WO2013047319A1 - Composition de revêtement par électrodéposition - Google Patents

Composition de revêtement par électrodéposition Download PDF

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Publication number
WO2013047319A1
WO2013047319A1 PCT/JP2012/074058 JP2012074058W WO2013047319A1 WO 2013047319 A1 WO2013047319 A1 WO 2013047319A1 JP 2012074058 W JP2012074058 W JP 2012074058W WO 2013047319 A1 WO2013047319 A1 WO 2013047319A1
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WO
WIPO (PCT)
Prior art keywords
electrodeposition coating
epoxy resin
amine
plasticizer
coating composition
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PCT/JP2012/074058
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English (en)
Japanese (ja)
Inventor
宗平 金子
健司 野嶋
克彦 庄
与志夫 児島
Original Assignee
日本ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority to CN201280047541.9A priority Critical patent/CN103857755B/zh
Publication of WO2013047319A1 publication Critical patent/WO2013047319A1/fr

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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
    • C09D5/4434—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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material

Definitions

  • the present invention relates to an electrodeposition coating composition with little loss on heating.
  • Electrodeposition coating is applied to metal materials for the purpose of imparting high corrosion resistance.
  • Electrodeposition coating is widely used as an undercoat for coatings that require high anti-corrosion properties because it can be applied to the details of the coatings with complex shapes and can be applied automatically and continuously. .
  • Electrodeposition coating usually has an electrodeposition process and a curing process.
  • the object to be coated is immersed in the electrodeposition coating composition, and in this state, a voltage is applied between the object to be coated and the electrodeposition coating composition. Then, the coating component is deposited on the surface of the object to be coated, so that an electrodeposition coating film is formed.
  • the electrodeposition coating film formed on the surface of the object to be coated is baked and cured at 120 ° C. to 260 ° C.
  • the electrodeposition coating composition is composed of an emulsion in which an ionized binder, pigment or the like is dispersed in an aqueous medium.
  • a thermosetting resin composition is usually used.
  • a curing system composed of a combination of an amine-modified epoxy resin and a blocked isocyanate curing agent has good corrosion resistance, adhesion, throwing power, etc., and is widely used as a binder for cationic electrodeposition coatings.
  • the curing reaction proceeds by removing the blocking agent of the blocked isocyanate by heating.
  • the detached blocking agent becomes a scum and adheres to the drying furnace or the like, or volatilizes in the air and causes air pollution.
  • VOC volatile organic compounds
  • the present invention has been made in view of the above, and an object of the present invention is to provide an electrodeposition coating composition with less heat loss than before.
  • the present invention provides an electrodeposition coating composition with little loss on heating, which is substantially free of a crosslinking agent and formed by electrodeposition coating at 105 ° C. for 3 hours. After drying, an electrodeposition coating composition having a heating loss of 10% by mass or less when heated at 200 ° C. for 25 minutes is provided.
  • the electrodeposition coating composition comprises a plasticizer comprising an amine-modified epoxy resin (A) obtained by modifying an epoxy resin having a bisphenol skeleton with an amine compound, and a plasticizer (B-1) comprising an aromatic alcohol compound (B) is preferably included.
  • the plasticizer (B-1) has a structure represented by the following general formula (1), and is mixed with the amine-modified epoxy resin (A) at a mass ratio of 10 times the amine-modified epoxy resin (A). It is preferable to dissolve the epoxy resin (A).
  • R is C p H 2p (p is an integer of 1 to 3, the same shall apply hereinafter), O (C m H 2m O) p (m is an integer of 2 to 5) The same shall apply hereinafter) or CH 2 O— (C m H 2m O) n (n is 1 or 2), and X is H or OCH 3 .
  • R is C p H 2p (p is an integer of 1 to 3, the same shall apply hereinafter), O (C m H 2m O) p (m is an integer of 2 to 5) The same shall apply hereinafter) or CH 2 O— (C m H 2m O) n (n is 1 or 2), and X is H or OCH 3 .
  • the plasticizer (B) further includes a plasticizer (B-2) other than the plasticizer (B-1), and the plasticizer (B-2) is water-insoluble with a viscosity of 1000 mPa ⁇ s or less.
  • the amine-modified epoxy resin (A) is dissolved when an equal amount of the amine-modified epoxy resin (A) is mixed in a mass ratio.
  • the total content of the plasticizer (B-1) and the plasticizer (B-2) is preferably 39% by mass or more based on the amine-modified epoxy resin (A).
