WO2017138445A1 - カチオン電着塗料組成物の製造方法 - Google Patents
カチオン電着塗料組成物の製造方法 Download PDFInfo
- Publication number
- WO2017138445A1 WO2017138445A1 PCT/JP2017/003905 JP2017003905W WO2017138445A1 WO 2017138445 A1 WO2017138445 A1 WO 2017138445A1 JP 2017003905 W JP2017003905 W JP 2017003905W WO 2017138445 A1 WO2017138445 A1 WO 2017138445A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating composition
- cationic electrodeposition
- electrodeposition coating
- polyisocyanate compound
- parts
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- 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
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
-
- 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
-
- 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
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
- C25D13/16—Wires; Strips; Foils
Definitions
- the present invention relates to a method for producing a cationic electrodeposition coating composition having excellent storage stability, low-temperature curability, coating finish, and corrosion resistance.
- cationic electrodeposition paints are widely used in automobile parts, electrical equipment parts, and other industrial equipments that require these performances because of the excellent coating workability and good corrosion resistance of the formed coating film. ing.
- a cationic electrodeposition coating composition is aqueous by mixing a resin component composed of a cationic resin (for example, an amino group-containing epoxy resin) and a curing agent (also referred to as a crosslinking agent, for example, a blocked polyisocyanate compound). It is provided in a mixed form of two components, a resin emulsion component dispersed in a medium and a pigment dispersion paste component containing a pigment dispersed in a pigment dispersion resin.
- a resin component composed of a cationic resin (for example, an amino group-containing epoxy resin) and a curing agent (also referred to as a crosslinking agent, for example, a blocked polyisocyanate compound).
- This coating composition is used in a coating bath, energized with the object to be coated as a cathode and the counter electrode as an anode to form a deposited film on the object to be coated, and then the deposited film is heated to cure by crosslinking. A coated film is formed.
- the heating temperature at the time of forming the coating film is usually higher than 160 ° C. However, in order to reduce energy costs, it is required to perform at a low temperature (80 to 160 ° C., preferably 80 to 130 ° C.). It has been. This is called low temperature baking.
- Patent Document 1 discloses an oxime-blocked isocyanate. It is disclosed that low-temperature curing is performed using a cationic electrodeposition coating composition containing the same.
- Patent Document 2 discloses a low-temperature baking type electrodeposition coating at 100 to 160 ° C., where the blocked polyisocyanate compound blocked with an oxime and lactam is dissociated at a relatively low temperature. (Reaction) is described as being possible.
- Patent Document 3 discloses that by using a self-crosslinking resin having a specific blocked isocyanate group, it can be cured at a low temperature of 120 ° C. or less and can also be used as a cationic electrodeposition coating.
- the electrodeposition coating composition with improved reactivity at low temperatures has insufficient long-term storage stability (bath stability), and as a result, the finish and anticorrosion properties of the coating film may be inferior. .
- Patent Document 4 was obtained by electrodeposition-coating a base resin (amine-added epoxy resin) and then electrodepositing an aqueous dispersion of a blocked polyisocyanate curing agent imparted with water-dispersibility.
- a method of forming a coating film by low-temperature baking in which the coating film is heated and dried at 60 to 150 ° C. is disclosed.
- the storage stability (bath stability) of the paint is improved by separating the base resin and the curing agent paint / coating, the anti-corrosion property etc., since the curing agent may not exist uniformly in the coating film. Was inferior.
- the painting process and cleaning process increased, it was necessary to add new facilities.
- the problem to be solved by the present invention is to provide a method for producing a cationic electrodeposition coating composition having excellent storage stability, low-temperature curability, finished film properties, and anticorrosion properties.
- the inventors have determined that the three components of the low-temperature curable blocked polyisocyanate compound, the amino group-containing epoxy resin, and the pigment dispersion paste are separately dispersed in water and mixed. It has been found that the solution of the above-mentioned problems can be achieved by the production method of the cationic electrodeposition coating composition, which has the characteristics, and the present invention has been completed.
- the present invention provides the following method for producing a cationic electrodeposition coating composition and a coated article obtained by electrodeposition-coating the cationic electrodeposition coating composition on an object to be coated.
- Item 1 Cationic electrodeposition obtained by mixing three components of an aqueous dispersion of an amino group-containing epoxy resin (A), an aqueous dispersion of a blocked polyisocyanate compound (B), and a pigment dispersion paste (C) A method for producing a coating composition.
- the aqueous dispersion (B) of the blocked polyisocyanate compound contains the blocked polyisocyanate compound (b) and an emulsifier, and the content of the emulsifier is 0 based on the resin solid content of the aqueous dispersion (B).
- Item 3. Item 3.
- the aqueous dispersion (B) of the blocked polyisocyanate compound contains the blocked polyisocyanate compound (b) obtained by reacting the isocyanate compound (b-1) with the blocking agent (b-2), and an emulsifier.
- An aqueous dispersion (B) of a blocked polyisocyanate compound contains a blocked polyisocyanate compound (b) obtained from (consisting of) the reaction of an isocyanate compound (b-1) and a blocking agent (b-2).
- the blocking agent (b-2) is at least one selected from the group consisting of pyrazole compounds, active methylene compounds, oxime compounds, phenol compounds, lactam compounds and alcohol compounds. 5.
- the method for producing a cationic electrodeposition coating composition according to any one of the above items 1 to 4.
- Item 6 A method for producing a cationic electrodeposition coating composition, wherein the gel fraction measured by the following conditions is 90% or more using the cationic electrodeposition coating composition obtained by the production method of items 1 to 5 above .
- Electrodeposition coating is performed on a metal coating, and baking is performed at a temperature of 160 ° C. or lower.
- Method. Item 8. A coating film, characterized in that a cationic electrodeposition coating composition obtained by the production method of Items 1 to 6 above is used to electrodeposit-coat on a metal object and is baked at a temperature of 80 to 130 ° C. Forming method.
- the cationic electrodeposition coating composition obtained by the production method of the present invention ensures good coating stability (bath stability), and even when a low-temperature curable blocked polyisocyanate compound is used as a curing agent, The obtained coating film is excellent in finish and corrosion resistance.
- the automobile body coated with the product of the present invention has a good finish of the coating film, and has little corrosion deterioration even when traveling for a long time in an environment where snow melting salt is sprayed.
- the cationic coating composition obtained by the production method of the present invention has good storage stability over a long period of time.
- the present invention is obtained by mixing three components of an aqueous dispersion of an amino group-containing epoxy resin (A), an aqueous dispersion of a blocked polyisocyanate compound (B), and a pigment dispersion paste (C).
- the present invention relates to a method for producing a cationic electrodeposition coating composition.
