widely used as conventional epoxy-based lacquers via the composition of the active hydrogen of Mannich reaction low temperature curing agent.Know, introduce epoxy hardener, then under room temperature and low temperature, obtain good curing performance if this kind comprised the Mannich reaction products of the active hydrogen of amine compound.In the present invention, different with the conventional Mannich reaction products that is used for conventional epoxy-based lacquers, use contains the Mannich modification glycidyl ether-amine deutero-polyvalent alcohol type compound of reactive hydroxyl, it be by the active hydrogen of removing amine compound from Mannich reaction products and in Mannich reaction after obtain, so can have various structures and application by further reaction.The present invention introduces glycidyl ether-amine deutero-polyol compound cross-linking agent resin in the electrodeposition resin composition and causes the coating that obtains to have good curing performance with the urethane reaction of isocyanate group.As a result, the present invention can improve erosion resistance.
The phenolic compound that is used for Mannich reaction can be selected from, but is not limited to: cresols, butylphenol, octyl phenol, nonylphenol and phenol, be preferably selected from octyl phenol, nonylphenol and phenol, and more preferably be selected from nonylphenol and phenol.Described phenolic compound can use individually or use with the mixture that is selected from two kinds of compounds of above-mentioned group.The amine compound that is used for Mannich reaction is aliphatic series or aromatic amine compound preferably, more preferably is selected from ethylene diamine, trimethylene diamines, hexamethylene-diamine, eight methylene diamine, diethylenetriamine, Triethylenetetramine (TETA), tetracthylene pentamine and m-xylene diamine.Described amine compound can use individually or use with the mixture that is selected from two or more compounds of above-mentioned group.
The amount that is used for the phenolic compound of Mannich reaction is 20-50wt%, preferred 25-45wt%, and more preferably 30-40wt% is based on the amount of Mannich reaction products.If the amount of phenolic compound is less than 20wt%, erosion resistance may reduce.If the amount of phenolic compound is greater than 50wt%, viscosity and state of cure may excessively increase.The amount that is used for the amine compound of Mannich reaction is 20-50wt%, preferred 25-45wt%, and more preferably 30-40wt% is based on the amount of Mannich reaction products.If the amount of amine compound is less than 20wt%, then unreacted material remains in the reaction product, so may can not get sufficient coating performance.If the amount of amine compound greater than 50wt%, then forms urea functional group, so during reaction or afterwards may produce insoluble particle.The amount that is used for the formalin of Mannich reaction is 15-45wt%, preferred 20-40wt%, and more preferably 25-35wt% is based on the amount of Mannich reaction products.If the amount of formalin is less than 15wt%, then unreacted amine may produce in large quantities.If greater than 45wt%, then there is the risk of gelation in the amount of formalin, reason is that viscosity may exceedingly increase.
Can prepare various Mannich reaction products according to phenolic compound and amine compound.Preferred Mannich product has, but is not limited to the structure of following formula 1.
[formula 1]
Wherein each among the R is represented phenolic compound independently, preferred cresols, butylphenol, octyl phenol, nonylphenol or phenol.
Preferably, the glycidyl ether-amine deutero-polyol compound that is used for cross-linking agent resin is the reaction product of Mannich reaction products, hydroxyl amine compound and glycidyl ether compound.Described hydroxyl amine compound is hydroxyl aliphatic series or aromatic amine compound preferably, more preferably be selected from monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), single ehtylethanolamine and monomethyl-ethanolamine, be more preferably and be selected from ehtylethanolamine and Mono Methyl Ethanol Amine.Described glycidyl ether compound is preferably selected from phenyl glycidyl ether and butylglycidyl ether.
