CN102186934A - Resin composition for cation electrodeposition paint with excellent inner permeability, containing aromatic sulfonic acid and urethane functional rheology modifier - Google Patents
Resin composition for cation electrodeposition paint with excellent inner permeability, containing aromatic sulfonic acid and urethane functional rheology modifier Download PDFInfo
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- CN102186934A CN102186934A CN2009801412862A CN200980141286A CN102186934A CN 102186934 A CN102186934 A CN 102186934A CN 2009801412862 A CN2009801412862 A CN 2009801412862A CN 200980141286 A CN200980141286 A CN 200980141286A CN 102186934 A CN102186934 A CN 102186934A
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
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- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
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- 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
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
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- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
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Abstract
The present invention relates to a resin composition for cation electrodeposition paint with excellent inner permeability, containing aromatic sulfonic acid and urethane functional rheology modifier, and to a use thereof. More particularly, the present invention relates to a resin composition for cation electrodeposition paint, comprising (1) a base resin containing reaction products of polysulfide compounds and epoxy compounds and reaction products of amine compounds and epoxy compounds; (2) a curing agent resin containing reaction products of modified polyol compounds derived from analogous-Mannich reaction products of phenol compounds, aliphatic or aromatic amine compounds and formalin, and blocked polyisocyanate compounds; (3) aromatic sulfonic acid; and (4) a rheology modifier having an urethane function group.; The resin composition of the present invention is specially suitable as a primer for vehicle and industrial use as the resin composition of the present invention is excellent in water-dispersion stability, inner permeability, and anti-bacterial property, exhibits superior flexibility, anti-corrosion property, and coating property of the film of paint, and exhibits improved anti-corrosion property at the edge of the film of paint. The present invention also relates to a cation electrodeposition paint comprising the resin composition.
Description
Technical field
The present invention relates to contain the cation electrodeposition coating with excellent intrinsic permeability (or covering power) resin combination and its application of aromatic sulfonic acid and carbamate functional rheology modifiers (or rheology control agent).More particularly, the present invention relates to the cation electrodeposition coating resin combination, it comprises the base resin that (1) contains the reaction product of the reaction product of polysulfide compound and epoxy compounds and amine compound and epoxy compounds; (2) contain the curing agent resin of the reaction product of modified multicomponent alkylol cpd and blocked polyisocyanates compound, wherein said modified polyalcohol compound deriving is from the product of the similar Mannich reaction (Mannich-like reaction) of phenolic compound, aliphatic series or aromatic amine compound and formalin; (3) aromatic sulfonic acid; (4) has the rheology control agent of carbamate-functional, excellent flexible, antiseptic property and coating property (or film forming) that it shows excellent water-dispersion stability, covering power and anti-microbial property and shows coating, with improved edge rust resistance, and therefore especially be suitable as the base paint that vehicle and industrial use are used; With the cation electrodeposition coating that comprises said composition.
Background technology
From twentieth century middle period of at first being applied to car when electrocoating paint so far, cation electrodeposition coating is because performance and workability continued exploitation above 40 years.By this kind technological development, electrodeposited coating as rust protection base paint coatings applications in most of car.In company with this together, the needs to electrocoating paint with product coating efficiency, quality uniformity and environment friendly increase.As the most important component in the electrodeposition coating composition, use Resins, epoxy, and they has the carbamate consolidated structures has good quality with formation coating with excellent rust resistance.
Usually, as the base resin that is used for cationic electrodeposition, flexible Resins, epoxy is used typically and as curing agent resin, use vulcabond mostly and have the reaction product of the alkylol cpd of dissociable hydroxy functional group by having of obtaining of polyvalent alcohol and ethoxylation bis-phenol.Specifically, the common method preparation as follows of conventional cationic electrodeposition resin combination: will have 360～20, the Resins, epoxy of 000 number-average molecular weight mixes with bisphenol-A, its derivative or modified polyether type softening agent, in the presence of excessive solvent, make amine and glycol addition reaction under 70～170 ℃, at high temperature under vacuum, remove organic solvent from this reaction product, curing agent resin is mixed with described reaction product of having removed solvent also fully with the organic acid neutralization with to wherein adding deionized water 4～12 hours and being dispersed in the water.
In Korean patent No. 10-0831205 (KCC), to compare with general electrodeposition resin, the compound with polysulfide key is used to improve slickness, rust resistance and flexible.This patent provides the cationic electrodeposition resin combination, it comprises: contain the reaction product of polysulfide compound and epoxy compounds and have good coating slickness and the reaction product of flexible base resin and polyol compound and blocked polyisocyanates as curing agent resin, this polyol compound is derived from having good rust resistance and adherent Mannich reaction products.Yet disclosed electrodeposition resin composition uses general organic acid as neutralizing acid and after this have the water dispersion form in this patent, and contains the barium inner complex as catalyzer.As a result, slickness, rust resistance and flexible being improved and composition stable existence in general condition of storage at room temperature.Yet, because the water-soluble granular resin that is dispersed in the water is limited by general organic acid, so under low and high temperature, may have the storage stability problem.Specifically, viscosity problem under 5 ℃ or lower low temperature, increase and 60 ℃ or more relative superiority or inferiority may take place easily exposing 2 weeks or longer postprecipitation problem.That is, do not have the problem of condition of storage aspect for general application, but may have restriction application in place with dramatic temperature variation.In addition, because polysulfide is flexible, being coated in setting up period may be inadequate owing to flowing of edge.In addition, because resin prepares in deionized water, so may exist in the problem of bacterial growth under the neutrality condition.
U.S. Patent number 6,017,431 (PPG) have introduced thionamic acid, and it can suppress the bacterium in the electrodeposition bath and can be used as neutralizing agent.The thionamic acid of introducing in this patent is represented by following chemical structural formula.
In following formula, R represents hydrogen or alkyl (carbon number: 1～4).Preferably, it has following chemical structural formula.
Yet, when this kind thionamic acid during as the neutralizing agent that has to the Resins, epoxy of the polysulfide that wherein adds, in the thionamic acid and performance insufficient owing to have to the high molecular of the Resins, epoxy of the polysulfide that wherein adds, and therefore water dispersion stability is low and produce precipitation.
Korean Patent Application No. 10-1991-0010475 (PPG, " Cationic microgels and their use in electrodeposition ") discloses the rheology control agent that is used for galvanic deposit of the coating that can improve edge.This rheology control agent is prepared as follows: positively charged ion polyepoxide-amine reaction product and polyepoxide linking agent mixed, and heating and make this mixture crosslinked.This rheology control agent effectively improves edges cover (this prevents coating because the coating that the flowable during the coating curing causes approaches and fragility) and improves resistance to crocking.Yet if excessive use in product, rheology control agent control flowable also participates in curing on the coatingsurface, and therefore form the deterioration of vestige (mark) and outward appearance.
Japanese patent application No. 1990-207406 and 1991-348372 (KANSAI) use polyamide resin to be used to improve the curing performance of rust resistance and edge in base resin composition.Yet degree of crosslinking during polyamide resin promotion coating forms and outward appearance worsen and are flexible insufficient.In order to solve this situation, use softening agent jointly, but because its use causes the reduction of water tolerance and rust resistance.
Summary of the invention
The problem that solves
In order to solve the prior art problems of illustrating above, the purpose of this invention is to provide the resin combination that is used for cation electrodeposition coating, excellent flexible, antiseptic property and film forming that it shows excellent water-dispersion stability, covering power and anti-microbial property and shows coating, with improved edge rust resistance, and therefore especially be suitable as the base paint that is used for vehicle and industrial use; With the cation electrodeposition coating that comprises said composition.