  • the molecular weight of the epoxy resin having a bisphenol skeleton is preferably 2000 or more.
  • the present invention also provides an electrodeposition coating film forming method for forming an electrodeposition coating film by electrodeposition-coating the electrodeposition coating composition on a substrate.
  • the electrodeposition coating film formed by electrodeposition coating was dried at 105 ° C. for 3 hours and then heated at 200 ° C. for 25 minutes.
  • the weight loss upon heating can be reduced to 10% by mass or less, and an electrodeposition coating composition with less heat loss than before can be provided.
  • the electrodeposition coating film according to the present invention has the above-mentioned characteristics, it is possible to reduce the volatilization of chemical substances from the coating film after drying into the atmosphere, for example, heating at 200 ° C. for 40 minutes.
  • the high temperature loss on heating when the subsequent electrodeposition coating film is heated at 240 ° C. for 25 minutes can be 2% or less.
  • Electrodeposition coating composition In the electrodeposition coating composition of this embodiment, the electrodeposition coating film formed by electrodeposition coating is dried at 105 ° C. for 3 hours and then heated at 200 ° C. for 25 minutes. And an electrodeposition coating composition substantially free of a crosslinking agent. That is, in the conventional electrodeposition coating composition, the loss on heating exceeded 10% by mass, whereas in the electrodeposition coating composition of the present embodiment, the loss on heating was 10% by mass or less. Heat loss is reduced. Preferably, the loss on heating is 5% by mass or less.
  • the “heat loss” is specifically a value calculated by the following formula (1) by performing the following operations (a) to (g).
  • the heating loss cannot be calculated. Therefore, the range of “heating loss is 10% by mass or less” in this embodiment is used.
  • the film-forming property has a characteristic that the higher the temperature (bath temperature) of the electrodeposition coating composition is within a normal range, the higher the temperature is within a normal range, and the generally preferred bath temperature is within a range of 10 ° C. to 40 ° C. If the film forming property can be ensured and the heating loss is 10% by mass or less, it is included in the scope of the present embodiment.
  • test plate is precisely weighed to determine the test plate weight A before electrodeposition coating.
  • B The test plate is immersed in the electrodeposition coating composition, and electrodeposition coating is performed so that the film thickness after drying is 20 ⁇ m.
  • C After washing the test plate after electrodeposition coating, the wet film formed on the surface of the test plate is dried at 105 ° C. for 3 hours.
  • D After drying, the test plate is cooled to room temperature in a desiccator and then precisely weighed to determine the test plate weight B after drying.
  • E The test plate after drying is baked at 200 ° C. for 25 minutes.
  • F After baking, the test plate is cooled to room temperature in a desiccator and then precisely weighed to determine the test plate weight C after baking.
  • G Heat loss D by substituting the test plate weight A before electrodeposition coating, the test plate weight B after drying, and the test plate weight C after baking, obtained as described above, into the following formula (1). Is calculated.
  • the “high temperature loss on heating” means that among the operations (a) to (g), the drying condition (c) is performed at 200 ° C. for 40 minutes, and the drying condition (e) is 25 at 240 ° C. This means weight loss by heating when performed for a minute. It is possible to evaluate the volatilization of chemical substances from the coated film after drying into the atmosphere by high-temperature heat loss.
  • the electrodeposition coating composition of the present embodiment is a lacquer type electrodeposition coating composition in which a coating having anticorrosion properties can be obtained by volatilizing a solvent without depending on a crosslinking reaction.
  • the content of the crosslinking agent is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less with respect to the electrodeposition coating composition.
  • the electrodeposition coating composition of this embodiment is preferably a plasticizer (B-) comprising an amine-modified epoxy resin (A) obtained by modifying an epoxy resin having a bisphenol skeleton with an amine compound, and an aromatic alcohol compound.
  • a cationic electrodeposition coating composition comprising a plasticizer (B) comprising 1).
  • the amine-modified epoxy resin (A) can be obtained by modifying an epoxy resin having a bisphenol skeleton with an amine compound.
  • An epoxy resin having a bisphenol skeleton has high rigidity, and the resin itself has excellent corrosion resistance.
  • An epoxy resin having a typical bisphenol skeleton has a structure in which bisphenol A and diglycidyl ether of bisphenol A are condensed as represented by the following general formula (2).
  • n represents an integer. ...
  • the proportion of the bisphenol skeleton is preferably 90% by mass or more.