The amount of described hydroxyl amine compound is the 8-30 weight part, preferred 11-27 weight part, and more preferably 14-24 weight part is based on the total solid weight of the described Mannich reaction products of 100 weight parts.If the amount of described hydroxyl amine compound is less than 8 weight parts, reactive end hydroxyl deficiency then is so may carry out by halves with the curing reaction of isocyanate group.If the amount of described hydroxyl amine compound is greater than 30 weight parts, the stability of reaction product may reduce.The amount of described glycidyl ether compound is the 40-70 weight part, preferred 44-64 weight part, and more preferably 48-60 weight part is based on the total solid weight of the described Mannich reaction products of 100 weight parts.
Can be used for the preferred glycidyl ether derived from Mannich reaction products of the present invention-amine deutero-polyol compound has, but is not limited to the structure of following formula 2.
[formula 2]
Figure A20078004892600081
R wherein 1In each represent phenolic compound independently, preferred cresols, butylphenol, octyl phenol, nonylphenol or phenol; R 2In each represent glycidyl ether compound independently, preferred butylglycidyl ether or phenyl glycidyl ether; And R 3Represent the hydroxyl amine compound, preferred monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), single ehtylethanolamine or monomethyl-ethanolamine.
The amount that is used for the glycidyl ether-amine deutero-polyol compound of the present invention's cross-linking agent resin is 1-20wt%, preferred 1-10wt%, and more preferably 1-5wt% is based on the amount of this cross-linking agent resin.If the amount of described glycidyl ether-amine deutero-polyol compound is less than 1wt%, the effect of improving curing performance is insufficient.If the amount of described glycidyl ether-amine deutero-polyol compound is greater than 20wt%, then because viscosity that increases and initial cure fast, outward appearance may worsen.
Blocked polyisocyanates, it can react with the glycidyl ether-amine deutero-polyol compound that contains Mannich reaction products according to the present invention, can freely be selected from and be known as those that can be used for the cationic electrodeposition resin combination.Blocked polyisocyanates preferably but is not limited to the reaction product of diisocyanate cpd and hydroxy acryl acid ester cpds or alkylol cpd.The amount of blocked polyisocyanates is 80-99wt%, preferred 90-99wt%, and more preferably 95-99wt% is based on the amount of cross-linking agent resin.If the amount of blocked polyisocyanates is less than 80wt%, then may there be uncured problem.Become faster if the amount of blocked polyisocyanates greater than 99wt%, is then solidified, but erosion resistance may reduce.
Described diisocyanate cpd is aliphatic series or aromatic diisocyanate compound preferably, more preferably be selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-methylene-bis (phenyl diisocyanate), tetramethylene diisocyanate and hexamethylene diisocyanate.Described hydroxy acryl acid ester cpds is methacrylic acid 2-hydroxyl ethyl ester preferably.Described alkylol cpd is preferably selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, TriMethylolPropane(TMP) and propylene glycol.
The amount that is used for according to the cross-linking agent resin of cationic electrodeposition resin combination of the present invention is the 20-70 weight part, preferred 25-50 weight part, more preferably 30-40 weight part.If the amount of cross-linking agent resin is less than 20 weight parts, then solidification value increase and erosion resistance reduce owing to uncured.If the amount of cross-linking agent resin is greater than 70 weight parts, then because high cured density and outward appearance worsens, and erosion resistance reduces owing to lack the epoxy composition in the main material.
Base resin
The base resin that is used for general electrodeposition resin is the component that constitutes final coating with cross-linking agent resin.The characteristic that determines final coating according to the chemistry and the physicals of base resin.Epoxy compounds mainly is used as the main ingredient of base resin, because erosion resistance, adhesion property and thermotolerance that it provides for final coating.For the cationic electrodeposition resin, the reaction of epoxy compounds and amine compound to be providing hydroxyl, and this hydroxyl is to being necessary with the reaction of the disassociation isocyanate group of solidifying agent in coating procedure.Epoxy compounds especially has good erosion resistance, so be generally used for requiring the coating of the material of erosion resistance most.The molecular weight that is used for the epoxy compounds of base resin is 180-2,000.Epoxy compounds can be selected from those with one or two epoxy group(ing), and uses alone or in combination.Also have, by further bringing up to proper level with bisphenol-A reaction molecular amount.The main amine compound that uses is uncle or secondary aliphatic series, aromatics or cycloaliphatic amines.Aliphatic series, aromatics or the cycloaliphatic amines that has one or more active hydrogens or have one or two hydroxyl can be used for improving curing performance.The amount of epoxy compounds can be 60-90wt%, and the amount of amine compound can be 10-40wt%, based on the amount of base resin, but does not limit this.