- the production method of the present invention comprises a blocked polyisocyanate compound that is a curing agent, an amino group-containing epoxy resin that is a base resin component that reacts with the curing agent, and a pigment dispersion paste containing a pigment, a catalyst, and a pigment dispersion resin.
- storage stability bath stability
- it has an effect on the storage stability of a low-temperature baking paint that undergoes a curing reaction at 80 to 160 ° C (preferably 100 to 130 ° C).
- the aqueous dispersion (A), the aqueous dispersion (B), and the pigment dispersion paste (C), which are components of the cationic electrodeposition coating composition, are prepared by mixing the three components in the coating bath. Although used as a paint, it is also possible to mix the two components in advance until they are supplied to the paint bath. [For example, (A) and (B), (B) and (C), or (A) and (C) are mixed in advance, and then supplied to the paint bath, etc.].
- the “aqueous solvent” is a solvent containing water and / or a hydrophilic solvent as a main component (containing 50% by mass or more in the solvent).
- a hydrophilic solvent For example, ethylene glycol, ethylene glycol monoalkyl ether (eg, methyl ether, ethyl ether, butyl ether, etc.), diethylene glycol, diethylene glycol monoalkyl ether (eg, methyl ether, ethyl ether, butyl ether, etc.), glyme solvent (eg, ethylene glycol dimethyl ether, etc.) Diglyme solvents (eg, diethylene glycol dimethyl ether), alcohol solvents (eg, methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol), propylene glycol, propylene glycol Cole monoalkyl ethers (for example, methyl ether, ethyl ether, butyl ether, etc.),
- the “aqueous dispersion” refers to those in a state where the resin component does not dissolve in the aqueous solvent but exists in the form of particles. Details will be described below.
- Aqueous dispersion of amino group-containing epoxy resin (A) is a dispersion in which an amino group-containing epoxy resin (a) as a main component is dispersed in an aqueous solvent.
- the aqueous dispersion (A) can contain additives such as a neutralizing agent, an emulsifier, a catalyst, and other resin components as necessary.
- the content of the amino group-containing epoxy resin (a) in the aqueous dispersion (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on the solid content. .
- the acid compound known acid compounds can be used without particular limitation. Specifically, for example, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid; formic acid, acetic acid, propionic acid, lactic acid, etc. Examples include organic acids containing carboxylic acid compounds. These acid compounds can be used individually by 1 type or in combination of 2 or more types, Among these, an organic acid is preferable and especially a carboxylic acid compound can be used more preferably.
- inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid; formic acid, acetic acid, propionic acid, lactic acid, etc.
- organic acids containing carboxylic acid compounds These acid compounds can be used individually by 1 type or in combination of 2 or more types, Among these, an organic acid is preferable and especially a carboxylic acid compound can be used more preferably.
- Amino group-containing epoxy resin (a) examples include (1) an epoxy resin, a primary mono- and polyamine, and a secondary mono- And adducts with polyamines or primary and secondary mixed polyamines (see, e.g., U.S. Pat. No. 3,984,299); (2) epoxy resins and secondarys having ketiminated primary amino groups Adducts with primary mono- and polyamines (see, for example, US Pat. No. 4,017,438); (3) by etherification of an epoxy resin with a ketiminated hydroxy compound having a primary amino group Examples thereof include a reaction product obtained (for example, see JP-A-59-43013).
- the epoxy resin used for the production of the amino group-containing epoxy resin (a) is a compound having at least one, preferably two or more epoxy groups in one molecule, and the molecular weight is at least 300, preferably Having a number average molecular weight in the range of 400 to 4,000, more preferably in the range of 800 to 2,500 and an epoxy equivalent weight in the range of at least 160, preferably 180 to 2,500, more preferably 400 to 1,500 Is suitable.
- this epoxy resin what is obtained by reaction of a polyphenol compound and epihalohydrin (for example, epichlorohydrin etc.) can be used, for example.
- Examples of the polyphenol compound used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], bis ( 4-hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra ( 4-hydroxyphenyl) -1,1,2,2-ethane, 4, '- dihydroxydiphenyl sulfone, phenol novolak, and the like cresol novolak.
- epoxy resin obtained by the reaction between the polyphenol compound and epihalohydrin a resin represented by the following formula derived from bisphenol A is particularly preferable.
- Examples of such commercially available epoxy resins include those sold by Mitsubishi Chemical Corporation under the trade names jER828EL, jER1002, jER1004, and jER1007.
- an epoxy resin containing a polyalkylene oxide chain in the resin skeleton can be used as the epoxy resin.
- an epoxy resin is ( ⁇ ) a method of introducing a polyalkylene oxide chain by reacting an epoxy resin having at least one, preferably two or more epoxy groups, with an alkylene oxide or a polyalkylene oxide, ( ⁇ ) It can be obtained by a method of introducing a polyalkylene oxide chain by reacting the polyphenol compound with a polyalkylene oxide having at least one, preferably two or more epoxy groups. Further, an epoxy resin that already contains a polyalkylene oxide chain may be used.
- the alkylene group in the polyalkylene oxide chain is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a propylene group.
- the content of the above polyalkylene oxide chain is the content as a constituent component of the polyalkylene oxide, based on the solid content mass of the amino group-containing epoxy resin, from the viewpoint of improving coating stability, finish, and corrosion resistance.
- the range of 1.0 to 15% by mass, preferably 2.0 to 9.5% by mass, more preferably 3.0 to 8.0% by mass is appropriate.
- Examples of the primary mono- and polyamines, secondary mono- and polyamines, and primary and secondary mixed polyamines used in the production of the amino group-containing epoxy resin (a) of (1) above include monomethylamine, Mono- or di-alkylamines such as dimethylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine; monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, monomethylaminoethanol, etc.
- Alkanolamines alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and the like can be given.
- Examples of the secondary mono- and polyamines having a ketimized primary amino group used in the production of the amino group-containing epoxy resin (a) of (2) include the amine-added epoxy of (1) above.
- the primary and secondary mixed polyamines used in the production of the resin for example, ketimine compounds formed by reacting a ketone compound with diethylenetriamine or the like can be mentioned.
- Examples of the hydroxy compound having a ketiminated primary amino group used in the production of the amino group-containing epoxy resin (a) of (3) above include, for example, the amino group-containing epoxy resin (a) of (1) above.
- the primary mono- and polyamines secondary mono- and polyamines or primary and secondary mixed polyamines used in the production of the compounds having a primary amino group and a hydroxyl group, such as monoethanolamine, Examples thereof include a hydroxyl group-containing ketimine obtained by reacting a ketone compound with mono (2-hydroxypropyl) amine or the like.