  • the ratio which the bisphenol skeleton in an epoxy resin occupies is high, and the excellent anticorrosion property is obtained by using an epoxy resin with high rigidity.
  • the “bisphenol skeleton” means a skeleton represented by the general formula (2).
  • the molecular weight of the epoxy resin having a bisphenol skeleton is preferably 2000 or more. More preferably, it is 2000 to 9000, and still more preferably 3000 to 8000.
  • “molecular weight” means a value calculated by epoxy equivalent ⁇ 2 in the case of having a structure such as the above formula (2).
  • the epoxy equivalent in this invention can be determined by the method based on JISK7236, but using methyl ethyl ketone (MEK) instead of chloroform as a solvent which melt
  • MEK methyl ethyl ketone
  • the epoxy resin having a bisphenol skeleton commercially available products can be used as they are, and those synthesized by condensing bisphenol A and diglycidyl ether of bisphenol A can also be used. Any appropriate method is employed as the synthesis method. For example, a method of synthesizing by adding excessively diglycidyl ether of bisphenol A to bisphenol A and heating in an organic solvent such as methyl isobutyl ketone using an organic base such as dimethylbenzylamine as a catalyst can be mentioned. . Preferably, the reaction is traced by measuring the epoxy equivalent, and the reaction is terminated when the target epoxy equivalent is reached.
  • the electrodeposition coating composition of this embodiment may contain the organic solvent used at the time of the synthesis
  • the amine modification of an epoxy resin having a bisphenol skeleton is typically performed by ring-opening addition of an epoxy group of an epoxy resin as a raw material with an amine compound having active hydrogen.
  • the modification rate of the epoxy group is preferably 90% or more, and more preferably substantially all the epoxy groups are modified.
  • the “epoxy group modification rate” means the ratio of the total number of moles of amino groups of the amine compound to be added to the total number of moles of epoxy groups of the epoxy resin having a bisphenol skeleton.
  • the amount of modification of the amine-modified epoxy resin (A) is preferably 10% by mass or less. By setting the modification amount to 10% by mass or less, excellent anticorrosive properties can be obtained. Moreover, the lower limit of the modification amount is not particularly limited as long as the amine-modified epoxy resin (A) can be dispersed in water. This is because, as will be described later, whether or not the amine-modified epoxy resin (A) is dispersed in water is determined by various factors.
  • the “modified amount” means the amount of the ring-opening addition compound with respect to the total amount of the mass of the epoxy resin and the mass of the compound capable of ring-opening addition of the epoxy group of the epoxy resin (hereinafter also referred to as “ring-opening addition compound”).
  • Mass% ( mass of ring-opening addition compound / (mass of epoxy resin + mass of ring-opening addition compound) ⁇ 100).
  • the mass of a ring-opening addition compound means the quantity of the amine compound produced
  • Examples of the compound for ring-opening addition of the epoxy group of the epoxy resin include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, aminoethylethanolamine, and ketimine compounds of these amines.
  • amine compounds such as diethylenetriamine and diketiminates of diethylenetriamine; monophenols such as phenol, cresol, nonylphenol and nitrophenol; monoalcohols such as hexyl alcohol, 2-ethylhexanol, stearyl alcohol, ethylene glycol and monohexyl ether; Aliphatic monocarboxylic acids such as stearic acid and octylic acid; glycolic acid, dimethylolpropionic acid, hydroxypivalic acid Lactic acid, aliphatic hydroxycarboxylic acids such as citric acid; mercaptoalkanols mercaptoethanol, etc. and the like.
  • ring-opening addition compounds can be used alone or in combination of two or more.
  • diketiminates are preferably used.
  • a primary amino group can be expressed during neutralization described later, and the coating film properties such as adhesion are improved.
  • Arbitrary appropriate methods are employ
  • the amino group of the amine-modified epoxy resin (A) is preferably neutralized with an acid compound. Thereby, the amine-modified epoxy resin (A) can be uniformly dispersed in water.
  • the neutralization rate of the amine-modified epoxy resin (A), that is, the ratio of the equivalent of the acid compound to the equivalent of the amino group of the amine-modified epoxy resin (A) is preferably 10% to 100%.
