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WO2008088151A1 - Résine cationique pour dispersion de pigment et composition de peinture électrodéposable comprenant celle-ci - Google Patents

Résine cationique pour dispersion de pigment et composition de peinture électrodéposable comprenant celle-ci Download PDF

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Publication number
WO2008088151A1
WO2008088151A1 PCT/KR2008/000213 KR2008000213W WO2008088151A1 WO 2008088151 A1 WO2008088151 A1 WO 2008088151A1 KR 2008000213 W KR2008000213 W KR 2008000213W WO 2008088151 A1 WO2008088151 A1 WO 2008088151A1
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Prior art keywords
amine
acid
resin
pigment grinding
monoepoxide
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Ceased
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PCT/KR2008/000213
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English (en)
Inventor
Man Yong Jung
Deok Soo Son
Han Joo Yang
Seok Chan Hong
Nam Joo Lee
Dong Wan Son
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KCC Corp
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KCC Corp
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Priority to CN2008800022747A priority Critical patent/CN101583678B/zh
Publication of WO2008088151A1 publication Critical patent/WO2008088151A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G17/00—Connecting or other auxiliary members for forms, falsework structures, or shutterings
    • E04G17/06—Tying means; Spacers ; Devices for extracting or inserting wall ties
    • E04G17/065—Tying means, the tensional elements of which are threaded to enable their fastening or tensioning
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy 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
    • 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
    • C08G59/184—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 with amines
    • 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
    • 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
    • C08G59/40—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 characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G17/00—Connecting or other auxiliary members for forms, falsework structures, or shutterings
    • E04G17/04—Connecting or fastening means for metallic forming or stiffening elements, e.g. for connecting metallic elements to non-metallic elements
    • E04G17/047—Connecting or fastening means for metallic forming or stiffening elements, e.g. for connecting metallic elements to non-metallic elements simultaneously tying two facing forms

Definitions

  • the present invention relates to a cationic resin for pigment dispersion (also referred as "cationic pigment grinding resin”) and an electrodepositable paint (or coating) composition comprising the same. More specifically, the present invention relates to a cationic pigment grinding resin, as a polyepoxide-amine resin, comprising (i) acid- neutralizable amine group derived from a monoepoxide-amine compound resulting from the reaction of monoepoxide and amine having 3 and more active hydrogen, and (ii) a quaternary ammonium salt group, in the middle of its chain; and an electrodepositable coating composition comprising the same.
  • a cationic pigment grinding resin as a polyepoxide-amine resin, comprising (i) acid- neutralizable amine group derived from a monoepoxide-amine compound resulting from the reaction of monoepoxide and amine having 3 and more active hydrogen, and (ii) a quaternary ammonium salt group, in the middle of its chain; and
  • Electrodeposition coating refers to non-conductive coating film-forming techniques in which a charged polymer moves to an electrode of the opposite charge under the action of direct electrical current, and the polymer is educed by the change of pH resulting from electrolysis.
  • the superiority of electrodeposition coating over the non-electrophoretic method is that electrodeposition coating layer exhibits greater adhesiveness and has noticeable anti-corrosive effect, and the degree of the electrodepositing process' contamination of the environment is low.
  • the pigment grinding resin used to introduce pigment in the course of preparing the elctrodepositable paint should stabilize the pigment so that it does not precipitate, and should be electrically charged so that it will electophorese in the electric field.
  • the resin mainly used for pigment grinding is preferably the adduct of polyepoxide and amine having a similar structure to the electrodeposition base resin, and it is preferred that the resin contains hydrophobic groups in some parts for stabilization of pigment in an aqueous media by enclosing the pigment surface taking on hydrophobicity.
  • a typical example of a pigment grinding resin for cationic electrodeposition is the quaternary ammonium salt group containing resin described in U.S. Patent Nos. 4,007,154 and 4,186,124.
  • the resin disclosed in the above literatures has good wettability of the pigment and heat stability due to the introduction of quaternary ammonium salt, the resin poses shortcomings such as severe roughness in the paint coating appearance and difficulty in thickening of the film.