- the amine value of such an amino group-containing epoxy resin (a) is in the range of 10 to 100 mg KOH / g resin solid content, more preferably in the range of 30 to 80 mg KOH / g resin solid content. It is preferable from the point of improvement of property.
- the amino group-containing epoxy resin (a) can be modified with a modifying agent as necessary.
- a modifier is not particularly limited as long as it is a resin or compound having reactivity with an epoxy resin.
- a compound obtained by reacting an isocyanate compound, a lactone compound such as ⁇ -caprolactone, an acrylic monomer, a compound obtained by polymerizing an acrylic monomer, a xylene formaldehyde compound, or an epoxy compound can also be used as a modifier.
- These modifiers can be used alone or in combination of two or more.
- the use ratio of the above modifier is not strictly limited and can be appropriately changed according to the use of the coating composition, etc., but from the viewpoint of improving finish and anticorrosion, the amino group-containing epoxy resin A suitable amount is usually 0 to 50% by mass, preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the solid content.
- the above addition reaction of the amine compound and the modifier to the epoxy resin is usually performed in a suitable solvent at a temperature of about 80 to about 170 ° C., preferably about 90 to about 150 ° C. for about 1 to 6 hours, preferably It can be performed in about 1 to 5 hours.
- the solvent examples include hydrocarbons such as toluene, xylene, cyclohexane and n-hexane; esters such as methyl acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone. Amides such as dimethylformamide and dimethylacetamide; Alcohols such as methanol, ethanol, n-propanol and iso-propanol; Ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; or a mixture thereof Can be mentioned.
- hydrocarbons such as toluene, xylene, cyclohexane and n-hexane
- esters such as methyl acetate, ethyl acetate and butyl acetate
- ketones such as acetone, methyl
- the aqueous dispersion (B) of the blocked polyisocyanate compound that can be used in the present invention is a dispersion in which a component comprising the blocked polyisocyanate compound (b) is dispersed in an aqueous solvent,
- the isocyanate compound (b) is obtained by reacting the isocyanate compound (b-1) with the blocking agent (b-2).
- the aqueous dispersion (B) can contain additives such as a neutralizing agent and an emulsifier, other resin components, and the like, if necessary, in addition to the polyisocyanate compound (b).
- the content of the blocked polyisocyanate compound (b) in the aqueous dispersion (B) is preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 80% by mass or more, based on the solid content. .
- a method using an emulsifier is preferable.
- a cationic emulsifier is preferably used from the viewpoint of coating performance of cationic electrodeposition.
- a nonionic emulsifier, an anionic emulsifier, an amphoteric emulsifier, and the like can be used in combination as necessary.
- cationic emulsifier known ones can be used, and specific examples include resins having cationic functional groups such as amine salts, ammonium salts, pyridinium salts, phosphonium salts, sulfonium salts, and the like. These can be used alone or in combination of two or more.
- the content of the cationic functional group is preferably about 20 to 300, and preferably 30 to 200, as an amine value (mgKOH / g) in order to ensure the dispersibility of the aqueous dispersion (B). It is more preferable. If it is less than 20, dispersibility is inferior, and if it exceeds 300, the water resistance of the coating film may be adversely affected.
- the cationic emulsifier can be produced by adding a cationic functional group to the resin main chain by a known method.
- the resin skeleton of the cationic emulsifier is not particularly limited, and specific examples include epoxy resin, acrylic resin, liquid rubber (elastomer), polyurethane, polyether, and modified resins and composite resins thereof. These can be used alone or in combination of two or more.
- the resin having the epoxy resin as a resin skeleton can be synthesized by the same method as the amino group-containing epoxy resin (a) described above.
- the resin having the acrylic resin as a resin skeleton can be synthesized, for example, by a ring-opening addition reaction between an acrylic copolymer containing a glycidyl group in the molecule and an amine compound. That is, part or all of the glycidyl group with respect to the glycidyl group-containing acrylic resin obtained by copolymerizing an acrylic monomer having a glycidyl group such as glycidyl (meth) acrylate with another monomer. Can be reacted with an amine compound to obtain a cationic acrylic resin.
- an acrylic monomer having an amino group examples include N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.
- liquid rubber polyurethane and polyether resin skeletons
- a cationic group can be introduced by an addition reaction.
- the content of the emulsifier is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and further preferably 1 to 20% by mass based on the resin solid content of the aqueous dispersion (B). preferable.
- the active hydrogen group of the emulsifier reacting with the isocyanate group of the polyisocyanate compound (b-1) is small.
- the content of active hydrogen group in the emulsifier is preferably selected from the polyisocyanate compound (b- Based on the isocyanate group content of 1), it is preferably 50 mol% or less, more preferably 0 to 30 mol%, still more preferably 0 to 10 mol%.
- Blocked polyisocyanate compound (b) As the blocked polyisocyanate compound (b), which is a constituent of the aqueous dispersion (B) of the blocked polyisocyanate compound, an addition reaction between the polyisocyanate compound (b-1) and the blocking agent (b-2) is generated. It is a thing. If necessary, an active hydrogen-containing compound other than the blocking agent (b-2) can be used to react with the polyisocyanate compound (b-1) together with the blocking agent (b-2) (in the present invention, Of course, the compound obtained by the reaction using an active hydrogen-containing compound other than the blocking agent (b-2) is “addition reaction product of polyisocyanate compound (b-1) and blocking agent (b-2)”. Is included).
- polyisocyanate compound (b-1) known compounds can be used.
- Aromatic, aliphatic such as diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate or An alicyclic polyisocyanate compound; a cyclized polymer or biuret of these polyisocyanate compounds; or a combination thereof. It can gel.
- the blocking agent (b-2) is added and blocked to the isocyanate group of the polyisocyanate compound (b-1), and the blocked polyisocyanate compound (b) produced by the addition is stable at room temperature.
- the blocking agent (b-2) examples include oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol; n-butanol, 2-ethylhexanol, phenylcarbi Alcohol compounds such as diol, methyl phenyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, methoxymethanol; ⁇ -caprolactam Lactam compounds such as ⁇ -butyrolactam; dimethyl malonate, diethyl malonate, malon Active methylene compounds such as diisopropyl acid, ethyl acetoacetate, isopropyl acetoacetate, methyl acetoa
- the blocking agent (b-2) is composed of a pyrazole compound, an active methylene compound, an oxime compound, a phenol compound, a lactam compound, and an alcohol compound from the viewpoint of low-temperature curability (dissociation temperature). At least one selected from the group is preferred, pyrazole compounds and / or active methylene compounds are more preferred, and pyrazole compounds are particularly preferred. As the pyrazole compound, 3,5-dimethylpyrazole and / or 3-methylpyrazole is preferable, and 3,5-dimethylpyrazole is more preferable.