Technique means
In order to reach the purpose of illustrating above, the invention provides the resin combination that is used for cation electrodeposition coating, it comprises:
(1) contains the base resin of the reaction product of the reaction product of polysulfide compound and epoxy compounds and amine compound and epoxy compounds;
(2) contain the curing agent resin of the reaction product of modified multicomponent alkylol cpd and blocked polyisocyanates compound, wherein said modified polyalcohol compound deriving is from the product of the similar Mannich reaction of phenolic compound, aliphatic series or aromatic amine compound and formalin;
(3) aromatic sulfonic acid; With
(4) has the rheology control agent of carbamate-functional.
Another aspect of the present invention provides the cation electrodeposition coating that comprises resin combination of the present invention and pigment.
Effect of the present invention
The resin combination that is used for cation electrodeposition coating according to the present invention shows excellent water-dispersion stability, covering power and anti-microbial property and shows excellent flexible, the antiseptic property and the film forming of coating, with improved edge rust resistance, and therefore especially be suitable as the base paint that is used for vehicle and industrial use.In addition, it can prepare by only using reactor to need not independently to be used for the dispersive facility, and therefore can reduce production costs considerably.
Embodiment
To illustrate the resin combination that is used for cation electrodeposition coating of the present invention according to the formation component that describes in detail below.
Base resin
Generally speaking, the electrodeposition resin composition comprises base resin and curing agent resin as main ingredient.In the middle of them, base resin is the component that constitutes final coating with curing agent resin, and the performance of therefore final coating will be according to the chemical/physical properties decision of base resin.As base resin, most preferably use epoxy compounds, because they provide good rust resistance, adhesion, thermotolerance etc. to final coating.Under the situation of cationic electrodeposition resin, make the reaction of epoxy compounds and amine compound with provide with coating method during in curing agent resin the hydroxyl of necessity of dissociative isocyanic ester radical reaction.Because epoxy compounds especially has good rust resistance, so they generally are used to apply the base material that requires rust resistance mostly.Yet general epoxy compounds has poor flexible.
Be used for base resin of the present invention and contain the reaction product of polysulfide compound and epoxy compounds and the reaction product of amine compound and epoxy compounds.Therefore base resin of the present invention contains the reaction product of polysulfide compound and epoxy compounds, and improves the slickness of the coating that is formed by cationic electrodeposition resin combination according to the present invention and flexible.
In the present invention, without limits to the polysulfide compound that can be used for preparing base resin.Preferably, can use separately or use in combination by compound with following formula 1 expression:
[formula 1]
HS-(C
2H
4-O-CH
2-O-C
2H
4-S-S)n-C
2H
4-O-CH
2-O-C
2H
4-SH
In the formula 1, n represents the integer of 0-50 in the above.
Has preferred 100-2 with the epoxy compounds of the amine compound of above-mentioned polysulfide compound and elucidated hereinafter reaction, 000, more preferably 100-1,500, be more preferably 100-1,000 weight base molecular weight (weight-based molecular weight).If epoxy compounds has the weight base molecular weight less than 100, then flexible and rust resistance may be insufficient.Surpass 2,000 weight base molecular weight if epoxy compounds has, then high viscosity thus may cause and is difficult to handle during preparation process.
Without limits, epoxy compounds preferably is independently selected from one or more in the following compound: with the compound of following formula 2; Compound with following formula 3; Mixture with the compound of following formula 2 and 3; With one or more and reaction product in these compounds with the compound of following formula 4:
[formula 2]
[formula 3]
[formula 4]
HO-C
6-10Aryl-R4-C
6-10Aryl-OH
In following formula, R1 represents C
1-20Alkyl, R2 represents C
1-5Alkylidene group, R3 represents C
17-35Phenolic ether, R4 represents C
1-8Alkylidene group, aryl are meant aromatic ring for example phenyl or naphthalene.
More preferably, the compound of formula 2-4 is represented the compound with following formula 5-7 respectively:
[formula 5]
[formula 6]
[formula 7]
In following formula, m represents the integer of 0-6.
Without limits, the reaction product of polysulfide compound and epoxy compounds can comprise the compound with following formula 8 or 9:
[formula 8]
[formula 9]
In following formula, each R
1Represent C independently
1-20Alkyl, each R
2Represent C independently
1-5Alkyl, R
3Represent C
17-35Phenolic ether, n are represented the integer of 0-50 independently.
More preferably, the reaction product of polysulfide compound and epoxy compounds comprises the compound with following formula 10 and 11:
[formula 10]
[formula 11]
In following formula, each R
2Represent C independently
1-5Alkyl, n are represented the integer of 0-50, and m represents the integer of 0-6.
In base resin, the compound of formula 8-11 independently of one another can for the form of another kind of polysulfide compound or epoxy compounds combination.
According to one embodiment of the invention, the reaction of polysulfide compound and epoxy compounds can be by following reaction process 1 expression.
[reaction process 1]
In above-mentioned reaction process, R
1Represent C
1-20Alkyl, R
2Represent C
1-5Alkyl, R
3Represent C
17-35Phenolic ether, n are represented the integer of 0-50.
More specifically, the reaction of polysulfide compound and epoxy compounds can be by following reaction process 2 expressions.
[reaction process 2]
In the preparation of the base resin that is used for the electrodeposition resin composition, the amine compound that reacts with epoxy compounds is to know in this area.Without limits, preferably one or more are independently selected from HO-R5-NH-R5-OH and (CH to amine compound
3)
2N-R5-NH
2Compound, wherein each R5 represents C independently
1-8Alkyl.
In the middle of the compound of formation base resin, the content of described sulfide compound is 10-30 weight %, and preferred 10-25 weight % is more preferably 10-20 weight %, based on the weight of base resin.If the content of this compound is less than 10 weight %, then the slickness of coating, improvement flexible and rust resistance are insufficient.If the content of this compound is greater than 30 weight %, then the viscosity of reaction mixture improves and therefore its processing difficulty that becomes.In the middle of the compound of formation base resin, the content of described epoxy compounds is 40-80 weight %, and preferred 50-80 weight % is more preferably 60-80 weight %, based on the weight of base resin.If the content of this compound is less than 40 weight %, then for the number that reacts necessary hydroxyl with curing agent resin curing performance insufficient and therefore coating and the rust resistance reduction that becomes that becomes.If the content of this compound is greater than 80 weight %, then the viscosity of reaction mixture improves and therefore its processing difficulty that becomes, and the reduction that becomes of the flexible and weathering resistance of coating.In the middle of the compound of formation base resin, the content of described amine compound is 10-30 weight %, and preferred 10-25 weight % is more preferably 10-20 weight %, based on the weight of base resin.If the content of this compound is less than 10 weight %, then for the number that reacts necessary hydroxyl with curing agent resin curing performance insufficient and therefore coating and the rust resistance reduction that becomes that becomes.If the content of this compound is greater than 30 weight %, then the viscosity of reaction mixture during reaction improves too many and therefore has gelation danger.