  • U.S. Patent No. 4,230,552 discloses a pigment grinding resin which has a quaternary ammonium salt of diisocyanate-amine compound capped with alcohol of relatively large molecular weight such as aliphatic alkyl phenol.
  • the paint becomes unstable to the shearing force loaded onto it when passing through the recirculation pump. It is also known that the storage stability of the paint containing lead compound or carbon black is particularly bad. To compensate these defects, a mixture of sulfonium salt resin and quaternary ammonium salt resin was attempted, but this mixture also produced a rough appearance.
  • U.S. Patent No. 5,130,004 discloses a method for preparing a paint improving stability of heat transfer in paint containing lead by generating a sulfonium salt-quaternary ammonium salt mixture simultaneously by adding neutralized sulfide-amine mixture to epoxy resin which is flexibilized with nonyl phenol But it had the problem of low hydrophilicity.
  • resins containing primary, secondary and tertiary amine salts are disclosed as the resins for grinding. Although they smoothed out the electrodeposited paint coating, the resins had low stability after long storage in an electrodeposition bath solution and did not provide satisfactory pigment grinding. It is believed that because the above amine salts are the salt groups containing protons, the proton exchange reaction is occurred during pigment grinding and storage, so that storage stability becomes lowered after prolonged storage.
  • 365,214 and 380,264 disclose an epoxy type resin containing an oxazolidine group for pigment grinding.
  • the oxazolidine group in this resin still does not resolve the problem of poor storage in the bath solution but is being used due to its well pigment grinding.
  • the purpose of the present invention is to produce a pH and hydrophilicity adjustable cationic pigment grinding resin, which produces a good appearance, has good pigment grinding and remains stable even after prolonged storage, of various pigments in a electrodepositable coating composition, and an electrodepositable coating composition comprising this cationic resin.
  • the cationic pigment grinding resin as a polyepoxide-amine resin, comprising (i) an acid-neutralizable amine group derived from monoepoxide-amine compound resulting from the reaction of monoepoxide and amine which have 3 or more active hydrogen, and (ii) a quaternary ammonium salt group, in the middle of its chain is provided.
  • a pigment paste comprising the cationic pigment grinding resin of the present invention is provided.
  • the electrodepositable coating composition comprising the cationic pigment grinding resin of the present invention is provided.
  • the cationic pigment grinding resin of the present invention is basically a polyepoxide-amine resin.
  • the polyepoxide in the polyepoxide-amine resin usually has the 180-2,000 epoxide equivalent weight and has preferably 2 or more of 1,2-epoxide groups.
  • Examples of preferred polyepoxide resin are polyglycidyl ether of polyphenol, or the polyglycidyl ether of aromatic polyol such as bisphenol-A.
  • the polyepoxide resin is prepared by ether reaction of aromatic polyol with epihalohydrin such as epichlorohydrin or dichlorohydrin, or diepihalohydrin in the presence of an alkali.
  • polyepoxide resin is a modified polyepoxide resin which is derived from novlac resin, polyphenol resin, etc.
  • the molecular weight of the polyglycidyl ether of polyhydric materials can be increased by reacting polyglycidyl ether of aromatic diol with polyol which can react with epoxide group.
  • polyol applicable to the above reaction are ethylene glycol, diethylene glycol, triethylene glycol, 1 ,2-propylene glycol, 1 ,4-buthylene glycol, 1,5-pentanediol and bisphenol-A, etc.
  • the monoepoxide that can be used in the present invention is, for example, monoepoxide of Formula 1 below [Formula 1]
  • Rj is hydrogen or methyl
  • R 2 is hydrogen, alkyl including cycloalkyl (preferably Ci-Ci 8 alkyl), aryl (preferably C 6 -Cj 8 aryl), or substituted alkyl or aryl group which does not hinder the reaction between monoepoxide and amine.
  • Examples of the substituted alkyl or aryl group which does not hinder the reaction between monoepoxide and amine are as follows:
  • R 3 is alkyl including cycloalkyl (preferably Ci-Cj 8 alkyl) or C 6 -Ci 8 aryl]
  • glycidyl acetate which is glycidyl ester of mono-acid, glycidyl butyrate, glycidyl palmitate, glycidyl laurate, and glycidyl ester commercially available as CARDURA ETM
  • butyl glycidyl ether which is glycidyl ester of alcohol or phenol, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and p-(tertiary butyl)phenyl glycidyl ether or the like.