- Pigment dispersion paste (C) The pigment dispersion paste (C) that can be used in the present invention is obtained by dispersing pigments such as color pigments, rust preventive pigments, extender pigments, and curing catalysts in advance into fine particles, for example, pigment dispersion resins,
- a pigment-dispersed paste can be prepared by blending various additives such as a pigment and a neutralizing agent and dispersing in a dispersion mixer such as a ball mill, a sand mill, or a pebble mill.
- pigment dispersing resin known resins can be used without any particular limitation.
- epoxy resins having a hydroxyl group and a cationic group acrylic resins having a hydroxyl group and a cationic group
- acrylic resins having a hydroxyl group and a cationic group a tertiary amine type epoxy resin, a quaternary ammonium salt.
- Type epoxy resin, tertiary sulfonium salt type epoxy resin, tertiary amine type acrylic resin, quaternary ammonium salt type acrylic resin, tertiary sulfonium salt type acrylic resin and the like can be used.
- pigments can be used without particular limitation, for example, coloring pigments such as titanium oxide, carbon black, bengara, etc .; extender pigments such as clay, mica, barita, calcium carbonate, silica; can do.
- organotin compounds such as dibutyltin dibenzoate, dioctyltin oxide and dibutyltin oxide can be used as a catalyst. It is preferable not to use a tin compound.
- organic tin compounds inorganic compounds such as zinc compounds, bismuth compounds, titanium compounds, zirconium compounds and yttrium compounds; organic compounds such as phosphazene compounds, amine compounds and quaternary salt compounds; It is more preferable that the catalyst is not substantially used from the viewpoint of environmental considerations.
- the aqueous dispersion (A) of the amino group-containing epoxy resin is used. Can be contained.
- the amount of the pigment in the pigment dispersion paste (C) is preferably in the range of 1 to 100 parts by weight, particularly 10 to 50 parts by weight, per 100 parts by weight of the resin solid content of the cationic electrodeposition coating composition.
- the amino group-containing epoxy resin (a) contained in the water dispersion (A) and the water dispersion (B) The blending ratio of the blocked polyisocyanate curing agent (b) contained is 30 to 90 parts by weight, preferably 30 parts by weight of the component (a), based on the total resin solid mass of the above components (a) and (b).
- the amine value of the entire resin contained in the paint is more preferably in the range of usually 20 to 150 mgKOH / g based on the resin solid content. If the blending ratio is out of the above range, either the above-mentioned paint properties or coating film performance may be impaired, which is not preferable.
- the cationic electrodeposition coating composition includes an acrylic dispersion containing an amino group-containing epoxy resin, which is an essential component, an aqueous dispersion (B) of a blocked polyisocyanate compound, and a pigment dispersion paste (C).
- Resins such as resins, epoxy resins, urethane resins, and melamine resins; additives such as surfactants, surface conditioners, curing catalysts, and neutralizing agents; pigments; solvents and the like can be contained as necessary.
- Coating film forming method comprises a step of immersing a coating in an electrodeposition bath comprising the cationic electrodeposition coating composition obtained by the above-described manufacturing method, and a step of energizing with the coating as a cathode.
- a method for forming an electrodeposition coating film is provided.
- Examples of the object to be coated with the cationic electrodeposition coating composition of the present invention include an automobile body, two-wheeled vehicle parts, household equipment, other equipment, and the like.
- metal steel sheets to be coated examples include cold-rolled steel sheets, galvannealed steel sheets, electrogalvanized steel sheets, electrogalvanized steel double-layer plated steel sheets, organic composite plated steel sheets, Al materials, Mg materials, and these metals.
- the surface of the plate may be subjected to surface treatment such as phosphate chemical treatment, chromate treatment, complex oxide treatment, etc. after cleaning the surface such as alkali degreasing as required.
- the cationic electrodeposition coating composition can be applied to the surface of a desired substrate by cationic electrodeposition.
- the cationic electrodeposition method is generally diluted with deionized water or the like so that the solid content concentration is about 5 to 40% by mass, preferably 10 to 25% by mass, and the pH is 4.0 to 9.0%.
- the cationic electrodeposition coating composition adjusted in the range of 5.5 to 7.0 is used as a bath, usually adjusted to a bath temperature of 15 to 35 ° C., and a load voltage of 100 to 400V, preferably 150 to 350V.
- the current is applied by using the object to be coated as a cathode.
- After electrodeposition usually ultrafiltrate (UF filtrate), reverse osmosis permeate (RO water), industrial water, pure water, etc. are sufficient to remove the cationic electrodeposition paint that has adhered to the object. Wash with water.
- the film thickness of the electrodeposition coating film is not particularly limited, but can generally be in the range of 5 to 40 ⁇ m, preferably 10 to 30 ⁇ m based on the dry coating film.
- the coating film is baked and dried by using a drying facility such as an electric hot air dryer or a gas hot air dryer, and the temperature of the coated surface is higher than 160 ° C. and lower than 200 ° C. Generally, in the present invention, a temperature of preferably less than 160 ° C., more preferably 80 to 130 ° C., and particularly preferably 100 to 130 ° C. is preferable from the viewpoint of reducing energy costs.
- the baking time is 10 to 180 minutes, preferably 20 to 50 minutes by heating the electrodeposition coating film.
- a cured coating film can be obtained by baking and drying.
- Production and production example 1 of amino group-containing epoxy resin In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, jER828EL (trade name, epoxy resin manufactured by Japan Epoxy Resin, epoxy equivalent 190, number average molecular weight 350) 1000 parts, bisphenol A 400 parts, and dimethylbenzyl 0.2 parts of amine was added and reacted at 130 ° C. until an epoxy equivalent of 750 was reached. Next, 100 parts of ⁇ -caprolactone and 0.05 part of tetrabutoxytitanium were added, and the temperature was raised to 170 ° C. and reacted at 170 ° C. for 4 hours.
- jER828EL trade name, epoxy resin manufactured by Japan Epoxy Resin, epoxy equivalent 190, number average molecular weight 350
- Plaxel 205 (trade name, manufactured by Daicel Chemical Industries, Ltd., polycaprolactone polyol compound), 140 parts of diethanolamine, and 65 parts of a ketimine compound of diethylenetriamine and methylisobutylketone were added to this product at 120 ° C. After reacting for 4 hours, 400 parts of ethylene glycol monobutyl ether was added to obtain an amino group-containing epoxy resin solution having a resin solid content of 80%. The amine value per solid content of the resulting amino group-containing epoxy resin was 56 mgKOH / g.