In the middle of the reaction product that contains in described base resin, the content of the reaction product of sulfide compound and epoxy compounds is 30-70 weight %, and preferred 30-50 weight % is more preferably 30-40 weight %, based on the weight of base resin.If the content of this reaction product is less than 30 weight %, then the improvement of the flexible and rust resistance of coating is insufficient.If the content of this reaction product is greater than 70 weight %, then the viscosity of reaction mixture improves and therefore its processing difficulty that becomes.The content of the reaction product of described amine compound and epoxy compounds is 30-70 weight %, and preferred 50-70 weight % is more preferably 60-70 weight %, based on the weight of base resin.If the content of this reaction product less than 30 weight %, then is difficult to obtain from sulfide the slickness and the flexible improvement effect of coating.If the content of this reaction product is greater than 70 weight %, the then reaction stability of final electrodeposition resin product and the storage stability product reduction that becomes.
The amount that contains the base resin in cationic electrodeposition resin combination according to the present invention is 30-80 weight % preferably, and more preferably 50-75 weight % is more preferably 60-70 weight %, based on the gross weight of base resin and curing agent resin.If the amount of base resin is less than 30 weight %, based on the gross weight of base resin and curing agent resin, the then slickness of coating, the flexible and rust resistance reduction that becomes.If the amount of base resin is greater than 80 weight %, then the curing performance aspect has problems.
Curing agent resin
Curing agent resin and base resin reaction are to form final coating.More particularly, the hydroxyl in the isocyanate group in the curing agent resin and the base resin is than giving under the high temperature of fixed temperature reaction to form stable final coating.Because curing agent resin and base resin are with the preparation of uniform mixing state, so being reflected between the hydroxyl of the isocyanate group of use blocked isocyanate so that curing agent resin and base resin than not being initiated to the low temperature of fixed temperature.Curing agent resin forms coating and provides good curing performance, rust resistance and water tolerance to coating with base resin.
Be used for the reaction product that curing agent resin of the present invention contains modified multicomponent alkylol cpd and blocked polyisocyanates compound, wherein said modified polyalcohol compound deriving is from the product of the similar Mannich reaction of phenolic compound, aliphatic series or aromatic amine compound and formalin.
In the present invention, " similar Mannich reaction " is meant compound, uncle or secondary amine with aldehyde radical and the dehydration condensation between the phenolic compound, is different from the conventional Mannich reaction between compound, uncle or secondary amine with aldehyde radical and the compound with carbonyl.Be widely used as the low temperature curing agent of general epoxypaint like the product of Mannich reaction active hydrogen preparation and that have amine compound through kind thus.As everyone knows, if in epoxy curing agent, contain the product of similar Mannich reaction that this kind has the active hydrogen of amine compound, then at room temperature with low temperature under the curing performance improvement that becomes.
In the present invention, the product that is different from the conventional similar Mannich reaction that is used for general epoxypaint, active hydrogen by removing amine compound is also introduced the curing agent resin that modified polyalcohol that reactive hydroxyl obtains is used for the electrodeposition resin composition via addition reaction after similar Mannich reaction, by this curing agent resin impel with the urethane reaction of isocyanate group so that the coating with good solidification performance to be provided, and cause the improvement of rust resistance.
The phenolic compound that is used for similar Mannich reaction is selected from phenolic compound for example cresols, butylphenol, octyl phenol, nonylphenol and phenol, is preferably selected from phenol, octyl phenol and nonylphenol, more preferably is selected from phenol and nonylphenol.One or more can use individually or in combination in these compounds.The aliphatic series or the aromatic amine compound that are used for similar Mannich reaction are preferably selected from quadrol, trimethylene diamines, hexamethylene-diamine, oxygen methylene diamine, diethylenetriamine, Triethylenetetramine (TETA), penten and m-xylene diamine.One or more can use individually or in combination in these compounds.
Be used for the amount 10-30 weight % preferably of the phenolic compound of similar Mannich reaction, more preferably 15-25 weight % is more preferably 15-20 weight %, based on the gross weight of the added raw material of product of the similar Mannich reaction of preparation.If the amount of employed phenolic compound is less than 10 weight %, based on the gross weight of added raw material, then rust resistance may reduce.On the contrary, if described amount greater than 30 weight %, then viscosity and state of cure may increase too high.The amount that is used for the aliphatic series of similar Mannich reaction or aromatic amine compound is 10-30 weight % preferably, and more preferably 15-25 weight % is more preferably 20-25 weight %, based on the gross weight of the added raw material of product of the similar Mannich reaction of preparation.If the amount that is used for the aliphatic series of similar Mannich reaction or aromatic amine compound is less than 10 weight %, based on the gross weight of added raw material, then unreacted material may be residual and therefore coating performance may be insufficient.On the contrary, if described amount greater than 30 weight %, therefore then urea functional group may form and may be during reaction or produce insoluble particle afterwards.Be used for the amount 15-45 weight % preferably of the formalin of similar Mannich reaction, more preferably 20-40 weight % is more preferably 25-35 weight %, based on the gross weight of the added raw material of product of the similar Mannich reaction of preparation.If the amount of formalin that is used for similar Mannich reaction is less than 15 weight %, based on the gross weight of added raw material, then unreacted amine may be residual in a large number.On the contrary, if described amount greater than 45 weight %, therefore then viscosity may increase too high and may have gelation danger.
Can obtain various types of product according to phenolic compound and aliphatic series or aromatic amine compound like Mannich reaction.Without limits, the product of similar Mannich reaction preferably has the structure with following formula 12.
[formula 12]
In following formula, each R6 is derived from cresols, butylphenol, octyl phenol, nonylphenol or phenol, preferably derived from the replacement or the unsubstituted o-hydroxy-phenyl of nonylphenol or phenol independently.
Be used to prepare the amount 1-20 weight % preferably of product of the similar Mannich reaction of curing agent resin, more preferably 5-15 weight % is more preferably 5-10 weight %, based on 100 weight % of the curing agent resin of gained.If the amount of the product of similar Mannich reaction is less than 1 weight %, then the improvement of curing performance may be insufficient.If the amount of the product of similar Mannich reaction is greater than 20 weight %, then initial solidification may be faster and therefore outward appearance may become poorer.
Preferably, the modified polyalcohol that is used for curing agent resin is the reaction product that the product of the similar Mannich reaction illustrated above and being used to provides the compound of hydroxyl, and this is used to provide the compound of hydroxyl to be selected from amine, epoxy compounds and their mixture of hydroxyl.The amine of described hydroxyl is preferably selected from monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), single ehtylethanolamine and monomethyl-ethanolamine, more preferably is selected from ehtylethanolamine and Mono Methyl Ethanol Amine.Described epoxy compounds is preferably selected from phenyl glycidyl ether and butylglycidyl ether.
Be used to prepare the amount 5-20 weight part preferably of compound that is used to provide hydroxyl of modified polyalcohol, more preferably the 6-15 weight part is more preferably the 7-10 weight part, based on the product of the similar Mannich reaction of 100 weight parts.If the amount of compound that is used to provide hydroxyl is less than 5 weight parts, based on the product of the similar Mannich reaction of 100 weight parts, then the number of end hydroxyl is insufficient and may not carry out with curing reaction isocyanate group therefore subsequently.On the contrary, if described amount greater than 20 weight parts, then the stability of reaction product may reduce.
Modified polyalcohol, it is the reaction product that the product and being used to of similar Mannich reaction provides the compound of hydroxyl, preferably have the structure with following formula 13, but it is not limited thereto.
[formula 13]
In following formula, each R6 is derived from cresols, butylphenol, octyl phenol, nonylphenol or phenol, preferably derived from the replacement or the unsubstituted o-hydroxy-phenyl of nonylphenol or phenol independently, each R7 is derived from glycidyl ether compound, preferably derived from the residue of butylglycidyl ether or phenyl glycidyl ether independently, and R8 is derived from monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), single ehtylethanolamine or monomethyl-ethanolamine, preferably derived from the residue of single ehtylethanolamine or monomethyl-ethanolamine.