The amount that is used for according to the base resin of cationic electrodeposition resin combination of the present invention is the 30-80 weight part, preferred 50-75 weight part, more preferably 60-70 weight part.If the amount of base resin is less than 30 weight parts, then outward appearance (or slickness), flexible and erosion resistance reduction.If the amount of base resin is greater than 80 weight parts, then curing performance becomes and is a problem.
The curing catalysts resin
Though general electrodeposition resin composition not necessarily comprises curing catalysts, electrodeposition resin composition of the present invention comprises the curing catalysts resin that contains curing catalysts individually.As everyone knows, if add in the electrodeposition resin metal to the then reductions that become such as the reaction stability of electrodeposition resin, storage stability, strainability independently as curing catalysts.This type of problem that reduces reaction stability, storage stability, strainability etc. can followingly solve: prepare metal-containing salt or the metallo-chelate curing catalysts resin as curing catalysts independently, and it is added in the electrodeposition resin.The effect of curing catalysts is to improve the hydroxyl in the base resin and the reaction of the isocyanate group in the cross-linking agent resin.Curing catalysts can reduce temperature of reaction through suitably selecting.
Cationic electrodeposition resin combination according to the present invention comprises metallic curing catalysts resin, and purpose is the control solidification rate.The metal that is used for the curing catalysts resin can selected among zirconium, zinc, calcium, lead, tin, bismuth, cobalt, titanium, aluminium, chromium and barium, and described metal can exist by salt or inner complex form.More preferably, metal-salt or metallo-chelate are hydrated barta, phenol-barium salt or phenol-barium inner complexs.Be more preferably, metallic curing catalysts resin contains phenol-barium salt or phenol-barium inner complex.
The amount that is used for the metal of curing catalysts resin is 1-20wt%, preferred 3-15wt%, and more preferably 5-10wt% is based on the amount of this curing catalysts resin.If the amount of metal is less than 1wt%, then curing performance is insufficient.If the amount of metal is greater than 20wt%, then solidification rate becomes too fast and the outward appearance deterioration that becomes.
The amount that is used for according to the metallic curing catalysts resin of cationic electrodeposition resin combination of the present invention is the 0.1-10 weight part, preferred 0.1-7 weight part, more preferably 0.1-5 weight part.If the amount of metallic curing catalysts resin is less than 0.1 weight part, then the desired temperature of the reaction of hydroxyl in the base resin and the isocyanate group in the cross-linking agent resin improves, and because the energy expenditure that increases causes cost to increase.If the amount of metal is greater than 10 weight parts, then the content of curing catalysts becomes greater than the desired appropriate amount of reaction, so may there be the problem of storage stability owing to the precipitation capacity increase of curing catalysts between the shelf lives of electrodeposition resin.
To illustrate the present invention in more detail by following examples and comparative example.Yet following examples only are used for illustrating the present invention, so should not be interpreted as by they restriction scope of the invention.
Embodiment 1
Prepare according to the glycidyl ether derived from Mannich reaction products of the present invention-amine deutero-polyol compound by the method for the component shown in the table 1 according to explained later.