  • the acid compound examples include organic acids including inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfamic acid, and carboxylic acid compounds such as formic acid, acetic acid, propionic acid and lactic acid. These acid compounds can be used alone or in combination of two or more. Among these, organic acids are preferably used, and carboxylic acid compounds are particularly preferably used. By neutralizing the amine-modified epoxy resin (A) with these acid compounds, more excellent corrosion resistance can be obtained. Among the carboxylic acid compounds, acetic acid is preferably used from the viewpoint of volatility. For example, a diethylene trimian-modified epoxy resin (A) neutralized with acetic acid is represented by the following general formula (3). In the following general formula (3), n represents an integer. ... General formula (3)
  • amine-modified epoxy resin (A) Whether or not the amine-modified epoxy resin (A) is dispersed in water depends on the molecular weight and amino group equivalent of the amine-modified epoxy resin (A), the type of amine compound used for modification, the type and amount of acid compound (neutralization) Rate) and the like. For this reason, it can emulsify by adjusting these parameters.
  • the plasticizer (B) includes a plasticizer (B-1) made of an aromatic alcohol compound.
  • a plasticizer (B-1) made of an aromatic alcohol compound.
  • the plasticizer (B-1) has a structure represented by the following general formula (1), and when mixed with the amine-modified epoxy resin (A) in a mass ratio of 10 times, the amine-modified epoxy resin (A) is dissolved.
  • “dissolved” means that when the amine-modified epoxy resin (A) and the plasticizer (B-1) are mixed at a mass ratio of 1:10, a transparent solution can be obtained by mixing uniformly without turbidity. means.
  • R is C p H 2p (p is an integer of 1 to 3, the same shall apply hereinafter), O (C m H 2m O) p (m is an integer of 2 to 5) The same shall apply hereinafter) or CH 2 O— (C m H 2m O) n (n is 1 or 2), and X is H or OCH 3 . ]
  • plasticizer (B-1) examples include benzyl alcohol (BzOH), 2-phenylethyl alcohol (2-pH-EtOH), 3-phenyl-1-propanol (3-pH-1-PrOH), 4 -Methoxybenzyl alcohol (4-MeO-BzOH), phenyl glycol (PhG), benzyl glycol (BzG) and the like.
  • benzyl alcohol having a low boiling point is preferably used.
  • the plasticizer (B) may further contain a plasticizer (B-2) other than the plasticizer (B-1).
  • the plasticizer (B-2) is liquid at room temperature (25 ° C.) and has a viscosity of 1000 mPa ⁇ s or less, preferably 500 mPa ⁇ s or less.
  • the plasticizer (B-2) is insoluble in water.
  • water-insoluble means a state that is not freely miscible with water, and means a state that does not substantially dissolve in water.
  • the water solubility of the plasticizer (B-2) is preferably 10 parts by mass or less with respect to 100 parts by mass of water at room temperature (25 ° C.).
  • the viscosity of the plasticizer (B-2) is a value measured at 20 ° C. using an E-type viscometer (for example, manufactured by Toki Sangyo Co., Ltd.).
  • the plasticizer (B-2) dissolves the amine-modified epoxy resin (A) when mixed in an equal amount to the amine-modified epoxy resin (A) in a mass ratio.
  • the plasticizer (B-2) is mixed with the amine-modified epoxy resin (A) at a mass ratio of 10 times the amine-modified epoxy resin (A).
  • the phase cannot be dissolved and phase separation occurs.
  • “dissolved” means that when an equal amount of the amine-modified epoxy resin (A) and the plasticizer (B-2) are mixed, a transparent solution can be obtained by uniformly mixing without turbidity.
  • plasticizer (B-2) examples include diethylene glycol dibutyl ether (dibutyl diglycol, DBDG), dipropylene glycol monopropyl ether (propylpropylene diglycol, PFDG), propylene glycol monobutyl ether (PnB), dipropylene glycol.
  • DBDG diethylene glycol dibutyl ether
  • PFDG dipropylene glycol monopropyl ether
  • PnB propylene glycol monobutyl ether
  • Glycol ether compounds such as monobutyl ether (DPnB), butyl propylene diglycol (BFDG), tripropylene glycol monobutyl ether (TPnB) and polypropylene glycol # 1000, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), Diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diheptyl phthalate (DHP), di-n-octyl phthalate (N-DOP), butyl benzyl phthalate (BBP), ethyl phthalyl ethyl glycolate, di-2-ethylhexyl adipate (DOA) and dibutyl diglycol adipate (BXA), etc., carboxylic acid ester compounds, methyl isobutyl ketone ( MIBK), methyl ethyl ketone (MEK),
  • plasticizer (B-2) As a commercial product of the plasticizer (B-2), Solvesso 200 (manufactured by Exxon Chemical Co., Ltd.) can be mentioned. These plasticizers (B-2) can be used alone or in combination of two or more. Among these, from the viewpoint of long-term stability, a compound having no ester bond in the molecule is preferably used. From the viewpoint of odor, glycol ether compounds are preferably used.