  • diamine, triamine or tetramine compound can be used alone or in combination. It is more preferred that diamine or triamine be used.
  • preferred amine are ethylene diamine, hexamethylene diamine, tetrapentamethylene diamine, pentamethylene diamine, 2-methylpentamethylene diamine, polyoxy alkylene diamine, diethylenetriamine, aminoethylethanolamine, triethylenetetramine, or mixtures thereof.
  • the pigment grinding resin is prepared by using the monoepoxide-amine compound having 2 or more active hydrogen, a poly epoxide-amine having an amine group placed in middle of chain is formed by a chain-extension reaction with polyepoxide resin during the preparing process, thereby the molecular weight of the pigment grinding resin can be adjusted, and hydrophilicity is reinforced.
  • the monoepoxide located on the side-chain imparts not only hydrophobicity to resin but also steric hindrance to the pigment paste, resulting in excellent pigment dispersity and stability. Also, the monoepoxide located on the side-chain imparts flexibility to the pigment grinding resin, resulting in smooth surface of paint coating.
  • hydrophilicity can be reinforced by adding additional acid and neutralizing the amine group in the preparing of the pigment paste.
  • hydrophilicity can be reinforced by adding additional acid and neutralizing the amine group in the preparing of the pigment paste.
  • the quaternary ammonium salt group which is incorporated in the middle of the chain of the pigment grinding resin of the present invention is formed by reaction of the epoxide group of the above polyepoxide-amine and the tertiary amine salt, and then incorporated into the middle of the chain by a chain-extension reaction.
  • the above tertiary amine salt is obtained from urethane linkage of hydroxy group dialkylalkanolamine and diisocyanate, and neutralization with acid.
  • the dialkylalkanolamine represented by Formula 2 below may be used, preferably selected from the group comprising dimethylethanolamine, dimethylpropanolamine, diethylethanolamine, diethylpropanolamine, and mixtures thereof.
  • Ri is aliphatic hydrocarbon with 2-4 carbon atoms
  • R 2 is aliphatic hydrocarbon with 2-6 carbon atoms.
  • the diisocyanate forming the urethane linkage with the hydroxy group of the above dialkylakanolamine may be methylene diphenyl diisocyanate, toluene diisocyanate, or isophrone diisocyanate, more preferably methylene diphenyl diisocyanate.
  • acid used for forming the quaternary ammonium salt.
  • Organic carboxylic acid is preferable, and one or more carboxylic acids selected from group consisting of lactic acid, acetic acid, propionic acid, butyric acid, dimethylpropionic acid, dimethylbutanoic acid, formic acid and glycolic acid are more preferred.
  • dialkylalkanolamine and diisocyanate are reacted in a molar ratio of 1 :2, respectively.
  • the tertiary amine salt formed by the reaction of dialkylalkanolamine and diisocyanate is reacted with epoxide of the polyepoxide-amine to form a quaternary ammonium salt, and the chain is elongated simultaneously with the reaction to increase the molecular weight of the chain.
  • the quaternary ammonium salt is located in the middle of the pigment grinding resin chain.
  • the ratio of the amine group (i) neutralized with the acid and the quaternary ammonium salt group (ii) which are contained in the resin of the present invention is not limited to a specific ratio. However, 0.25-1.4 milliequivalents of the amine group (i) neutralized with the acid and the quaternary ammonium salt group (ii) per Ig of the pigment grinding resin is appropriate in view of the molecular weight dispersion or degree of hydrophilicity of the polymer. When the contents of the amine group (i) neutralized with the acid and the quaternary ammonium salt group (ii) are less than the content suggested above, the wettability of the pigment becomes poor.
  • the pigment grinding resin of the present invention has excellent dispersity, and at the same time, allows the pigment paste and electrodepositable coating composition comprising the same to be highly stable.
  • the pigment paste of the present invention is prepared by grinding various pigment components with the pigment grinding resin of the present invention.