[table 1]
The component of preparation glycidyl ether-amine deutero-polyol compound
Component Amount
(A) nonylphenol 184.9g
(B) m-xylene diamine 192.1g
(C) formalin 151.0g
(D) water of Hui Shouing -125.0g
(E) Mono Methyl Ethanol Amine 76.9g
(F) butylglycidyl ether 220.1g
(G) methoxypropanol 300.0g
Amount to 1000.0g
To the three neck 2L flasks that are equipped with thermometer, water cooler and mechanical stirrer, add nonylphenol (A) and m-xylene diamine (B) and temperature is brought up to 70 ℃ according to table 1.To wherein adding formalin (C) lentamente 1 hour, holding temperature kept 2 hours down at 95 ℃ then.Temperature is brought up to 125 ℃, and reclaim the water that produces by dehydration reaction.When the amount of the water (D) that reclaims during, reaction mixture is cooled to 90 ℃ up to 125g.To wherein adding Mono Methyl Ethanol Amine (E) and butylglycidyl ether (F) and keeping this reaction mixture 2 hours.Temperature is brought up to 125 ℃, and reclaimed unreacted diamines 30 minutes.Reaction mixture is cooled to 110 ℃, and dilutes with termination reaction with methoxypropanol (G).React carefully, because reaction mixture is easy to during reaction seethe with excitement.If the rate of recovery of unreacted diamines is insufficient, then can under vacuum, at high temperature reclaim unreacted diamines.As above the product of Huo Deing has 70% solids content.
Embodiment 2
Prepare according to cross-linking agent resin of the present invention by the method for the component shown in the table 2 according to explained later.
[table 2]
Preparation is according to the component of cross-linking agent resin of the present invention
Component Amount
(A) 4,4 '-methylene-bis (phenyl diisocyanate) 446.0g
(B) methyl iso-butyl ketone (MIBK) 22.1g
(C) 2-hydroxyl ethanol methacrylic ester 331.0g
(D) TriMethylolPropane(TMP) 59.8g
(E) reaction product of embodiment 1 16.6g
(F) methoxypropanol 124.5g
Amount to 1000.0g
To the three neck 2L flasks that are equipped with thermometer, water cooler and mechanical stirrer, add phenyl diisocyanate (A) and methyl iso-butyl ketone (MIBK) (B) and temperature is brought up to 40 ℃ according to table 2.Under the injection air, dropwise added 2-hydroxyl ethanol methacrylic ester (C) lentamente 2 hours, detect isocyanate content simultaneously, and when isocyanate content becomes 5.0-5.5%, the reaction product (E) of TriMethylolPropane(TMP) (D) and embodiment 1 is added in the reactor.Temperature is brought up to 80 ℃ and kept 30 minutes, detect isocyanate content simultaneously, and become 0.2% or still less the time, termination reaction when isocyanate content.After termination reaction, under situation, reaction mixture is cooled to 80 ℃ to finish the preparation method with methoxypropanol (F) dilution by the naturally cooling mode.During reaction, abundant temperature with reaction mixture is controlled at 85 ℃ or lower.The resin of preparation has 85% solids content.
Embodiment 3
Prepare general cross-linking agent resin by the component shown in the table 3 according to the method for explained later.
[table 3]
The component for preparing general cross-linking agent resin
Component Amount
(A) 4,4 '-methylene-bis (phenyl diisocyanate) 484.7g
(B) methyl iso-butyl ketone (MIBK) 24.2g
(C) ethylene glycol butyl ether 288.9g
(D) TriMethylolPropane(TMP) 74.5g
(E) methoxypropanol 127.7g
Amount to 1000.0g
To the three neck 2L flasks that are equipped with thermometer, water cooler and mechanical stirrer, add phenyl diisocyanate (A) and methyl iso-butyl ketone (MIBK) (B) and temperature is brought up to 45 ℃ according to table 3.Dropwise added ethylene glycol butyl ether (C) lentamente 2 hours, and detected isocyanate content simultaneously, and when isocyanate content became 5.0-5.5%, (D) added in the reactor with TriMethylolPropane(TMP).Temperature is brought up to 80 ℃ and kept 30 minutes, detect isocyanate content simultaneously, and become 0.2% or still less the time, termination reaction when isocyanate content.After termination reaction, under situation, reaction mixture is cooled to 80 ℃ to finish the preparation method with methoxypropanol (E) dilution by the naturally cooling mode.The resin of preparation has 85% solids content.