- Production and production example 2 of aqueous dispersion of amino group-containing epoxy resin The resin solid content 80% amino group-containing epoxy resin obtained in Production Example 1 125 parts (solid content 100 parts) and 10% formic acid 8 parts were blended and stirred uniformly, and then deionized water was gradually added while stirring vigorously. And an aqueous dispersion of an amino group-containing epoxy resin having a solid content of 32.0% was obtained.
- Production Example 4 8.3 parts of pigment dispersion resin obtained in Production Example 3 (5 parts of solid content), 14.5 parts of titanium oxide, 9.0 parts of purified clay, 0.3 part of carbon black, and 20.3 parts of deionized water And dispersed with a ball mill for 20 hours to obtain a pigment dispersion paste No. 5 having a solid content of 55%. 2 was obtained.
- Production Example 5 8.3 parts of pigment dispersing resin obtained in Production Example 3 (5 parts of solid content), 14.5 parts of titanium oxide, 7.0 parts of purified clay, 0.3 part of carbon black, 2 parts of dioctyltin oxide and deionized 20.3 parts of water was added and dispersed in a ball mill for 20 hours. 3 was obtained.
- the NCO amount means the amount (%) of NCO groups with respect to 100 parts by mass of the resin solid content.
- Production Example 8 A four-necked flask equipped with a stirrer, a heating device, a cooling device, and a decompression device was charged with 272 parts of hexamethylene diisocyanate and 214 parts of methyl ethyl ketone and heated to 60 ° C. Next, 169 parts of methyl ethyl ketoxime was gradually added over 1 hour with stirring. Then, after making it react at 60 degreeC for 2 hours, 59 parts of trimethylol propane was gradually added so that temperature might not become 70 degreeC or more. Under stirring, the reaction mixture was reacted at 60 ° C. until no free isocyanate groups were detected by infrared spectroscopy. After completion of the reaction, the blocked polyisocyanate compound no. 3 was obtained. The resulting blocked polyisocyanate compound had an NCO content of 16.4%.
- Production Example 11 In a four-necked flask equipped with a stirrer, a heating device, a cooling device, and a decompression device, 250 parts of “Sumijour N3300” (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate derived from hexamethylene diisocyanate) and 125 parts of methyl ethyl ketone and 20 parts of PEG-1000 (manufactured by Sanyo Chemical Co., Ltd., polyethylene glycol) were added and reacted at 70 ° C. for 2 hours.
- “Sumijour N3300” trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate derived from hexamethylene diisocyanate
- PEG-1000 manufactured by Sanyo Chemical Co., Ltd., polyethylene glycol
- the obtained cationic emulsifier had an amine value of 107 mgKOH / g, a hydroxyl value of 0 mgKOH / g, an active hydrogen group value (amine value conversion) of 0 mgKOH / g, and a weight average molecular weight of 10,000.
- a mixture of 0.5 part of t-butyl peroxyoctanoate and 10 parts of isobutanol was added dropwise for 1 hour.
- 40 parts of 10% formic acid was added and a cationic emulsifier No. 5 having a solid concentration of 50% was added. 2 was obtained.
- the obtained cationic emulsifier had an amine value of 107 mgKOH / g, a hydroxyl value of 194 mgKOH / g, an active hydrogen group value (amine value conversion) of 194 mgKOH / g, and a weight average molecular weight of 10,000.
- the obtained cationic emulsifier had an amine value per solid content of 180 mgKOH / g and an active hydrogen group value (amine value conversion) of 397 mgKOH / g.
- cationic emulsifier No. 80 having a solid content of 80% was added.
- the obtained cationic emulsifier had an amine value of 115 mgKOH / g per solid and an active hydrogen group value (amine value conversion) of 306 mgKOH / g.
- Production Example 1 of Cationic Electrodeposition Coating Composition The blocked polyisocyanate compound No. 1 obtained in Production Example 6 was used. 1 42.9 parts (solid content 30 parts) and the cationic emulsifier No. obtained in Production Example 12. 1 After blending 15 parts (solid content 7.5 parts) and stirring uniformly, deionized water was gradually added dropwise with vigorous stirring to obtain an aqueous dispersion of a blocked polyisocyanate compound having a solid content of 32.0%. (B) was obtained. Next, 218.8 parts (solid content 70 parts) of the amino group-containing epoxy resin aqueous dispersion obtained in Production Example 2 were added to the aqueous dispersion, and the pigment dispersion paste No. 5 having a solid content of 55% obtained in Production Example 3 was used. 1 52.4 parts (solid content 28.8 parts) and pure water were gradually added with stirring to obtain a cationic electrodeposition coating composition X-1 having a solid content of 20%.
- Examples 2-14 Cationic electrodeposition coating compositions X-2 to X-14 were produced in the same manner as in Example 1, except that the composition of the cationic electrodeposition coating composition X-1 of Example 1 was changed to Table 1 below.
- the compounding quantity in following Table 1 is a value of an active ingredient or solid content.
- Comparative Example 1 The amino group-containing epoxy resin obtained in Production Example 1 87.5 parts (solid content 70 parts) and the blocked polyisocyanate compound No. obtained in Production Example 6 were used. 1 After mixing 42.9 parts (solid content 30 parts), and further mixing 13 parts of 10% acetic acid and stirring uniformly, deionized water was gradually added dropwise with vigorous stirring to give an emulsion with a solid content of 34%. Got. Next, 294 parts of the emulsion (100 parts solids), 55% pigment dispersion paste No. obtained in Production Example 3 were used. 1 52.4 parts (solid content 28.8 parts) and deionized water 350 parts were added to produce a cationic electrodeposition coating composition X-15 having a solid content of 20%.
- Comparative Example 1 is manufactured by a conventional method in which an amino group-containing epoxy resin and a blocked polyisocyanate compound are mixed, dispersed in water, and then mixed with a pigment dispersion paste.
- Neugen EA-167 trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., nonionic emulsifier (polyoxyethylene alkyl styrenated ether).
- Test plates (before storage test, after storage test) creating chemical conversion (trade name, PALBOND # 3020, Nihon Parkerizing Co., zinc phosphate treatment agent) cold rolled was subjected to steel (150 mm (vertical) ⁇ 70 mm (width) A cold-rolled steel sheet (0.8 mm ⁇ 150 mm ⁇ 70 mm) subjected to ⁇ 0.8 mm (thickness) is used as an object to be coated, and the dry film thickness is 17 ⁇ m using the cationic electrodeposition paint obtained in Examples and Comparative Examples. Electrodeposition coating was carried out as described above, and baked and dried at 120 ° C. for 30 minutes to obtain a test plate (before the storage test).