  • Conventional electrodepositable paints usually cause a problem of transfer instability according to the pigment.
  • the pigment grinding resin of the present invention helps to stabilize the transfer.
  • the pigment components used in preparing the pigment paste may include titanium dioxide, antimony oxide, zinc oxide, barium carbonate, calcium carbonate, aluminum silicate, silica, magnesium carbonate and/or magnesium silicate.
  • the coloring pigment such as cadmium yellow, cadmium red, carbon black, phthalocyanine blue, chrome yellow, toluidine red and hydrated iron oxide may also be used.
  • the carbon black frequently exhibits poor heat stability in storage due to its small particle size and strong hydrophobicity.
  • the pigment grinding resin of the present invention can help to stabilize the carbon black in storage under heat.
  • the pigment paste may comprise optional components such as humectant, surfactant and antifoaming agent in addition to the above pigment components and the pigment grinding resin component.
  • the grinding is usually performed until the pigment is reduced to the desired size, preferably by using a ball mill, sand mill, and continuous mill until the pigment is wetted or dispersed by the grinding vehicle.
  • the particle size of the pigment after grinding is 10 micron or less, preferably 6-8, more preferably 7-8 on the Hegman gauge.
  • the grinding of the pigment component is done in an aqueous dispersion liquid of the vehicle. Since the amount of the water in the aqueous dispersion liquid should be sufficient for forming continuous phase, the electrodepositable paint usually comprises solids of 30-70% by weight. If there is too little water, the phenomenon of continous increase in viscosity can occur.
  • the weight ratio of the pigment component to the solid in the pigment grinding resin usually remains about 1.5:1 to 10:1, preferably 3:1 to 6:1.
  • the cationic electrodepositable resin which is a resin already known in the field, for cationic electrodeposition and the pigment paste of the present invention is combined
  • electrodepositable coating composition of the present invention is obtained.
  • the final electrodepositable coating composition has pigment/binder ratio of approximately 0.1 to 0.5.
  • a bath containing pigment and resin solids of 5-25% by weight is usually used in the electrodeposition process, and therefore, the final electrodepositable coating composition may further comprise sub resin, solvent, antioxidant, surfactant etc. in addition to the pigment paste and the electrodepositable main resin.
  • the aqueous electrodepositable coating composition is laid to contact with the electrical cathode and anode, and then, the electrodeposition is performed under direct current voltage of several V to several hundreds V and a current density of 0.25-15 A/ft .
  • water washing process and curing process is applied to produce the final paint coating.
  • the curing process is usually carried out at temperatures of 150-200 ° C for 15-60 minutes.
  • the electrodepositable coating composition of the present invention comprises capped isocyanate as a curing agent.
  • the above capped isocyanate is organic polyisocyanate, and may be a polyisocyanate whose isocyanate group is reacted with the capping compound so that the capped isocyanate group remains stable with active hydrogen at room temperature but reacts with active hydrogen at high temperatures.
  • the aliphatic (including cyclic aliphatic) or aromatic polyisocyanate can be used to prepare the above capped polyisocyante curing agent.
  • Typical examples are 2,4- or 2,6-tolulene diisocyanate or a mixture thereof, p-phenylene diisocyanate, tetramethylene or hexamethylene diisocyanate, dicyclohexylmethane-4,4 '-diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate and polymethylene polyphenyl isocyanate.
  • a higher polyisocyanate such as tri-isocyanate may be used.
  • triphenylmethane -4,4',4"-triisocyanate may be used.
  • a NCO- prepolymer such as reaction products of polyisocyanate with polyol such as neopentylglycol and trimethylol propane, or with polymer polyol such as polycaprolactone diol and triol may be used.
  • the capped polyisocyanate curing agent can be used in two ways. First, the completely capped form, in which no free isocyanate remains, can be used. In this form, it exists as 2-component resin system through the blending with the epoxy main chain. Second, after capping in parts, the capped polyisocyanate curing agent is reacted with active hydrogen in the epoxy polymer backbone to prepare a 1 -component resin. In the view of the stability of resin, the latter in which the epoxy main chain and urethane curing agent form a chemical bond so that the water-dispersion stability is more stable.