Embodiment 4
Prepare according to phenol of the present invention-barium salt resin by the method for the component shown in the table 4 according to explained later.
[table 4]
Preparation is according to the component of phenol of the present invention-barium salt resin
Component Amount
(A) phenol 80.6g
(B) deionized water 800.0g
(C) hydrated barta 80.6g
(D) lactic acid 38.8g
Amount to 1000.0g
To the three neck 2L flasks that are equipped with thermometer, water cooler and mechanical stirrer, add phenol (A) and deionized water (B) and stirred 30 minutes according to table 4.Add hydrated barta (C), and lentamente temperature is brought up to 60 ℃ and kept 4 hours, reaction mixture is cooled to 30 ℃ or lower then.Add lactic acid (D) and kept reaction mixture 1 hour, then termination reaction.The resin of preparation has 20% solids content.
Embodiment 5
By the component shown in the table 5 according to the reaction product of the method for explained later preparation according to phenol of the present invention-barium salt resin, general base resin and general cross-linking agent resin.
[table 5]
The component of preparation feedback product
Component Amount
(A)YD-128 1) 525.1g
(B)PPG1000 2) 201.6g
(C) bisphenol-A 104.3g
(D) methoxypropanol 38.1g
(E) diethanolamine 103.7g
(F) reaction product of embodiment 3 581.9g
(G) formic acid 24.8g
(H) deionized water 1637.6g
(I) reaction product of embodiment 4 72.8g
(J) deionized water 710.1g
Amount to 4000.0g
1)Bisphenol-A type liquid epoxies (molecular weight: 380; Kukdo Chemical Co., Ltd.)
2)Propylene glycol (molecular weight: 1000; Korea Polyol Co., Ltd.)
To the divergence type 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, it is following 3 hours at 140 ℃ to add YD-128 (A) and PPG1000 (B) and holding temperature according to table 5.Then, interpolation bisphenol-A (C) and methoxypropanol (D) and holding temperature are following 2 hours at 125 ℃.Reaction mixture is cooled to 110 ℃ then.Add diethanolamine (E) down and kept reaction mixture 30 minutes at 110 ℃, and add the reaction product (F) of embodiment 3.Reaction mixture being cooled to 100 ℃ or when lower, add formic acid (G) and deionized water (H) and mixing.Under further reaction mixture, add the reaction product (I) of embodiment 4 and add deionized water (J) 3 hours lentamente so that reaction mixture is dispersed in the water.During dispersion steps, by injecting water coolant occasionally reaction mixture is cooled to 50 ℃ or lower, because be higher than the stability of 50 ℃ temperature reduction water dispersion for a long time.After finishing dispersion steps, injection nitrogen 10 minutes to be removing the bubble in the reaction mixture, and keeps reaction mixture 2 hours.In said process,, from taking place, the thermal control temperature raises so consider this kind because the reaction heat of emitting after amine adds acutely produces.As above the product of Huo Deing has 36% solids content.
Embodiment 6
Prepare according to the reaction product of cross-linking agent resin of the present invention by the method for the component shown in the table 6 with general base resin according to explained later.
[table 6]
The component of preparation feedback product
Component Amount
(A)YD-128 1) 534.8g
(B)PPG1000 2) 205.4g
(C) bisphenol-A 106.3g
(D) methoxypropanol 38.8g
(E) diethanolamine 105.7g
(F) reaction product of embodiment 2 592.7g
(G) formic acid 25.2g
(H) deionized water 1668.0g
(I) deionized water 723.1g
Amount to 4000.0g
1)Bisphenol-A type liquid epoxies (molecular weight: 380; Kukdo Chemical Co., Ltd.)
2)Propylene glycol (molecular weight: 1000; Korea Polyol Co., Ltd.)