In the present invention, be used to prepare the amount 1-20 weight % preferably of the modified multicomponent alkylol cpd of curing agent resin, more preferably 5-15 weight % is more preferably 5-10 weight %, based on the gross weight that is used to prepare the added raw material of curing agent resin.If the amount of modified multicomponent alkylol cpd is less than 1 weight %, based on the gross weight that is used to prepare the added raw material of curing agent resin, then the improvement of curing performance may be insufficient.If described amount is greater than 20 weight %, then too high the and initial solidification of viscosity may be faster, and therefore outward appearance may become poorer.
In the preparation of curing agent resin of the present invention, can freely be selected from the known conventional blocked polyisocyanates that can be used for the cationic electrodeposition resin combination with the blocked polyisocyanates of modified multicomponent alkylol cpd reaction.Without limits, preferably aliphatic series or the acrylic compound of aromatic diisocyanate and hydroxyl or the reaction product of alkylol cpd of blocked polyisocyanates.
Aliphatic series or aromatic diisocyanate are preferably selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, ditan-4,4 '-vulcabond and tetramethylene and hexamethylene diisocyanate, more preferably be selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, ditan-4,4 '-vulcabond and tetramethylene and hexamethylene diisocyanate.The acrylic compound of hydroxyl is methacrylic acid 2-hydroxyl ethyl ester preferably.Alkylol cpd is preferably selected from ethylene glycol monobutyl ether, Diethylene Glycol single-butyl ether, TriMethylolPropane(TMP) and propylene glycol.
In the present invention, be used to prepare the amount 20-75 weight % preferably of the blocked polyisocyanates of curing agent resin, more preferably 25-60 weight % is more preferably 30-40 weight %, based on the gross weight that is used to prepare the added raw material of curing agent resin.If the amount of blocked polyisocyanates is less than 20 weight %,, then may there be uncured problem based on the gross weight that is used to prepare the added raw material of curing agent resin.If described amount is greater than 75 weight %, then solidification rate may increase, but rust resistance may reduce.
The amount of the curing agent resin that contains in cationic electrodeposition resin combination according to the present invention is 20-70 weight % preferably, and more preferably 25-50 weight % is more preferably 30-40 weight %, based on the gross weight of base resin and curing agent resin.If the amount of solidifying agent is less than 20 weight %, based on the gross weight of base resin and curing agent resin, then solidification value increase and rust resistance may reduce owing to uncured.If the amount of curing agent resin is greater than 70 weight %, then cured density high and therefore outward appearance may become poorer, and the epoxy component in the major constituent is insufficient and therefore rust resistance may reduce.
Aromatic sulfonic acid
For example formic acid, acetate and lactic acid are different as the conventional cationic electrodeposition resin combination of neutralizing agent with only using general organic acid, cationic electrodeposition resin combination of the present invention be characterised in that comprise aromatic sulfonic acid and general organic acid for example formic acid, acetate and lactic acid together as neutralizing agent.
The aromatic sulfonic acid that contains in cationic electrodeposition resin combination of the present invention can obtain via the reaction of sulfuric acid and aromatic substance and for example, can have following structural formula, but it be not limited thereto.
1～4) or hydroxyl in following formula, R can be an alkyl (carbon number:.The aromatic sulfonic acid that contains in cationic electrodeposition resin combination of the present invention is the xylene monosulfonic acid of following structural formula preferably.
According to one embodiment of the invention, more particularly, aromatic sulfonic acid is prepared as follows: with sulfuric acid and aromatic substance (for example, dimethylbenzene) add in the reactor and under 110-140 ℃, carry out dehydration reaction, under reduced pressure from the mixture of gained, remove unreacted organic constituent then and to wherein adding distilled water.For example formic acid, lactic acid, acetate and methanesulfonic one are used from the electrodeposition resin composition, the bacteriostatic effect that produced by its germicidal action of stable resin raising and obtain thus for Zhi Bei aromatic sulfonic acid and conventional acid like this.
The amount of the aromatic sulfonic acid that contains in the cationic electrodeposition resin combination according to the present invention is the 0.1-5 weight part preferably, and more preferably the 0.3-3 weight part is more preferably the 0.5-2 weight part, based on the total amount of 100 weight part base resins and curing agent resin.If the amount of aromatic sulfonic acid is less than 0.1 weight part, based on the total amount of 100 weight part base resins and curing agent resin, then water dispersion stability reduces and therefore may precipitate.If amount is greater than 5 weight parts, then viscosity becomes too high owing to excessively neutralize, and may have coating dissolved problem again.
Rheology control agent
Cationic electrodeposition resin combination feature of the present invention also is to comprise the rheology control agent with carbamate-functional together with said components.Being used for rheology control agent of the present invention is water-soluble, the urethane-modified epoxy-amine resin with carbamate-functional and gel particle form.The erosion resistance that it can be used to improve the edge coating property of general electrodeposition resin and therefore improve the edge.This rheology control agent controls effectively because polysulfide derivative in the resin combination and the excessive flexibility during curing that causes of high boiling point organic constituent and flowable and the performance of the resin combination under the marginal flow easily.
Though conventional rheology control agent is controlled at the flowable of edge effectively, they have the side effect of poor levelling on horizontal plane.Yet, be used for the rheology control agent with carbamate-functional of the present invention and be controlled at the flowable of edge and simultaneously by the feature of gel particle effectively, the flexural properties that it can be by carbamate-functional on horizontal plane with chemical mode keep slickness.
According to one embodiment of the invention, rheology control agent with carbamate-functional can be by making polyepoxide-amine compound, vulcabond and having the amine reaction of hydroxyl, then addition reaction polyamine diamines and preparing with organic acid neutral mode if desired for example.
As vulcabond, preferred aliphatic vulcabond for example hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenylene vulcabond or their mixture of using more preferably uses polymethylene polyphenylene vulcabond.
In the present invention, be used to prepare the amount 1-10 weight % preferably of the vulcabond of rheology control agent, more preferably 2-5 weight % is based on the gross weight that is used to prepare the added raw material of rheology control agent.If the amount of vulcabond is less than 1 weight %, based on the gross weight that is used to prepare the added raw material of rheology control agent, then the carbamate feature becomes insufficient and performance may reduce.If greater than 10 weight %, then adhering to, described amount may reduce.
As polyepoxide-amine compound, for example, can use for example reaction product of alkylamine and oxyamine of poly epoxy resin (it is the polymerisate of polyvalent alcohol and polyepoxide) and amine compound.
In the present invention, be used to prepare the amount 5-20 weight % preferably of the polyepoxide-amine compound of rheology control agent, more preferably 10-15 weight % is based on the gross weight that is used to prepare the added raw material of rheology control agent.If the amount of polyepoxide-amine compound is less than 5 weight %, based on the gross weight that is used to prepare the added raw material of rheology control agent, then may be in existing problems aspect the water dispersion stability.If described amount is greater than 20 weight %, then workability may be owing to high viscosity reduces.
As polyamine, for example, can use for example quadrol of amine compound.