  • the total content of the plasticizer (B-1) and the plasticizer (B-2) is preferably 39% by mass or more based on the mass of the amine-modified epoxy resin (A). Thereby, the film forming property at the time of electrodeposition can be improved more, and the electrodeposition coating film provided with the high corrosion resistance by the rigidity of an epoxy resin can be obtained more reliably.
  • the content of the plasticizer (B-1) is 26% by mass or more, and the total content of the plasticizer (B-1) and the plasticizer (B-2) is more preferably 49% by mass or more. preferable.
  • the electrodeposition coating composition of this embodiment contains water as a main component and may contain an organic solvent other than the plasticizer (B).
  • the organic solvent may contain an organic solvent that dissolves in water.
  • Specific examples of the organic solvent include alcohols such as methanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and methoxypropanol, ethers such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and diethylene glycol monobutyl ether, and acetylacetone. Examples include ketones, esters such as ethylene glycol monoethyl ether acetate, and hexane. These organic solvents may be used alone or in combination. However, from the viewpoint of VOC emission regulations, the amount of organic solvent is preferably as small as possible.
  • the content of the amine-modified epoxy resin (A) is preferably 5% by mass to 30% by mass.
  • the electrodeposition coating composition of this embodiment may contain a pigment.
  • the pigment include coloring pigments such as titanium white, carbon black and bengara, extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica, clay and silica, iron phosphate, aluminum phosphate, Examples thereof include rust preventive pigments such as calcium phosphate, aluminum tripolyphosphate, aluminum molybdate, calcium molybdate and aluminum phosphomolybdate. These pigments are preliminarily dispersed in an aqueous medium at a high concentration to form a paste, which is added to the electrodeposition coating composition.
  • the pigment concentration in an electrodeposition coating composition is the quantity which does not exceed 50 mass% with respect to the total solid of an electrodeposition coating composition.
  • the electrodeposition coating composition of this embodiment may contain an additive.
  • the additive include a dispersant, a viscosity modifier, a surface conditioner, an antifoaming agent, a film-forming aid, an ultraviolet absorber, and an antioxidant.
  • an amine-modified epoxy resin (A), a plasticizer (B), an acid compound, and other components are added in a predetermined amount to an aqueous medium at appropriate timings.
  • the amine-modified epoxy resin (A) is then dispersed in an aqueous medium.
  • a specific production example is as follows.
  • an amine-modified epoxy resin (A) is synthesized in an appropriate plasticizer (B) or an organic solvent, and then the plasticizer (B) is added to the solution, and an acid compound is further added to prepare a mixture. . Subsequently, the obtained mixture is dropped and dispersed in the aqueous medium, or the aqueous medium is added to and dispersed in the obtained mixture. Subsequently, solvent replacement is performed by distilling off the organic solvent as necessary. Finally, an electrodeposition coating composition is obtained by adding a predetermined amount of a plasticizer (B), if necessary, water or an acid such as acetic acid, formic acid and nitric acid. Furthermore, you may add a pigment paste as needed.
  • a plasticizer (B) if necessary, water or an acid such as acetic acid, formic acid and nitric acid.
  • the plasticizer (B) is added to the electrodeposition coating composition by post-adding into the emulsion of the amine-modified epoxy resin (A), and the amine-modified epoxy resin (A). By using it as a synthetic solvent for emulsification, it is blended in the electrodeposition coating composition.
  • the usage-amount of organic solvents other than a plasticizer (B) can be reduced by using a plasticizer (B) as a synthetic solvent.
  • the electrodeposition coating film formation method of this embodiment forms an electrodeposition coating film by electrodeposition-coating the electrodeposition coating composition of the said embodiment on the base material as a to-be-coated object.
  • the electrodeposition coating method is not particularly limited, and a conventionally known cationic electrodeposition coating method is employed.
  • a voltage is applied between the step of immersing the coating object in the electrodeposition coating composition of the above embodiment and the anode with the coating object as a cathode.
  • the substrate as the object to be coated is not particularly limited as long as it has conductivity.
  • metal iron, steel, copper, aluminum, magnesium, tin, zinc, etc. and alloys containing these metals
  • iron plate iron plate
  • steel plate aluminum plate and surface treatment (for example, phosphoric acid, chromic acid or zirconium)
  • surface treatment for example, phosphoric acid, chromic acid or zirconium
  • the bath temperature of the electrodeposition coating composition is preferably 10 ° C. to 40 ° C., more preferably 10 ° C. to 30 ° C.