- each cationic electrodeposition coating material obtained in Examples and Comparative Examples was placed in a cylindrical sealed container (diameter 20 cm ⁇ height 15 cm) shown in FIG. 1 and stirred at a temperature of 30 ° C. for 30 days (width 8 cm).
- X Stored while stirring with a stirring blade having a height of 3 cm at a rotational speed of 700 rpm.
- Electrodeposition coating was performed using the cationic electrodeposition paint after the storage test so as to have a dry film thickness of 17 ⁇ m, and baked and dried at 120 ° C. for 30 minutes to obtain a test plate (after the storage test).
- the surface roughness value (Ra) was measured at a cutoff of 0.8 mm on the coated surface of the test plate and evaluated according to the following criteria: did. In the evaluation, A to C are acceptable and D is unacceptable. A: The surface roughness value (Ra) is less than 0.2. B: The surface roughness value (Ra) is 0.2 or more and less than 0.25. C: The surface roughness value (Ra) is 0.25 or more and less than 0.3. D: The surface roughness value (Ra) is 0.3 or more.
- a cross-cut flaw is made in the coating film with a cutter knife so as to reach the base of the test plate, and this is subjected to a salt spray test at 35 ° C. for 840 hours in accordance with JIS Z-2371. Evaluation was made according to the following criteria according to the width. In the evaluation, A to C are acceptable and D is unacceptable. In A, the maximum width of rust and swelling is 2.0 mm or less on one side from the cut part. In B, the maximum width of rust and blisters is greater than 2.0 mm and 2.8 mm or less on one side from the cut part. C has a maximum width of rust and swelling of more than 2.8 mm and not more than 3.5 mm on one side from the cut part. In D, the maximum width of rust and blisters exceeds 3.5 mm on one side from the cut part.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
しかしながら、基体樹脂と硬化剤の塗料・塗装を分けることで塗料の貯蔵安定性(浴安定性)は改善されるものの、塗膜内に硬化剤が均一に存在しない場合があることから防食性などが劣ることがあった。また、塗装工程や洗浄工程が増えるため、新たに設備を増設する必要があった。
項2.ブロック化ポリイソシアネート化合物の水分散体(B)が、ブロック化ポリイソシアネート化合物(b)及び乳化剤を含有し、該乳化剤の含有量が、水分散体(B)の樹脂固形分を基準として、0.01~40質量%であることを特徴とする前記項1に記載のカチオン電着塗料組成物の製造方法。
項3.乳化剤が、カチオン性乳化剤であることを特徴とする前記項2に記載のカチオン電着塗料組成物の製造方法。
項4.ブロック化ポリイソシアネート化合物の水分散体(B)が、イソシアネート化合物(b-1)とブロック剤(b-2)とを反応して得られるブロック化ポリイソシアネート化合物(b)、及び乳化剤を含有し、該ポリイソシアネート化合物(b-1)のイソシアネート基含有量を基準として、乳化剤の活性水素基含有量が、50mol%以下であることを特徴とする前記項2又は3に記載のカチオン電着塗料組成物の製造方法。
項5.ブロック化ポリイソシアネート化合物の水分散体(B)が、イソシアネート化合物(b-1)とブロック剤(b-2)とを反応して得られる(からなる)ブロック化ポリイソシアネート化合物(b)を含有し、該ブロック剤(b-2)が、ピラゾール系化合物、活性メチレン系化合物、オキシム系化合物、フェノール系化合物、ラクタム系化合物及びアルコール系化合物からなる群より選ばれる少なくとも1種であることを特徴とする前記項1~4のいずれか1項に記載のカチオン電着塗料組成物の製造方法。
項6.前記項1~5の製造方法で得られたカチオン電着塗料組成物を用い、下記条件により測定したゲル分率が、90%以上である事を特徴とするカチオン電着塗料組成物の製造方法。
〔ゲル分率の測定条件〕
カチオン電着塗料組成物を硬化塗膜が20μmの膜厚となるように金属板に電着塗装し、120℃で30分間加熱する。得られた硬化塗膜の塗膜質量(Wa)を測定し、アセトンに浸漬して5時間加熱還流させた。次いで、アセトンに浸漬した塗膜を110℃で1時間乾燥した後の塗膜質量(Wb)を測定し、下記式に従って得られる不溶塗膜残存率(%)をゲル分率とする。
ゲル分率(%)=(Wb/Wa)×100
項7.前記項1~6の製造方法で得られたカチオン電着塗料組成物を用いて、金属被塗物に電着塗装して、160℃以下の温度で焼付けをする事を特徴とする塗膜形成方法。
項8.前記項1~6の製造方法で得られたカチオン電着塗料組成物を用いて、金属被塗物に電着塗装して、80~130℃の温度で焼付けをする事を特徴とする塗膜形成方法。
以下、詳細に述べる。
本発明で用いることができるアミノ基含有エポキシ樹脂の水分散体(A)は、主成分であるアミノ基含有エポキシ樹脂(a)を水性溶媒中に分散させた分散体である。