In the present invention, be used to prepare the amount 0.1-5 weight % preferably of the polyamine of rheology control agent, more preferably 0.5-1 weight % is based on the gross weight that is used to prepare the added raw material of rheology control agent.If the amount of polyamine is less than 0.1 weight %, based on the gross weight that is used to prepare the added raw material of rheology control agent, then gel formation speed may hang down and therefore the rheology control agent of gained may bring into play its function deficiently.If the problem that described amount greater than 5 weight %, then may during preparation exist gel to produce.
The amount of the rheology control agent with carbamate-functional that contains in cationic electrodeposition resin combination according to the present invention is the 1-10 weight part preferably, more preferably 2-8 weight part, be more preferably the 3-6 weight part, based on the total amount of 100 weight part base resins and curing agent resin.Be less than 1 weight part if having the amount of the rheology control agent of carbamate-functional, based on the total amount of 100 weight part base resins and curing agent resin, then edges cover may be insufficient.If described amount is greater than 10 weight parts, then coating appearance may become poorer.
To illustrate the present invention in more detail by following examples and comparative example.Yet embodiment only plans to illustrate the present invention and scope of the present invention is not limited by they.
Embodiment
Preparation embodiment 1
As the aromatic sulfonic acid compound that in electrodeposition resin composition of the present invention, contains, prepare the xylene monosulfonic acid compound according to the composition of following table 1 method by elucidated hereinafter.
The preparation of [table 1] xylene monosulfonic acid compound
| Raw material | Weight |
| (A) sulfuric acid | 45.3g |
| (B) dimethylbenzene | 17.9g |
| (C) sulfuric acid | 10.0g |
| The part of (D) removing (comprising water) | -23.2g |
| (E) distilled water | 950.0g |
| Amount to | 1000.0g |
In the 3-neck 2L flask that is equipped with thermometer, water cooler and mechanical stirrer, add sulfuric acid (A) and dimethylbenzene (B) as shown in table 1 and be heated to 110 ℃, kept then 2 hours.Lentamente to wherein adding sulfuric acid (C) and under 125 ℃, keeping 2 hours.Under 125 ℃, from reactor, remove the part that 23.2g comprises water (D), then with reactor cooling to 90 ℃.To wherein adding distilled water (E) and kept 1 hour, and with reactor cooling to being lower than 60 ℃ with termination reaction.React carefully, because reaction mixture tends to during reaction boil over.The product of preparation has the solids content of 5 weight %.
Preparation embodiment 2
For electrodeposition resin composition of the present invention, has the rheology control agent of carbamate-functional by the method preparation of elucidated hereinafter according to the composition of following table 2.
The preparation of [table 2] rheology control agent
| Raw material | Weight |
| (A) Resins, epoxy YD-128 | 115.2g |
| (B) ethoxylation bisphenol-A | 36.5g |
| (C) dimethylbenzene | 40.0g |
| (D) benzyldimethylamine | 1.6g |
| The part of (E) removing (comprising water) | -40.0g |
| (F) methoxypropanol | 20.0g |
| (G) 4,4 '-methylene-bis (phenyl diisocyanate) | 37.3g |
| (H) dimethylethanolamine | 6.4g |
| (I) quadrol | 3.1g |
| (J) distilled water | 780.0g |
| Amount to | 1000.1g |
In the 3-neck 2L flask that is equipped with thermometer, water cooler and mechanical stirrer, add YD-128 (A) and ethoxylation bisphenol-A (B) as shown in table 2 and be heated to 140 ℃, then to wherein adding dimethylbenzene (C) and benzyldimethylamine (D) and under 140 ℃, keeping 4 hours.Behind cooling reactor to 120 ℃, under reduced pressure from reactor, remove the part that comprises water (E), and reactor further is cooled to 100 ℃.Add methoxypropanol (F) then and reactor further is cooled to 80 ℃.Under 80 ℃, dropwise added premixed vulcabond (G) and dimethylethanolamine (H) lentamente 1 hour, and under 80 ℃, kept 1 hour then.Behind cooling reactor to 60 ℃, dropwise add the mixture 4 hours of quadrol (I) and distilled water (J) lentamente and keep 1 hour under 40 ℃ to finish reaction being lower than.The product of preparation has the solids content of 20 weight %.
Preparation embodiment 3
In order in the curing agent resin that in electrodeposition resin composition of the present invention, contains of preparation, to use, prepare the modified multicomponent alkylol cpd according to the composition of following table 3 method by elucidated hereinafter.
The preparation of [table 3] modified multicomponent alkylol cpd
| Raw material | Weight |
| (A) phenol | 120.7g |
| (B) m-xylene diamine | 201.8g |
| (C) formalin | 162.0g |
| The part of (D) removing (comprising water) | -105.0g |
| (E) Mono Methyl Ethanol Amine | 82.9g |
| (F) butylglycidyl ether | 237.6g |
| (G) methoxypropanol | 300.0g |
| Amount to | 1000.0g |
In the 3-neck 2L flask that is equipped with thermometer, water cooler and mechanical stirrer, add phenol (A) and m-xylene diamine (B) as shown in table 3 and be heated to 70 ℃, then lentamente to wherein adding formalin (C) 1 hour and under 95 ℃, keeping 2 hours.Under 125 ℃, from reactor, remove the part that 105g comprises water (D), then with reactor cooling to 90 ℃.To wherein adding Mono Methyl Ethanol Amine (E) and butylglycidyl ether (F), be heated to 125 ℃ and kept 2 hours with heat release, be cooled to then 110 ℃ and with methoxypropanol (G) dilution with termination reaction.React carefully, because reaction mixture tends to during reaction boil over.The product of preparation has the solids content of 70 weight %.
Preparation embodiment 4
For electrodeposition resin composition of the present invention, prepare curing agent resin according to the composition of following table 4 method by elucidated hereinafter.
The preparation of [table 4] curing agent resin
| Raw material | Weight |
| (A) 4,4 '-methylene-bis (phenyl diisocyanate) | 459.1g |
| (B) methyl iso-butyl ketone (MIBK) | 23.9g |
| (C) ethylene glycol butyl ether | 314.9g |
| (D) TriMethylolPropane(TMP) | 63.9g |
| (E) product of preparation embodiment 3 | 12.0g |
| (F) methoxypropanol | 126.2g |
| Amount to | 1000.0g |
In the 3-neck 2L flask that is equipped with thermometer, water cooler and mechanical stirrer, add isocyanic ester (A) and methyl iso-butyl ketone (MIBK) (B) as shown in table 4 and be heated to 45 ℃, then lentamente to wherein dropwise adding ethylene glycol butyl ether (C) 2 hours.Detect isocyanate content and when it becomes 5.0%～5.5%, TriMethylolPropane(TMP) (D) and the product (E) for preparing embodiment 3 are added in this reactor.Then this reactor is heated to 80 ℃ and kept 30 minutes.Detect isocyanate content and when it becomes when being lower than 0.2%, allow reaction mixture to be cooled to be lower than 80 ℃ and dilute to finish reaction with methoxypropanol (F).During reaction, control reaction temperature is so that be no more than 85 ℃.The product of preparation has the solids content of 85 weight %.
Embodiment 1
Prepare cationic electrodeposition resin combination of the present invention according to the composition of following table 5 method by elucidated hereinafter.