  • the applied voltage is preferably 50V to 450V, and more preferably 100V to 400V.
  • the energization time is preferably 1 second to 300 seconds, and more preferably 30 seconds to 180 seconds.
  • the baking temperature is preferably 260 ° C. or less, and more preferably 60 ° C. to 220 ° C.
  • the dry film thickness of the electrodeposition coating film is preferably 5 ⁇ m to 25 ⁇ m. By satisfying these conditions, a good electrodeposition coating film can be obtained more reliably.
  • a conventionally known top coating is applied, and a multilayer coating film can be obtained on the substrate.
  • Example 1 1939 parts of diglycidyl ether of bisphenol A and 1061 parts of bisphenol A were dissolved in 1000 parts of methyl isobutyl ketone (hereinafter referred to as “MIBK”). Thereto, 4 parts of dimethylbenzylamine was added, and the reaction was continued until the epoxy equivalent was 3000 and the molecular weight was 6000. Thereby, an epoxy resin having a bisphenol skeleton as a raw material was obtained.
  • MIBK methyl isobutyl ketone
  • DETA diketimine 324 parts of MIBK diketimine of diethylenetriamine (hereinafter referred to as “DETA diketimine”) was added to the epoxy resin having the bisphenol skeleton obtained above, and reacted at 120 ° C. for 1 hour. As a result, an amine-modified epoxy resin (A) having a modification amount of 3% was obtained.
  • Example 2 ⁇ Examples 2 to 6> Instead of BzOH added later in Example 1, 800 parts of 2-phenylethyl alcohol (hereinafter referred to as “2-pH-EtOH”) (corresponding to 26 mass% with respect to the amine-modified epoxy resin (A)) was added later. An electrodeposition coating composition obtained by performing the same operation as in Example 1 except that it was added was designated as Example 2. Similarly, 800 parts of 3-phenyl-1-propanol (hereinafter referred to as “3-pH-1-PrOH”) (corresponding to 26% by mass with respect to the amine-modified epoxy resin (A)) was added later.
  • 2-pH-EtOH 2-phenylethyl alcohol
  • 3-pH-1-PrOH 3-phenyl-1-propanol
  • Example 3 was prepared by adding 800 parts of 4-methoxybenzyl alcohol (hereinafter referred to as “4-MeO-BzOH”) (corresponding to 26% by mass based on the amine-modified epoxy resin (A)) as Example 4.
  • 4-MeO-BzOH 4-methoxybenzyl alcohol
  • Phenyl glycol (hereinafter referred to as “PhG”) 800 parts (corresponding to 26% by mass relative to the amine-modified epoxy resin (A)) was added as Example 5 and benzyl glycol (hereinafter referred to as “BzG”).
  • BzG benzyl glycol
  • Example 7 Instead of BzOH added as a synthesis solvent in Example 1, 1059 parts of dipropylene glycol monobutyl ether (hereinafter referred to as “DPnB”) corresponding to the plasticizer (B-2) (based on the amine-modified epoxy resin (A)) Example 1 except that an addition of 32 parts of 90% acetic acid in addition to water and a plasticizer (B-1) to be added at the end (equivalent to a neutralization rate of 65%) was added.
  • An electrodeposition coating composition obtained by performing the same operation as in Example 7 was designated as Example 7.
  • Example 8 the electrodeposition paint composition obtained by performing the same operation as in Example 2 was set as Example 8, and the electrodeposition paint composition obtained by performing the same operation as in Example 3 was otherwise obtained.
  • the electrodeposition paint composition obtained by performing the same operation as in Example 4 except for Example 9 was used as Example 10, and the electrodeposition paint composition obtained by performing the same operation as in Example 5 except that.
  • the electrodeposition coating composition obtained by performing the same operation as in Example 6 except that the product was Example 11.
  • Example 13 1059 parts (amine-modified epoxy resin) of propylene glycol monobutyl ether (hereinafter referred to as “PnB”) corresponding to the plasticizer (B-2)
  • Example 14 to 17 A battery obtained by performing the same operation as in Example 1 except that the amount of BzOH added later in Example 1 was 620 parts (corresponding to 20% by mass with respect to the amine-modified epoxy resin (A)).
  • the coating composition was Example 14.