To the divergence type 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, it is following 3 hours at 140 ℃ to add YD-128 (A) and PPG1000 (B) and holding temperature according to table 6.Then, interpolation bisphenol-A (C) and methoxypropanol (D) and holding temperature are following 2 hours at 125 ℃.Reaction mixture is cooled to 110 ℃ then.Add diethanolamine (E) down and kept reaction mixture 30 minutes at 110 ℃, and add the reaction product (F) of embodiment 2.Reaction mixture being cooled to 100 ℃ or when lower, add formic acid (G) and deionized water (H) and mixing.Under further reaction mixture, add deionized water (I) 3 hours lentamente so that reaction mixture is dispersed in the water.During dispersion steps, by injecting water coolant occasionally reaction mixture is cooled to 50 ℃ or lower, because be higher than the stability of 50 ℃ temperature reduction water dispersion for a long time.After finishing dispersion steps, injection nitrogen 10 minutes to be removing the bubble in the reaction mixture, and keeps reaction mixture 2 hours.In said process,, from taking place, the thermal control temperature raises so consider this kind because the reaction heat of emitting after amine adds acutely produces.As above the product of Huo Deing has 36% solids content.
Embodiment 7
By the component shown in the table 7 according to the reaction product of the method for explained later preparation according to phenol of the present invention-barium salt resin, general base resin and general cross-linking agent resin.
[table 7]
The component of preparation feedback product
Component Amount
(A)YD-128 1) 521.1g
(B)PPG1000 2) 203.6g
(C) bisphenol-A 106.3g
(D) methoxypropanol 39.1g
(E) diethanolamine 101.5g
(F) reaction product of embodiment 2 584.2g
(G) formic acid 24.8g
(H) deionized water 1635.9g
(I) reaction product of embodiment 4 71.4g
(J) deionized water 712.1g
Amount to 4000.0g
1)Bisphenol-A type liquid epoxies (molecular weight: 380; Kukdo Chemical Co., Ltd.)
2)Propylene glycol (molecular weight: 1000; Korea Polyol Co., Ltd.)
To the divergence type 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, it is following 3 hours at 140 ℃ to add YD-128 (A) and PPG1000 (B) and holding temperature according to table 7.Then, interpolation bisphenol-A (C) and methoxypropanol (D) and holding temperature are following 2 hours at 125 ℃.Reaction mixture is cooled to 110 ℃ then.Add diethanolamine (E) down and kept reaction mixture 30 minutes at 110 ℃, and add the reaction product (F) of embodiment 2.Reaction mixture being cooled to 100 ℃ or when lower, add formic acid (G) and deionized water (H) and mixing.Under further reaction mixture, add the reaction product (I) of embodiment 4 and add deionized water (J) 3 hours lentamente so that reaction mixture is dispersed in the water.During dispersion steps, by injecting water coolant occasionally reaction mixture is cooled to 50 ℃ or lower, because be higher than the stability of 50 ℃ temperature reduction water dispersion for a long time.After finishing dispersion steps, injection nitrogen 10 minutes to be removing the bubble in the reaction mixture, and keeps reaction mixture 2 hours.In said process,, from taking place, the thermal control temperature raises so consider this kind because the reaction heat of emitting after amine adds acutely produces.As above the product of Huo Deing has 36% solids content.
The comparative example 1
In order to contrast, prepare the reaction product of general base resin and general cross-linking agent resin according to the method for explained later by the component shown in the table 8 with the present invention.
[table 8]
The component of preparation feedback product
Component Amount
(A)YD-128 1) 519.3g
(B)PPG1000 2) 199.4g
(C) bisphenol-A 103.2g
(D) methoxypropanol 37.7g
(E) diethanolamine 146.6g
(F) reaction product of embodiment 3 575.5g
(G) formic acid 24.5g
(H) deionized water 1619.6g
(I) deionized water 774.2g
Amount to 4000.0g
1)Bisphenol-A type liquid epoxies (molecular weight: 380; Kukdo Chemical Co., Ltd.)
2)Propylene glycol (molecular weight: 1000; Korea Polyol Co., Ltd.)