The preparation of [table 5] cationic electrodeposition resin combination of the present invention
| Raw material | Weight |
| (A)Cardura?E-10P *1 | 85.7g |
| (B) polysulfide LP3 *2 | 58.2g |
| (C)Epoxy?YD-128 *3 | 562.5g |
| (D) bisphenol-A | 94.5g |
| (E) methoxypropanol | 40.0g |
| (F) benzyldimethylamine | 4.0g |
| (G) Mono Methyl Ethanol Amine | 125.0g |
| (H) product of preparation embodiment 4 | 560.3g |
| (I) formic acid | 37.3g |
| (J) deionized water | 850.1g |
| (K) product of preparation embodiment 2 | 200.0g |
| (L) product of preparation embodiment 1 | 12.2g |
| (M) deionized water | 1370.2g |
| Amount to | 4000.0g |
1HEXION: neodecanoic acid glycidyl ester (molecular weight: 240)
2TORAY?CHEMICAL：THIOKOL?LP3
3KUKDO CHEMICAL: bisphenol-A type liquid epoxies (molecular weight: 380)
In the separable 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, add Cardura E-10P (A) and polysulfide (B) as shown in table 5 and under 80 ℃, kept 1 hour, then to wherein adding YD-128 (C), bisphenol-A (D), methoxypropanol (E) and benzyldimethylamine (F) and being heated to 125 ℃.Under 125 ℃, keep reactor 2 hours and be cooled to 110 ℃.Add Mono Methyl Ethanol Amine (G) down at 110 ℃, and temperature is brought up to 125 ℃, kept 1 hour, be cooled to 110 ℃ then with heat release.Add down the product slurry (H) of preparation embodiment 4 and kept 30 minutes at 110 ℃, and to wherein mixing and adding formic acid (I) and deionized water (J).After cooling, add the product slurry (K) of preparation embodiment 2 and kept under 50 ℃ 1 hour being lower than.In the water-dispersion step, if temperature is being higher than under 50 ℃ for a long time, then water dispersion stability becomes poorer.Therefore, add water coolant sometimes to maintain the temperature at 50 ℃ or lower.50 ℃ or lower keep 1 hour after, being lower than product slurry (L) and the deionized water (M) that mixes lentamente under 40 ℃ and add preparation embodiment 1, and keep 30 minutes to finish preparation.The product of preparation has the solids content of 36 weight %.
The comparative example 1
Embodiment does not as a comparison contain the cationic electrodeposition resin combination of xylene monosulfonic acid by the method preparation of elucidated hereinafter according to the composition of following table 6.
[table 6] do not contain the preparation of the cationic electrodeposition resin combination of xylene monosulfonic acid
| Raw material | Weight |
| (A)Cardura?E-10P *1 | 85.7g |
| (B) polysulfide LP3 *2 | 58.2g |
| (C)Epoxy?YD-128 *3 | 562.5g |
| (D) bisphenol-A | 94.5g |
| (E) methoxypropanol | 40.0g |
| (F) benzyldimethylamine | 4.0g |
| (G) Mono Methyl Ethanol Amine | 125.0g |
| (H) product of preparation embodiment 4 | 560.3g |
| (I) formic acid | 40.7g |
| (J) deionized water | 850.1g |
| (K) product of preparation embodiment 2 | 200.0g |
| (L) deionized water | 1379.0g |
| Amount to | 4000.0g |
1HEXION: neodecanoic acid glycidyl ester (molecular weight: 240)
2TORAY?CHEMICAL：THIOKOL?LP3
3KUKDO CHEMICAL: bisphenol-A type liquid epoxies (molecular weight: 380)
In the separable 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, add Cardura E-10P (A) and polysulfide (B) as shown in table 6 and under 80 ℃, kept 1 hour, then to wherein adding YD-128 (C), bisphenol-A (D), methoxypropanol (E) and benzyldimethylamine (F) and being heated to 125 ℃.Under 125 ℃, keep reactor 2 hours and be cooled to 110 ℃.Add Mono Methyl Ethanol Amine (G) down at 110 ℃, and temperature is brought up to 125 ℃, kept 1 hour, be cooled to 110 ℃ then with heat release.Add down the product slurry (H) of preparation embodiment 4 and kept 30 minutes at 110 ℃, and to wherein mixing and adding formic acid (I) and deionized water (J).After cooling, add the product slurry (K) of preparation embodiment 2 and kept under 50 ℃ 1 hour being lower than.In the water-dispersion step, if temperature is being higher than under 50 ℃ for a long time, then water dispersion stability becomes poorer.Therefore, add water coolant sometimes to maintain the temperature at 50 ℃ or lower.50 ℃ or lower keep 1 hour after, add deionized water (L) lentamente being lower than 40 ℃, and keep 30 minutes to finish preparation.The product of preparation has the solids content of 36 weight %.
The comparative example 2
As another comparative example, the method preparation by elucidated hereinafter does not contain xylene monosulfonic acid and has the cationic electrodeposition resin combination of the rheology control agent of carbamate-functional according to the composition of following table 7.
[table 7] do not contain the preparation of the xylene monosulfonic acid and the cationic electrodeposition resin combination of the rheology control agent with carbamate-functional
| Raw material | Weight |
| (A)Cardura?E-10P *1 | 85.7g |
| (B) polysulfide LP3 *2 | 58.2g |
| (C)Epoxy?YD-128 *3 | 562.5g |
| (D) bisphenol-A | 94.5g |
| (E) methoxypropanol | 40.0g |
| (F) benzyldimethylamine | 4.0g |
| (G) Mono Methyl Ethanol Amine | 125.0g |
| (H) product of preparation embodiment 4 | 560.3g |
| (I) formic acid | 40.7g |
| (J) deionized water | 850.1g |
| (K) deionized water | 1579.0g |
| Amount to | 4000.0g |
1HEXION: neodecanoic acid glycidyl ester (molecular weight: 240)
2TORAY?CHEMICAL：THIOKOL?LP3
3KUKDO CHEMICAL: bisphenol-A type liquid epoxies (molecular weight: 380)
In the separable 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, add Cardura E-10P (A) and polysulfide (B) as shown in table 7 and maintain 80 ℃ following 1 hour, then to wherein adding YD-128 (C), bisphenol-A (D), methoxypropanol (E) and benzyldimethylamine (F) and being heated to 125 ℃.Under 125 ℃, keep reactor 2 hours and be cooled to 110 ℃.Add Mono Methyl Ethanol Amine (G) down at 110 ℃, and temperature is brought up to 125 ℃, kept 1 hour, be cooled to 110 ℃ then with heat release.Add down the product slurry (H) of preparation embodiment 4 and kept 30 minutes at 110 ℃, and to wherein mixing and adding formic acid (I) and deionized water (J).After cooling, add deionized water (K) lentamente and be lower than 40 ℃ so that temperature is reduced to.In the water-dispersion step, if temperature is being higher than under 50 ℃ for a long time, then water dispersion stability becomes poorer.Therefore, add water coolant sometimes to maintain the temperature at 40 ℃ or lower.After adding deionized water, keep reaction mixture 30 minutes to finish preparation.The product of preparation has the solids content of 36 weight %.
Preparation embodiment 5
The general solidifying agent that is used for cationic electrodeposition according to the composition of following table 8 by the method preparation of elucidated hereinafter.
The preparation of [table 8] general solidifying agent
| Raw material | Weight |
| (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 |
In the 3-neck 2L flask that is equipped with thermometer, water cooler and mechanical stirrer, add phenyl diisocyanate (A) and methyl iso-butyl ketone (MIBK) (B) as shown in table 8 and be heated to 45 ℃, then lentamente to wherein dropwise adding ethylene glycol butyl ether (C) 2 hours.Also when it became 5.0%～5.5%, (D) added in the reactor detection isocyanate content with TriMethylolPropane(TMP).Then this reactor is heated to 80 ℃ and kept 30 minutes.Detect isocyanate content and when it becomes when being lower than 0.2%, allow reaction mixture to be cooled to be lower than 80 ℃ and dilute to finish reaction with methoxypropanol (E).The product of preparation has the solids content of 85 weight %.