  • the amount of BzOH added later was 464 parts (corresponding to 15% by mass with respect to the amine-modified epoxy resin (A)) as Example 15, and 310 parts (amine-modified epoxy resin (A))
  • Example 16 was designated as Example 16
  • Example 17 was designated as 155 parts (corresponding to 5% by mass relative to the amine-modified epoxy resin (A)).
  • Example 18 to 21 A battery obtained by performing the same operation as in Example 7 except that the amount of BzOH added later in Example 7 was changed to 620 parts (corresponding to 20% by mass with respect to the amine-modified epoxy resin (A)).
  • the coating composition was designated as Example 18.
  • the amount of post-added BzOH added was 464 parts (corresponding to 15% by mass with respect to the amine-modified epoxy resin (A)) as Example 19, and 310 parts (amine-modified epoxy resin (A))
  • Example 20 corresponds to 10% by mass
  • Example 21 corresponds to 155 parts (corresponding to 5% by mass with respect to the amine-modified epoxy resin (A)).
  • Example 22 1005 parts of diglycidyl ether of bisphenol A and 495 parts of bisphenol A were dissolved in 500 parts of methyl isobutyl ketone (hereinafter referred to as “MIBK”). Thereto, 2 parts of dimethylbenzylamine was added, and the reaction was continued until the epoxy equivalent was 1500 and the molecular weight was 3000. Thereby, an epoxy resin having a bisphenol skeleton as a raw material was obtained.
  • MIBK methyl isobutyl ketone
  • Example 23 As an epoxy resin having a bisphenol skeleton as a raw material, while adding 4000 parts of an epoxy resin having an epoxy equivalent of 4000 (manufactured by Japan Epoxy Resin Co., Ltd., Grade 1010) to 1167 parts of MIBK, 100 parts of diethanolamine is added at 120 ° C. The reaction was carried out for 1 hour. As a result, an amine-modified epoxy resin (A) having a modification amount of 3% was obtained.
  • TPnB tripropylene glycol monobutyl ether
  • plasticizer B-2
  • neutralization was performed by adding 41 parts of 90% acetic acid as an acid compound (neutralization rate 65%). While stirring at 90 ° C., 5426 parts of water was gradually added to achieve homogenization. Subsequently, solvent replacement was performed by distilling off 2333 parts of a mixture of MIBK and water at 50 ° C. under reduced pressure.
  • Example 24 As an epoxy resin having a bisphenol skeleton as a raw material, an electrodeposition coating composition (water) was obtained in the same manner as in Example 22 except that the epoxy resin was changed to an epoxy resin having an epoxy equivalent of 925 (Japan Epoxy Resin, Grade 1004). Dispersion) was obtained.
  • Example 25 Instead of BzOH added later in Example 1, MIBK corresponding to plasticizer (B-2) was added except that 800 parts (corresponding to 26% by mass with respect to amine-modified epoxy resin (A)) were added later.
  • An electrodeposition coating composition obtained by the same operation as in Example 1 was referred to as Example 25.
  • Example 26 1627 parts of diglycidyl ether of bisphenol A, 873 parts of bisphenol A and 22 parts of octylic acid were dissolved in 834 parts of MIBK. Thereto, 4 parts of dimethylbenzylamine was added, and the reaction was continued until the epoxy equivalent was 2500 and the molecular weight was 5000. Thereby, an epoxy resin having a bisphenol skeleton as a raw material was obtained. To this epoxy resin having a bisphenol skeleton, 288 parts of DETA diketimine was added and reacted at 120 ° C. for 1 hour. As a result, an amine (and octylic acid) -modified epoxy resin (A) having a modification amount of 4% was obtained.
  • Comparative Example 5 was an electrodeposition coating composition obtained by performing the same operation as Comparative Example 1 except that DPnB corresponding to the plasticizer (B-2) was not added afterwards.
  • cationic electrodeposition coating composition 210 parts of amine-modified epoxy resin (B), 57 parts of blocked isocyanate curing agent (1) and 35 parts of blocked isocyanate curing agent (2) were mixed uniformly. This was neutralized with 5 parts of acetic acid and 1 part of zinc acetate, and then diluted by adding 100 parts of deionized water to obtain a main emulsion (solid content: 36.0%).
  • test plate (zinc phosphate-treated plate) was precisely weighed to determine a test plate weight A before electrodeposition coating.