To the divergence type 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, it is following 3 hours at 140 ℃ to add YD-128 (A) and PPG1000 (B) and holding temperature according to table 8.Then, interpolation bisphenol-A (C) and methoxypropanol (D) and holding temperature are following 2 hours at 125 ℃.Reaction mixture is cooled to 110 ℃ then.Add diethanolamine (E) down and kept reaction mixture 30 minutes at 110 ℃.Then, under 125 ℃, keep reaction mixture 1 hour and be cooled to 110 ℃.In the reaction product (F) of in the injection air, adding embodiment 3 under 110 ℃.Reaction mixture is being cooled to 100 ℃ or lower, is adding formic acid (G) and deionized water (H) and mixing.Under further reaction mixture, add deionized water (I) 3 hours lentamente so that reaction mixture is dispersed in the water.During dispersion steps, by injecting water coolant occasionally reaction mixture is cooled to 50 ℃ or lower, because be higher than the stability of 50 ℃ temperature reduction water dispersion for a long time.After finishing dispersion steps, injection nitrogen 10 minutes to be removing the bubble in the reaction mixture, and keeps reaction mixture 2 hours.In said process,, from taking place, the thermal control temperature raises so consider this kind because the reaction heat of emitting after amine adds acutely produces.As above the product of Huo Deing has 36% solids content.
Embodiment 8-10 and comparative example 2
For embodiment 8-10 and comparative example 2, be prepared as follows every kind of cationic electrodeposition resin combination: will mix equably 24 hours by 4 to 1 ratio of mixture with the pigment paste composition respectively according to the cationic electrodeposition resin of embodiment 5-7 and comparative example's 1 acquisition.
Be used to prepare of the method preparation of the pigment paste composition of cationic electrodeposition resin combination according to explained later.
In the 3L glass flask, add 680 weight part YD-128 (it is a liquid epoxies), 290 weight part bisphenol-As, 89 weight part dimethylethanolamines and 260 weight part polymethylene multi-phenenyl isocyanates, and reacted 2 hours down at 150 ℃.Then, under 60 ℃ or lower temperature, add 80 weight part acetate and produce pigment dispersing resin with 300 parts by weight of deionized water diluted reaction mixtures.In the pigment dispersing resin that 260 weight parts are obtained, add 450 parts by weight of deionized water, and under agitation to wherein adding 270 parts by weight of titanium dioxide, 74 weight part pure aluminium silicate, 24 weight part carbon blacks and 16 weight part dibutyl tin oxides.Stir this mixture by high speed agitator and produce the pigment paste composition.
Experimental example
(90mm * 200mm) goes up and carries out galvanic deposit under the electrostatic potential at 300V and applied 2 minutes cation electric deposition paint composition by using embodiment 8-10 and comparative example 2 respectively, and this cold-rolled steel sheet has carried out surface treatment with zinc phosphate primary surface treatment agent at cold-rolled steel sheet.Water washes formed coating, and toasts 20 minutes and the coating of formation uniform thickness down at 160 ℃ in baking oven.Test the electrodeposited coating that is obtained, and the test-results of coating performance is illustrated in the following table 9.
[table 9]
The test-results of coating performance
Figure A20078004892600201
1)Gloss: ASTM D523
2)Roughness: measure with roughmeter, Surtronic3+ (Taylor-Hobson Co., Ltd.)
3)Impact: ASTM D2794
4)Cupping: IS0 1520
5)Crooked: ASTM D522
6)MIBK friction: fabric in the solvent (methyl iso-butyl ketone (MIBK)) or cotton paper (tissue) coating to be tested that rubs is destroyed up to coating with immersing." 20 times or more " are meant that friction can not damage coating at least 20 times, shows that coating is a solidified.