上記水分散体(A)は、アミノ基含有エポキシ樹脂(a)以外に、中和剤、乳化剤、触媒等の添加剤、その他の樹脂成分などを必要に応じて含有することが出来る。
上記アミノ基含有エポキシ樹脂の水分散体(A)の構成成分であるアミノ基含有エポキシ樹脂(a)としては、例えば、(1)エポキシ樹脂と第1級モノ-及びポリアミン、第2級モノ-及びポリアミン又は第1、2級混合ポリアミンとの付加物(例えば、米国特許第3,984,299号明細書参照);(2)エポキシ樹脂とケチミン化された第1級アミノ基を有する第2級モノ-及びポリアミンとの付加物(例えば、米国特許第4,017,438号 明細書参照);(3)エポキシ樹脂とケチミン化された第1級アミノ基を有するヒドロキシ化合物とのエーテル化により得られる反応物(例えば、特開昭59-43013号公報参照)等を挙げることができる。
ポリアルキレンオキシド鎖中のアルキレン基としては、炭素数が2~8のアルキレン基が好ましく、エチレン基、プロピレン基またはブチレン基がより好ましく、プロピレン基が特に好ましい。
本発明で用いることができるブロック化ポリイソシアネート化合物の水分散体(B)は、ブロック化ポリイソシアネート化合物(b)からなる成分を水性溶媒中に分散させた分散体であって、該ブロック化ポリイソシアネート化合物(b)は、イソシアネート化合物(b-1)とブロック剤(b-2)とを反応して得られるものである。
上記水分散体(B)は、ポリイソシアネート化合物(b)以外に、中和剤、乳化剤等の添加剤、その他の樹脂成分などを必要に応じて含有することが出来る。
カチオン性官能基の含有量としては、水分散体(B)の分散性を確保するため、アミン価(mgKOH/g)相当量として、20~300程度であることが好ましく、30~200であることがより好ましい。20未満であると分散性が劣り、300を超えると塗膜の耐水性等に悪影響が出る場合がある。
上記ブロック化ポリイソシアネート化合物の水分散体(B)の構成成分であるブロック化ポリイソシアネート化合物(b)としては、ポリイソシアネート化合物(b-1)とブロック剤(b-2)との付加反応生成物である。また、必要に応じて、ブロック剤(b-2)以外の活性水素含有化合物を用い、ブロック剤(b-2)と共にポリイソシアネート化合物(b-1)と反応することができる(本発明においては、かかるブロック剤(b-2)以外の活性水素含有化合物を用いた反応により得られる化合物も当然に、「ポリイソシアネート化合物(b-1)とブロック剤(b-2)との付加反応生成物」に包含される)。
本発明で用いることができる顔料分散ペースト(C)は、着色顔料、防錆顔料、体質顔料、及び硬化触媒などの顔料をあらかじめ微細粒子に分散したものであって、例えば、顔料分散用樹脂、顔料、及び中和剤などの各種添加剤を配合し、ボールミル、サンドミル、ペブルミル等の分散混合機中で分散処理して、顔料分散ペーストを調製することができる。
有機錫化合物の代替触媒として、亜鉛化合物、ビスマス化合物、チタン化合物、ジルコニウム化合物、イットリウム化合物などの無機化合物;フォスファゼン化合物、アミン化合物、4級塩化合物などの有機化合物;これらの複合物等を用いること、若しくは触媒を実質的に用いないことが、環境面への配慮の観点から、更に好ましい。
尚、本発明の製造方法で得られるカチオン電着塗料組成物において、硬化触媒に有機化合物を用いる場合は、顔料分散ペースト(C)以外に、アミノ基含有エポキシ樹脂の水分散体(A)に含有することができる。
本発明の製造方法で得られるカチオン電着塗料組成物において、水分散体(A)中に含まれるアミノ基含有エポキシ樹脂(a)及び水分散体(B)中に含まれるブロック化ポリイソシアネート硬化剤(b)の配合割合としては、上記成分(a)及び(b)の樹脂固形分合計質量を基準にして、成分(a)を30~90質量部、好ましくは40~85質量部、成分(b)を10~70質量部、好ましくは10~60質量部の範囲内であることが、貯蔵安定性が良好で、仕上がり性、防食性に優れた塗装物品を得る為にも好ましい。また、塗料中に含まれる樹脂全体のアミン価としては、樹脂固形分を基準として、アミン価が、通常20~150mgKOH/gの範囲内であることがより好ましい。配合割合が上記範囲を外れると、上記の塗料特性及び塗膜性能のいずれかを損うことがあり好ましくない。
本発明は、前述の製造方法で得られたカチオン電着塗料組成物からなる電着浴に被塗物を浸漬する工程、及び被塗物を陰極として通電する工程を含む、カチオン電着塗膜の形成方法を提供する。
製造例1
攪拌機、温度計、窒素導入管および還流冷却器を取りつけたフラスコに、jER828EL(商品名、ジャパンエポキシレジン社製エポキシ樹脂、エポキシ当量190、数平均分子量350)1000部、ビスフェノールA400部、及びジメチルベンジルアミン0.2部を加え、130℃でエポキシ当量750になるまで反応させた。次に、ε-カプロラクトン100部、テトラブトキシチタン0.05部を加え、170℃に昇温し、4時間、170℃で反応させた。次に、このものにプラクセル205(商品名、ダイセル化学工業社製、ポリカプロラクトンポリオール化合物)を100部、ジエタノールアミンを140部、及びジエチレントリアミンとメチルイソブチルケトンとのケチミン化物65部を加え、120℃で4時間反応させた後、エチレングリコールモノブチルエーテルを400部加え、樹脂固形分80%のアミノ基含有エポキシ樹脂溶液を得た。得られたアミノ基含有エポキシ樹脂の固形分当たりのアミン価は56mgKOH/gであった。
製造例2
製造例1で得た樹脂固形分80%アミノ基含有エポキシ樹脂125部(固形分100部)、及び10%ギ酸8部を配合し、均一に攪拌した後、強く攪拌しながら脱イオン水を徐々に滴下し、固形分32.0%のアミノ基含有エポキシ樹脂の水分散体を得た。
製造例3
撹拌機、温度計、滴下ロートおよび還流冷却器を取り付けたフラスコに、jER828EL(ジャパンエポキシレジン株式会社製、商品名、エポキシ樹脂)1010部に、ビスフェノールAを390部、プラクセル212(ポリカプロラクトンジオール、ダイセル化学工業株式会社、商品名、重量平均分子量約1,250)240部及びジメチルベンジルアミン0.2部を加え、130℃でエポキシ当量が約1090になるまで反応させた。次に、ジメチルエタノールアミン134部及び濃度90%の乳酸水溶液150部を加え、120℃で4時間反応させた。次いで、メチルイソブチルケトンを加えて固形分を調整し、固形分60%のアンモニウム塩型エポキシ樹脂系の顔料分散用樹脂を得た。
次に、上記顔料分散用樹脂8.3部(固形分5部)、酸化チタン14.5部、精製クレー7.0部、カーボンブラック0.3部、水酸化ビスマス2部及び脱イオン水20.3部を加え、ボールミルにて20時間分散し、固形分55%の顔料分散ペーストNo.1を得た。
製造例3で得た顔料分散用樹脂8.3部(固形分5部)、酸化チタン14.5部、精製クレー9.0部、カーボンブラック0.3部、及び脱イオン水20.3部を加え、ボールミルにて20時間分散し、固形分55%の顔料分散ペーストNo.2を得た。