  • B The test plate was immersed in the electrodeposition coating composition, and cationic electrodeposition coating was applied so that the film thickness after drying was 20 ⁇ m. Electrodeposition coating was carried out under conditions where the bath temperature was 30 ° C. and 40 ° C.
  • C After washing the test plate after electrodeposition coating, the wet film formed on the surface of the test plate was dried at 105 ° C. for 3 hours.
  • D After drying, the test plate was cooled to room temperature in a desiccator and then precisely weighed to determine the test plate weight B after drying.
  • E The test plate after drying was baked at 200 ° C.
  • Comparative Examples 1 to 7 containing no crosslinking agent no good film forming property was obtained, and no electrodeposition coating film could be formed. That is, it was confirmed that these Comparative Examples 1 to 7 were not included in the range of “loss on heating of 10% by mass or less” of the present invention. Further, in Comparative Example 8, which corresponds to Example 1 of Patent Document 1 and contains a crosslinking agent, the loss on heating exceeds 10% by mass in both the bath temperature 30 ° C. coating film and the 40 ° C. coating film. It was confirmed that it was not included in the range.
  • Examples 1 to 26 containing no cross-linking agent good film-forming properties were obtained at a bath temperature of 40 ° C., and the loss on heating was less than 5% by mass. Is included in the range of “10% by mass or less”. Moreover, it was also confirmed that the high-temperature heat loss is 2% by mass or less due to the above characteristics.
  • a plasticizer (B-1) such as BzOH irrespective of whether it is an addition as a synthetic solvent or a post-addition
  • the total content of the plasticizer (B-1) and the plasticizer (B-2) is 39% by mass or more based on the amine-modified epoxy resin (A)
  • the loss of heat was 10% by mass or less. In this case, it was also found that the high-temperature loss on heating was 2% by mass or less.
  • the electrodeposition paint composition of the present invention is an electrodeposition paint composition having a reduced weight loss compared to the prior art, it is an environment-friendly electrodeposition paint composition that takes into consideration the use environment of products having an electrodeposition coating film. Is preferably used.

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

Abstract

L'invention a pour but de proposer une composition de revêtement par électrodéposition qui présente une perte de chaleur réduite par comparaison avec des compositions classiques de revêtement par électrodéposition. Une composition de revêtement par électrodéposition de la présente invention ne contient sensiblement pas d'agent réticulant et un film de revêtement par électrodéposition de celle-ci, qui est formé par revêtement par électrodéposition, a une perte thermique de 10 % en masse ou moins lorsqu'il est chauffé à 200°C pendant 25 minutes après avoir été séché à 105°C pendant 3 heures. La composition de revêtement par électrodéposition de la présente invention contient, de préférence, (A) une résine époxy modifiée par amine qui est obtenue par modification d'une résine époxy ayant un squelette de bisphénol avec un composé amine et (B) un plastifiant qui est composé d'un composé alcool aromatique.
PCT/JP2012/074058 2011-09-30 2012-09-20 Composition de revêtement par électrodéposition WO2013047319A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2014095139A1 (fr) * 2012-12-17 2014-06-26 Evonik Industries Ag Utilisation d'alcools benzyliques substitués dans des systèmes époxydes réactifs

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JP6398025B1 (ja) * 2018-02-06 2018-09-26 日本ペイント・インダストリアルコ−ティングス株式会社 電着塗料組成物及び電着塗装方法
CN111393683B (zh) * 2020-04-20 2023-05-23 广东科德环保科技股份有限公司 一种改性阳离子微凝胶及其制备方法和应用

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JPH0710969A (ja) * 1992-08-06 1995-01-13 Hoechst Ag エポキシ樹脂を基礎とする架橋したポリマーミクロ粒子、その製法およびその用途
JP2005194390A (ja) * 2004-01-07 2005-07-21 Nippon Paint Co Ltd 無鉛性カチオン電着塗料組成物
JP2006089623A (ja) * 2004-09-24 2006-04-06 Nippon Paint Co Ltd エン・チオール硬化系を利用したカチオン電着塗料組成物および電着塗膜形成方法
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WO2014095139A1 (fr) * 2012-12-17 2014-06-26 Evonik Industries Ag Utilisation d'alcools benzyliques substitués dans des systèmes époxydes réactifs
US10472460B2 (en) 2012-12-17 2019-11-12 Evonik Degussa Gmbh Use of substituted benzyl alcohols in reactive epoxy systems

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CN103857755A (zh) 2014-06-11
JP5846828B2 (ja) 2016-01-20
JP2013075982A (ja) 2013-04-25

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