7)Salt fog resistance: ASTM B117
As shown in table 9, obtain best curing performance from embodiment 10.Can recognize that excellent curing performance more particularly, comprises the cross-linking agent resin composition of the phenol-barium salt of Mannich modification glycidyl ether-amine deutero-polyol compound and raising curing reaction from the cross-linking agent resin composition that increases cured density.The bigger value of MIBK friction means better curing performance.Estimate erosion resistance by salt-fog test.Salt-fog test result's littler value means better erosion resistance.As shown in table 9, use embodiment 8 to show than the embodiment 9 better erosion resistances of only using titanate catalyst according to cross-linking agent resin of the present invention.The embodiment 10 of cross-linking agent resin and titanate catalyst that uses simultaneously according to the present invention shows optimum corrosion resistance.Generally speaking, when water dispersed resin being applied to the cationic electrodeposition lacquer, obtained excellent erosion resistance and curing performance, kept the outward appearance that shows the coating slickness simultaneously and show and conventional those are compared and are in quite or better the flexible machinery and the adhesion property of level.
Industrial applicability
The present invention relates to have the high functionality cationic electrodeposition resin combination of improved corrosion resistance and curing performance. Because the present composition comprises the product of polyol compound that glycidol ether-amine derives and blocked polyisocyanates compound and uses metallic curing catalysts resin, so the present composition can provide with the cationic electrodeposition resin-phase that uses conventional base resin and cross-linking agent resin than improved corrosion resistance and curing performance for coating.

Claims (9)

1. cationic electrodeposition resin combination, it comprises the cross-linking agent resin that the 20-70 weight part contains the reaction product of glycidyl ether-amine deutero-polyol compound and blocked polyisocyanates compound; 30-80 weight part base resin; With the metallic curing catalysts resin of 0.1-10 weight part, wherein said glycidyl ether-amine deutero-polyol compound is derived from the Mannich reaction products of phenolic compound, amine compound and formalin.
2. according to the composition of claim 1, wherein said phenolic compound is one or both compounds that are selected from cresols, butylphenol, octyl phenol, nonylphenol and phenol; With described amine compound be one or both or the more compounds that is selected from ethylene diamine, trimethylene diamines, hexamethylene-diamine, eight methylene diamine, diethylenetriamine, Triethylenetetramine (TETA), tetracthylene pentamine and m-xylene diamine.
3. according to the composition of claim 1, wherein said Mannich reaction products is the compound of following formula 1:
[formula 1]
Figure A2007800489260002C1
Wherein each among the R is represented phenolic compound independently.
4. according to the composition of claim 1, wherein said glycidyl ether-amine deutero-polyol compound is the reaction product of the compound of following formula 2 as Mannich reaction products, hydroxyl amine compound and glycidyl ether compound; And the amount of described glycidyl ether-amine deutero-polyol compound is 1-20wt% based on described cross-linking agent resin:
[formula 2]
Figure A2007800489260002C2
R wherein 1In each represent phenolic compound, R independently 2In each represent glycidyl ether compound independently, and R 3Represent the hydroxyl amine compound.
5. according to the composition of claim 4, wherein said hydroxyl amine compound is selected from monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), single ehtylethanolamine and monomethyl-ethanolamine; And described glycidyl ether compound is selected from phenyl glycidyl ether and butylglycidyl ether.
6. according to the composition of claim 1, wherein said blocked polyisocyanates compound is the reaction product of diisocyanate cpd and hydroxy acryl acid ester cpds or alkylol cpd; And the amount of described polyisocyanate compound is 80-99wt% based on the amount of described cross-linking agent resin.
7. according to the composition of claim 6, wherein said diisocyanate cpd is selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-methylene-bis (phenyl diisocyanate), tetramethylene diisocyanate and hexamethylene diisocyanate; Described hydroxy acryl acid ester cpds is a methacrylic acid 2-hydroxyl ethyl ester; And described alkylol cpd is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, TriMethylolPropane(TMP) and propylene glycol.
8. according to the composition of claim 1, wherein said metal selected among zirconium, zinc, calcium, lead, tin, bismuth, cobalt, titanium, aluminium, chromium and barium; And described metal exists with salt or inner complex form.
9. according to the composition of claim 1, wherein said metallic curing catalysts resin contains phenol-barium salt or phenol-barium inner complex.
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