The comparative example 3
As another comparative example, the method preparation by elucidated hereinafter contains general curing agent resin but does not contain xylene monosulfonic acid and have the cationic electrodeposition resin combination of the rheology control agent of carbamate-functional according to the composition of following table 9.
[table 9] contains general curing agent resin but do not contain xylene monosulfonic acid and have the preparation of cationic electrodeposition resin combination of the rheology control agent of carbamate-functional
| Raw material | Weight |
| (A)YD-128 1 | 534.8g |
| (B)PPG1000 2 | 205.4g |
| (C) bisphenol-A | 106.3g |
| (D) methoxypropanol | 38.8g |
| (E) Mono Methyl Ethanol Amine | 105.7g |
| (F) product of preparation embodiment 5 | 592.7g |
| (G) formic acid | 25.2g |
| (H) deionized water | 1668.0g |
| (I) deionized water | 723.1g |
| Amount to | 4000.0g |
1KUKDO CHEMICAL: bisphenol-A type liquid epoxies (molecular weight: 380)
2KOREA POLYOL: propylene glycol (molecular weight: 1000)
In the separable 5L flask that is equipped with mechanical stirrer, water cooler, well heater and thermometer, add YD-128 (A) and PPG-1000 (B) as shown in table 9 and maintain 140 ℃ following 3 hours, then to wherein adding bisphenol-A (C) and methoxypropanol (D) and being heated to 125 ℃.Under 125 ℃, keep reactor 2 hours and be cooled to 110 ℃.Descend to add diethanolamine (E) and kept 30 minutes at 110 ℃, and add the product slurry (F) of preparation embodiment 5.After being cooled to be lower than 100 ℃, to wherein mixing and add formic acid (G) and deionized water (H), and when keeping cooling, added deionized water (I) lentamente 3 hours so that with the reaction mixture water-dispersion.In the water-dispersion step, if temperature is being higher than under 50 ℃ for a long time, then water dispersion stability becomes poorer.Therefore, add water coolant sometimes to maintain the temperature at 50 ℃ or lower.After the water-dispersion program is finished, by nitrogen injection 10 minutes with the mixture degassing of gained removing bubble wherein, and kept stable state 2 hours.In said procedure, the reaction after adding amine is the height heat release, and considers this kind exothermic characteristic when temperature improves or keeps.The product of preparation has the solids content of 36 weight %.
Performance test
With each and cationic electrodeposition in the electrodeposition resin composition of the water-dispersion for preparing among embodiment (Ex.) 1 and comparative example (Com.Ex.) 1-3 with conventional colo(u)rant dispersion paste with 4: 1 mixed and stirred 24 hours.By using rectifier (rectifier) to form the coating and the curing of 20～25 μ m thickness by the mixture of gained.Solidified sample is carried out the various tests of coating performance.Test-results is shown in the following table 10.
The test-results of [table 10] coating performance
1At high temperature store: be placed on the 400ml sample in the 500mlPVC bottle and in thermostatic chamber, store 2 weeks, the states of observation sample then down at 60 ℃.
2Store at low temperatures: be placed on the 400m1 sample in the 500mlPVC bottle and in thermostatic chamber, store 2 weeks, the states of observation sample then down at 5 ℃.
3Erosion resistance: punching press ferroelectric sample mechanically applies with electrodeposition coating composition, then 2 weeks of test in the salt-fog test machine.After test, measure a side length of the part of peeling off owing to corrosion.
4Film forming: after the galvanic deposit of sharp knife blade applies, with the state of electron microscope observation coating.
5Roughness: measure by equipment Surtronic 3+ (TAYLOR-HOBSON)
6Shock strength: measure according to ASTM D2794
7Flexural strength: measure according to ISO 1520
8Crooked: as to measure according to ASTM D522
9Resistance to salt(spray)fog: measure according to ASTM B117
In addition, in order to estimate the antibacterial effect of electrodeposited coating, by using the electrodeposition resin preparation of compositions coating of the water-dispersion for preparing among embodiment (Ex.) 1 and comparative example (Com.Ex.) 1-3.The coating of preparation and the washing water that produced by washing after galvanic deposit applies program are carried out the bacterial surveys test.The results are shown in the following table 11.
The result of [table 11] bacterial surveys test
1At room temperature store: in thermostatic chamber,, test by use Cult-dip Combi kit (MERCK) then 25 ℃ of following 1 weeks of stored sample
2At high temperature store: in thermostatic chamber,, test by use Cult-dip Combi kit (MERCK) then 40 ℃ of following 1 weeks of stored sample
The test-results of table 10 shows that in the time will being applied to cation electrodeposition coating according to the electrodeposition resin composition of water-dispersion of the present invention compare with the comparative example 3 who is prior art products, coating performance is improved significantly.At first, in view of water dispersion stability, after storing, the product that contains the embodiment 1 of xylene monosulfonic acid shows that satisfactory stability keeps under high temperature and low temperature.The Ra value represents the slickness of the slickness of coating and the low more indication coating of Ra good more.According to table 10, the Ra of embodiment 1 can know thus that far below comparative example 3 Ra the slickness of the coating that is formed by electrodeposition resin composition according to the present invention is much better than product of the prior art.Conjecture is caused by the flexible of polysulfide compound that contains in the base resin in electrodeposition resin composition of the present invention for the better slickness of coating.
In addition, compare with the product of the embodiment 1 that comprises the rheology control agent with carbamate-functional, the comparative example 2 and 3 who does not contain this kind rheology control agent shows relatively poor anti-edge corrosion and film forming.In addition, in view of shock strength and flexural strength (Erichsen), the high more indication coating of its intermediate value flexible good more, embodiment 1 shows that comparison is than embodiment 3 better results.In addition, in view of the rust resistance of the coating of estimating by salt-fog test, the low more indication rust resistance of its intermediate value is good more, and embodiment 1 shows comparison than embodiment 3 better rust resistances, and is as shown in table 10.
In a word, test-results from the performance of the electrodeposited coating that forms by electrodeposition resin composition according to the present invention, confirmation the present invention compares with prior art products provides the better slickness of better water dispersion stability, coating, rust resistance and flexible and improved anti-edge corrosion of while.
In addition, different with the comparative example in the bacterial surveys test of coating for preparing and washing water as can be seen from Table 11, the inhibition effect that embodiment 1 shows bacterium.Conjecture is because electrodeposition resin composition of the present invention contains xylene monosulfonic acid for this kind suppresses effect.Therefore, the caused generation of defects of bacterium in the washing water used of the application of the electrodeposition resin composition of the present invention pipeline that can prevent to adopt in the actual electrical deposition coating procedure is for example by crackle and pollution.
Claims (10)
1. be used for the resin combination of cation electrodeposition coating, it comprises:
(1) contains the base resin of the reaction product of the reaction product of polysulfide compound and epoxy compounds and amine compound and epoxy compounds;
(2) contain the curing agent resin of the reaction product of modified multicomponent alkylol cpd and blocked polyisocyanates compound, wherein said modified polyalcohol compound deriving is from the product of the similar Mannich reaction of phenolic compound, aliphatic series or aromatic amine compound and formalin;
(3) aromatic sulfonic acid; With
(4) has the rheology control agent of carbamate-functional.