  • a curing catalyst such as a tin catalyst
  • the hardening catalyst may be for example, dibutyltin dilaurate and dibutyltin oxide.
  • the preferable amount of the tin component is about 0.05-1% by weight of the total weight of the resin solids.
  • Monoepoxide-amine compound was prepared from the ingredients shown in TABLE 1 below. TABLE 1 Preparation composition of monoepoxide-amine compound
  • the 2-methylpentamethylene diamine and 2-buthoxyethanol were added to the reactor, and heated to 70 ° C with slow agitation. With the temperature maintained at 70-
  • the monoepoxide was slowly added. After the addition was completed, the reaction mixture was heated to 100°C and agitated for 2 hours to prepare the monoepoxide-amine compound.
  • Monoepoxide-amine compound was prepared from the ingredients shown in TABLE 2 below. TABLE 2 Preparation composition of the monoepoxide-amine compound
  • the diethylenetriamine and 2-buthoxyethanol were added to the reactor, and heated to 70 ° C with slow agitation. With the temperature maintained at 70-80 ° C, the 2- ethylhexyl glycidyl ether was slowly added. After the addition was completed, the reaction mixture was heated to 100 0 C and agitated for 2 hours to prepare the monoepoxide-amine compound.
  • a tertiary amine salt was prepared as a quaternizing agent from the ingredients in TABLE 3 below.
  • PAPI2940 Polymeric methylene diphenyl diisocyanate commercially available from Dow Chemical Co.
  • the PAP 12940 and methyl isobutyl ketone were placed in reaction vessel, and dimethylethanolamine was added. At that time, the exothermal reaction occurred.
  • the reaction mixture was heated to 80 ° C . With the temperature held at 80 ° C , the reaction mixture was agitated for 3 hours. The reaction mixture was then cooled to 60 °C and a 2-butoxy ethanol was added. An acetic acid was then added, and the mixture was agitated at 65 ° C for about 1 hour to synthesize the quaternizing agent.
  • the pigment grinding resin was prepared from the ingredients shown in TABLE 4 below. TABLE 4 Preparation composition of the pigment grinding resin
  • the pigment grinding resin was prepared from ingredients shown in TABLE 5 below.
  • N8010 and 2-butoxyethanol( 1 st) were added to the reaction vessel, and then heated to 90 ° C with agitation.
  • the monoepoxy-amine compound of the Preparation Example 2 was added slowly. At this time, some heat was generated.
  • the reaction temperature was increased to 120 ° C and retained for 2 hours. The reaction was retained to reach 1,300 of epoxy equivalents. When the epoxy equivalents reached 1,300, 2- butoxyethanol(2nd) was added.
  • the reaction mixture was cooled to 85-90 ° C and deionized water was added followed by the addition of the quaternizing agent of the preparation Example 3. Until the acid value reached about 1, the temperature of the reaction mixture was held at 80-85 ° C, and then 2-butoxyethanol(3rd) was added to prepare the pigment grinding resin.
  • a quaternizing agent was prepared from the ingredients shown in TABLE 6 below.
  • a pigment grinding resin was prepared from the ingredients shown in TABLE 7 below. TABLE 7 Preparation composition of pigment grinding resin
  • EPON 829 and bisphenol A were added to the reaction vessel in the atmosphere of nitrogen, and heated to 150-160°C to initiate exothermal reaction.
  • the reaction was conducted at 150-160 ° C for 1 hour.
  • the reaction mixture was then cooled to 120 ° C , and the toluene diisocyanate half-capped with 2-ethylhexanol in the solvent of methyl isobutyl ketone was added.
  • the temperature of the reaction mixture was retained between 110-120 ° C , and then the 2-butoxyethanol was added.
  • the reaction mixture was cooled to 85-90 °C , the deionized water was added followed by the addition of the quaternizing agent. Until the acid value reached about 1, the temperature of the reaction mixture was held at 80 to 85 ° C .
  • a Dibutyltin oxide paste was prepared from the ingredients shown in TABLE 8 below.
  • Example 2 While the pigment grinding resin prepared in Example 1 was being agitated, a dibutyltin oxide was added. When the viscosity became high according to the increase of the pigment powder, deionized water(lst) was added and the mixture was well agitated until the pigment powder got homogenized. Finally, the mixture was diluted with deionized water (2nd). The above mixture was dispersed to Hegman number 8 by SL- 703 mill (BYK).
  • Each dibutyltin oxide paste of Preparation Example 5 and Comparative Preparation Example 2 were prepared by the same method of Preparation Example 4, using the resin of Example 2 and Comparative Example 1 as the pigment grinding resin, respectively.
  • a pigment paste was prepared from the ingredients shown in TABLE 9 below. TABLE 9 Preparation composition of pigment paste
  • ASP 200 Aluminum silicate commercially available from Engelhard Co.
  • Surfynol 104 Hexyne diol-based humectant commercially available from Air Products]
  • Example 4 Preparation of pigment paste
  • a pigment paste was prepared by the same method of Example 3, except that the pigment grinding resin of Example 2 and dibutyltin oxide paste of Preparation Example of 5 were used.
  • a pigment paste was prepared by the same method of Example 3, except that the pigment grinding resin of Comparative Example 1 and dibutyltin oxide paste of Comparative Preparation Example 2 were used.
  • a urethane curing agent used in the cationic electrodepositable resin was prepared from the ingredients shown in TABLE 10 below. TABLE 10 Preparation composition of urethane curing agent
  • the PAPI 2940, methyl isobutyl ketone and dibutyltin dilaurate were put into a reaction flask and heated to 30 ° C under a nitrogen atmosphere.
  • the 2-(2- butoxyethoxy)ethanol(lst) was added slowly while holding the temperature between 60- 65 " C . After the addition was completed, the reaction mixture was retained at 65 ° C for 90 minutes.
  • the trimethylol propane was subsequently added and the mixture was heated to 110 0 C and held at that temperature for 3 hours.
  • the 2-(2- butoxyetoxy)ethanol(2nd) was then added. The temperature was continuously held at 110 °C until no more of the unreactive NCO could be detected by ultraviolet detection.
  • a cationic electrodeposition main resin dispersion was prepared from the ingredients shown in TABLE 11 below.
  • KT-22 Product of Air Products Co.; diketimine which is diethylenetriamine capped with methylisobutylketone, 73% solution in methylisobutylketone]
  • the EPON 828, bisphnol A-ethylene oxide adduct, bisphenol A and methyl isobutyl ketone were placed in a reaction vessel and heated to 30 ° C under a nitrogen atmosphere.
  • the benzyldimethylamine(lst) was added, and the reaction mixture was allowed to exotherm to about 185 "C .
  • the existing water was then removed azeotropically by reflux.
  • the reaction mixture was cooled to 160 ° C and held at that temperature for 30 minutes.
  • the mixture was further cooled to 145 ° C and then, the benzyldimethylamine(2nd) was added. The temperature was held at 145 ° C until the epoxy equivalents weight reached 1,100-1,140.
  • the urethane curing agent of Preparation Example 6, KT22 and N-methyl ethanol amine were added sequentially. After the mixture was allowed to exotherm, the reaction mixture was cooled to 125 ° C . After remaining at 125 °C for 2 hours, the reaction mixture was slowly added to the mixture comprising formic acid and deionized water(lst) with sufficient agitation to disperse. Subsequently, deionized water(2nd) and deionized water(3rd) were slowly added in order for further dilution, and the organic solvent was removed by vacuum stripping to produce a cationic electrodepositable water dispersable resin having solids content of 36%.
  • Examples 5-6 and Comparative Example 3 Preparation of electodepositable coating composition in the form of an electrodeposition bath While agitating the mixture of 3,318 parts by weight of water-dispersable resin synthesized by the method of the above Preparation Example 7 and 3,638 parts by weight of deionized water, 536 parts by weight of each of the pigment paste prepared in Example 3, Example 4 and Comparative Example 2 were added to prepare the cationic electrodepositable coating compositions having a solid content of 20% for Examples 5-6 and Comparative Example 3, respectively.