2. according to the resin combination that is used for cation electrodeposition coating of claim 1, wherein said polysulfide compound is by the compound with following formula 1 expression:
[formula 1]
HS-(C
2H
4-O-CH
2-O-C
2H
4-S-S)n-C
2H
4-O-CH
2-O-C
2H
4-SH
Wherein n represents the integer of 0-50.
3. according to the resin combination that is used for cation electrodeposition coating of claim 1, the reaction product of wherein said polysulfide compound and epoxy compounds is by the compound with following formula 10 or 11 expressions:
[formula 10]
[formula 11]
Each R wherein
2Represent C independently
1-5Alkylidene group, n are represented the integer of 0-50, and m represents the integer of 0-6.
4. according to the resin combination that is used for cation electrodeposition coating of claim 1, wherein the product of similar Mannich reaction is by the compound with following formula 12 expressions:
[formula 12]
Wherein each R6 is replacement or the unsubstituted o-hydroxy-phenyl derived from cresols, butylphenol, octyl phenol, nonylphenol or phenol independently.
5. according to the resin combination that is used for cation electrodeposition coating of claim 1, the modified multicomponent alkylol cpd of wherein said product derived from similar Mannich reaction is by the compound with following formula 13 expressions:
[formula 13]
Wherein each R6 is replacement or the unsubstituted o-hydroxy-phenyl derived from cresols, butylphenol, octyl phenol, nonylphenol or phenol independently, each R7 is to be residue derived from monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), single ehtylethanolamine or monomethyl-ethanolamine derived from the residue of butylglycidyl ether or phenyl glycidyl ether and R8 independently.
6. according to the resin combination that is used for cation electrodeposition coating of claim 1, wherein said aromatic sulfonic acid is an xylene monosulfonic acid.
7. according to the resin combination that is used for cation electrodeposition coating of claim 1, wherein said rheology control agent with carbamate-functional be by make polyepoxide-amine compound, vulcabond and have hydroxyl the amine reaction, obtain with the polyamine addition reaction then.
8. according to the resin combination that is used for cation electrodeposition coating of claim 7, wherein said vulcabond is hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenylene vulcabond or their mixture.
9. according to the resin combination that is used for cation electrodeposition coating of claim 1, it comprises, based on 100 weight parts of base resin and curing agent resin total amount, 0.1-5 weight part aromatic sulfonic acid and 1-10 weight part have the rheology control agent of carbamate-functional.
10. cation electrodeposition coating, it comprises according to each resin combination and pigment among the claim 1-9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080096062A KR101005297B1 (en) | 2008-09-30 | 2008-09-30 | Resin composition for cathodic electrodeposition coating with good throw power comprising aromatic sulfonic acid and urethane-fuctional rheology control agent |
| KR10-2008-0096062 | 2008-09-30 | ||
| PCT/KR2009/004615 WO2010038943A2 (en) | 2008-09-30 | 2009-08-19 | Resin composition for cation electrodeposition paint with excellent inner permeability, containing aromatic sulfonic acid and urethane functional rheology modifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102186934A true CN102186934A (en) | 2011-09-14 |
| CN102186934B CN102186934B (en) | 2013-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801412862A Expired - Fee Related CN102186934B (en) | 2008-09-30 | 2009-08-19 | Resin composition for cation electrodeposition paint with excellent inner permeability, containing aromatic sulfonic acid and urethane functional rheology modifier |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR101005297B1 (en) |
| CN (1) | CN102186934B (en) |
| RU (1) | RU2467043C1 (en) |
| TR (1) | TR201103855T1 (en) |
| WO (1) | WO2010038943A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715722A (en) * | 2017-03-10 | 2018-10-30 | 株式会社Kcc | Cationic electrodeposition coating composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101029660B1 (en) | 2011-01-25 | 2011-04-15 | (주)새론테크 | Polyurea paint composition having excellent workability and superior toughness and method using the same |
| KR101863369B1 (en) * | 2011-12-30 | 2018-06-01 | 주식회사 케이씨씨 | Paint composition having polysilazane modified epoxy for chemical tank |
| US9068089B2 (en) * | 2013-03-15 | 2015-06-30 | Ppg Industries Ohio, Inc. | Phenolic admix for electrodepositable coating composition containing a cyclic guanidine |
| RU2662226C1 (en) * | 2013-12-20 | 2018-07-25 | БАСФ Коатингс ГмбХ | Aqueous primary dispersions, method of their production and use thereof |
| WO2015090441A1 (en) * | 2013-12-20 | 2015-06-25 | Basf Coatings Gmbh | Aqueous primary dispersions and methods for production and use thereof |
| KR102042239B1 (en) * | 2017-08-08 | 2019-11-08 | 주식회사 케이씨씨 | Cationic urethane curing agent and electro-deposition paint composition comprising the same |
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| US20040026248A1 (en) * | 2002-03-26 | 2004-02-12 | Satoru Uchidoi | Electrodeposition coating method using lead-free cationic electrodeposition coating composition |
| CN1671804A (en) * | 2002-06-27 | 2005-09-21 | Ppg工业俄亥俄公司 | Electrodepositable dielectric coating compositions to coat a substrate and methods to form dielectric coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8918086D0 (en) * | 1989-08-08 | 1989-09-20 | Ciba Geigy | Coating compositions |
| JP2000355795A (en) | 1999-06-15 | 2000-12-26 | Aisin Seiki Co Ltd | Surface treatment of aluminum and aluminum alloy |
| JP2002356646A (en) * | 2001-05-31 | 2002-12-13 | Nippon Paint Co Ltd | Lead-less cationic-electrodeposition paint composition containing crosslinked resin particle |
| US6811666B2 (en) * | 2002-02-20 | 2004-11-02 | E.I. Du Pont De Nemours And Company | Amine acid zwitterion additive for a cathodic electrocoating composition |
| KR100831205B1 (en) * | 2006-12-31 | 2008-05-21 | 주식회사 케이씨씨 | A cathodic electrodeposition coating compositions having improved appearance, anti-corrosion resistance and flexibility |
-
2008
- 2008-09-30 KR KR1020080096062A patent/KR101005297B1/en active IP Right Grant
-
2009
- 2009-08-19 WO PCT/KR2009/004615 patent/WO2010038943A2/en active Application Filing
- 2009-08-19 RU RU2011117554/05A patent/RU2467043C1/en not_active IP Right Cessation
- 2009-08-19 CN CN2009801412862A patent/CN102186934B/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040026248A1 (en) * | 2002-03-26 | 2004-02-12 | Satoru Uchidoi | Electrodeposition coating method using lead-free cationic electrodeposition coating composition |
| CN1671804A (en) * | 2002-06-27 | 2005-09-21 | Ppg工业俄亥俄公司 | Electrodepositable dielectric coating compositions to coat a substrate and methods to form dielectric coating |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715722A (en) * | 2017-03-10 | 2018-10-30 | 株式会社Kcc | Cationic electrodeposition coating composition |
| CN108715722B (en) * | 2017-03-10 | 2020-09-25 | 株式会社Kcc | Coating composition for cationic electrodeposition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010038943A3 (en) | 2010-07-01 |
| TR201103855T1 (en) | 2011-10-21 |
| RU2467043C1 (en) | 2012-11-20 |
| WO2010038943A2 (en) | 2010-04-08 |
| KR101005297B1 (en) | 2011-01-04 |
| CN102186934B (en) | 2013-09-11 |
| KR20100036708A (en) | 2010-04-08 |
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