  • the above prepared electrodepositable coating composition was passed through an ultrafilter to 20% of its initial volume, and then the ultrafiltrate was exchanged with deionized water. After remaining in an agitation state for one day, electodeposition coating was performed under direct current voltage of 210-270 V at 28 ° C for 2 minutes. A steel plate treated with phosphoric acid was used as a test sample. The sample was coated for 2 minutes and allowed to be cured at 170 ° C for 30 minutes. The various property values of the paint coating were measured and are shown in TABLE 12 below.
  • Heat storage stability was evaluated by storing the pigment paste at 60 ° C oven and measuring the elapsed time of gellation.
  • the pigment grinding resin prepared according to the present invention had good pigment dispersibility, and the pigment grinding resin itself and the pigment paste and paint composition prepared with the same remained stable even after prolonged storage, were resistant against the formation of pinholes and craters, and gave a smooth appearance.
  • a cationic pigment grinding resin giving good appearance, having good pigment dispersibility and providing good storage stability for various pigments, and a pigment paste and electrodepositable coating composition comprising the same can be produced.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Architecture (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
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  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

La présente invention concerne une résine de broyage de pigment cationique et une composition de revêtement électrodéposable comprenant celle-ci. Plus spécifiquement, la présente invention concerne une résine de broyage de pigment cationique, une résine de polyépoxyde-amine comprenant (i) un groupe amine neutralisable par un acide dérivé d'un composé de monoépoxyde-amine résultant de la réaction de monoépoxyde et d'une amine ayant 3 atomes d'hydrogène actif et plus, et (ii) un groupe de sel d'ammonium quaternaire, au milieu de sa chaîne, et une composition de revêtement électrodéposable comprenant celui-ci.
PCT/KR2008/000213 2007-01-16 2008-01-14 Résine cationique pour dispersion de pigment et composition de peinture électrodéposable comprenant celle-ci Ceased WO2008088151A1 (fr)

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KR1020070004865A KR100891156B1 (ko) 2007-01-16 2007-01-16 안료 분산용 양이온 수지 및 그를 포함하는 전착 도료조성물

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WO2015090469A1 (fr) * 2013-12-20 2015-06-25 Basf Coatings Gmbh Procédé de production d'une pâte pigmentaire, peinture aqueuse pour électrodéposition, son utilisation, procédé de peinture par électrodéposition cataphorétique et objet revêtu
CN112457721A (zh) * 2020-12-03 2021-03-09 上海瑞君电泳涂料有限公司 环氧电泳涂料用色浆、电泳涂料及其制备工艺

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JP5653310B2 (ja) * 2011-07-13 2015-01-14 日産自動車株式会社 塗料組成物及びそれを用いた塗膜形成方法
RU2486220C2 (ru) * 2011-09-07 2013-06-27 Закрытое акционерное общество "ОНТК-94" Композиция для катодного электроосаждения с высокой рассеивающей способностью, предназначенная для получения покрытий с повышенной твердостью и износостойкостью
KR101857296B1 (ko) * 2011-12-27 2018-06-20 주식회사 케이씨씨 외관이 향상된 박막형 전착 도료용 변성 폴리에폭사이드-아민 수지, 그 제조 방법 및 이를 포함하는 전착 도료 조성물
KR101940377B1 (ko) * 2016-08-18 2019-01-18 주식회사 케이씨씨 전착 도료 조성물
KR102341535B1 (ko) * 2017-03-10 2021-12-22 주식회사 케이씨씨 양이온 전착수지 조성물

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WO2015090469A1 (fr) * 2013-12-20 2015-06-25 Basf Coatings Gmbh Procédé de production d'une pâte pigmentaire, peinture aqueuse pour électrodéposition, son utilisation, procédé de peinture par électrodéposition cataphorétique et objet revêtu
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CN112457721B (zh) * 2020-12-03 2023-02-03 上海瑞君电泳涂料有限公司 环氧电泳涂料用色浆、电泳涂料及其制备工艺

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CN101583678B (zh) 2013-07-17
KR20080067491A (ko) 2008-07-21
KR100891156B1 (ko) 2009-04-06
TR200905327T1 (tr) 2009-09-23
CN101583678A (zh) 2009-11-18
RU2428444C2 (ru) 2011-09-10

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