製造例3で得た顔料分散用樹脂8.3部(固形分5部)、酸化チタン14.5部、精製クレー7.0部、カーボンブラック0.3部、ジオクチル錫オキシド2部及び脱イオン水20.3部を加え、ボールミルにて20時間分散し、固形分55%の顔料分散ペーストNo.3を得た。
製造例6
攪拌機、加熱装置、冷却装置、減圧装置を備えた4つ口フラスコに、「スミジュールN3300」(商品名、住化バイエルウレタン社製、ヘキサメチレンジイソシアネート由来のイソシアヌレート構造含有ポリイソシアネート)250部及びメチルエチルケトン125部を仕込み、30℃に加熱した。次いで、3,5-ジメチルピラゾール126部を攪拌しながら2時間かけて徐々に添加し、攪拌下、その反応混合物を赤外分光法によって、遊離のイソシアネート基が検出されなくなるまで30℃にて反応させた。更にメチルイソブチルケトンを加えて固形分70%のブロック化ポリイソシアネート化合物No.1を得た。得られたピラゾールブロックのブロック化ポリイソシアネート化合物のNCO量は14.4%であった。
なお、本明細書において、NCO量は、樹脂固形分100質量部に対するNCO基の量(%)を意味する。
攪拌機、加熱装置、冷却装置、減圧装置を備えた4つ口フラスコに、「スミジュールN-3300」(商品名、住化バイエルウレタン社製、ヘキサメチレンジイソシアネート由来のイソシアヌレート構造含有ポリイソシアネート)200部、メチルエチルケトン100部及びマロン酸ジイソプロピル196部を仕込み、窒素気流下で攪拌しながら、ナトリウムメトキシドの28%メタノール溶液1.6部を加え、65℃で8時間攪拌した。更にメチルイソブチルケトンを加えて固形分70%のブロック化ポリイソシアネート化合物No.2を得た。得られたブロック化ポリイソシアネート化合物のNCO量は11.0%であった。
攪拌機、加熱装置、冷却装置、減圧装置を備えた4つ口フラスコに、ヘキサメチレンジイソシアネート272部及びメチルエチルケトン214部を仕込み、60℃に加熱した。次いで、メチルエチルケトオキシム169部を攪拌しながら1時間かけて徐々に添加した。その後、60℃で2時間反応させた後、トリメチロールプロパン59部を温度が70℃以上にならないように徐々に添加した。攪拌下、その反応混合物を赤外分光法によって、遊離のイソシアネート基が検出されなくなるまで60℃にて反応させた。反応終了後、固形分70%のブロック化ポリイソシアネート化合物No.3を得た。得られたブロック化ポリイソシアネート化合物のNCO量は16.4%であった。
攪拌機、加熱装置、冷却装置、減圧装置を備えた4つ口フラスコに、「コスモネートM-200」(商品名、三井化学社製、クルードMDI)270部及びメチルイソブチルケトン127部を加え70℃に昇温した。この中にエチレングリコールモノブチルエーテル236部を1時間かけて滴下して加え、その後、100℃に昇温し、この温度を保ちながら、経時でサンプリングし、赤外線吸収スペクトル測定にて未反応のイソシアネート基の吸収がなくなったことを確認し、更にメチルイソブチルケトンを加えて固形分70%のブロック化ポリイソシアネート化合物No.4を得た。得られたブロック化ポリイソシアネート化合物のNCO量は16.7%であった。
攪拌機、加熱装置、冷却装置、減圧装置を備えた4つ口フラスコに、「スミジュールN3300」(商品名、住化バイエルウレタン社製、ヘキサメチレンジイソシアネート由来のイソシアヌレート構造含有ポリイソシアネート)250部及びメチルエチルケトン125部、トリメチロールプロパン2.7部を仕込み、70℃で2時間反応させた。次いで、3,5-ジメチルピラゾール120部を攪拌しながら2時間かけて徐々に添加し、攪拌下、その反応混合物を赤外分光法によって、遊離のイソシアネート基が検出されなくなるまで30℃にて反応させた。更にメチルイソブチルケトンを加えて固形分70%のブロック化ポリイソシアネート化合物No.5を得た。得られたピラゾールブロックのブロック化ポリイソシアネート化合物のNCO量は13.9%であった。
攪拌機、加熱装置、冷却装置、減圧装置を備えた4つ口フラスコに、「スミジュールN3300」(商品名、住化バイエルウレタン社製、ヘキサメチレンジイソシアネート由来のイソシアヌレート構造含有ポリイソシアネート)250部及びメチルエチルケトン125部、PEG-1000(三洋化成社製、ポリエチレングリコール)20部を仕込み、70℃で2時間反応させた。次いで、3,5-ジメチルピラゾール122.5部を攪拌しながら2時間かけて徐々に添加し、攪拌下、その反応混合物を赤外分光法によって、遊離のイソシアネート基が検出されなくなるまで30℃にて反応させた。更にメチルイソブチルケトンを加えて固形分70%のブロック化ポリイソシアネート化合物No.6を得た。得られたピラゾールブロックのブロック化ポリイソシアネート化合物のNCO量は13.4%であった。
製造例12
温度計、サーモスタット、撹拌器、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にメトキシプロパノール30部、イソブタノール30部の混合溶剤を入れ、110℃に加熱し、エチルアクリレート20部、n-ブチルアクリレート50部、N,N-ジメチルアミノエチルメタクリレート30部、イソブタノール10部、t-ブチルパーオキシオクタノエート4部からなる混合物を4時間かけて上記混合溶剤に加え、さらにt-ブチルパーオキシオクタノエート0.5部とイソブタノール10部からなる混合物を1時間滴下した。次いで1時間攪拌熟成した後、10%ギ酸40部を加えて固形分濃度50%のカチオン性乳化剤No.1を得た。得られたカチオン性乳化剤のアミン価は107mgKOH/g、水酸基価は0mgKOH/g、活性水素基価(アミン価換算)は0mgKOH/g、重量平均分子量は10,000であった。
温度計、サーモスタット、撹拌器、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にメトキシプロパノール30部、イソブタノール30部の混合溶剤を入れ、110℃に加熱し、n-ブチルアクリレート30部、N,N-ジメチルアミノエチルメタクリレート30部、2-ヒドロキシエチルアクリレート40部、イソブタノール10部、t-ブチルパーオキシオクタノエート4部からなる混合物を4時間かけて上記混合溶剤に加え、さらにt-ブチルパーオキシオクタノエート0.5部とイソブタノール10部からなる混合物を1時間滴下した。次いで1時間攪拌熟成した後、10%ギ酸40部を加えて固形分濃度50%のカチオン性乳化剤No.2を得た。得られたカチオン性乳化剤のアミン価は107mgKOH/g、水酸基価は194mgKOH/g、活性水素基価(アミン価換算)は194mgKOH/g、重量平均分子量は10,000であった。
攪拌機、温度計、窒素導入管および還流冷却器を取りつけたフラスコに、jER828EL(商品名、ジャパンエポキシレジン社製エポキシ樹脂、エポキシ当量190、数平均分子量350)608部に、ビスフェノールA 137部及びジメチルベンジルアミン0.2部を加え、130℃でエポキシ当量370になるまで反応させた。
攪拌機、温度計、窒素導入管および還流冷却器を取りつけたフラスコに、jER828EL(商品名、ジャパンエポキシレジン社製エポキシ樹脂、エポキシ当量190、数平均分子量350)608部に、ビスフェノールA 137部及びジメチルベンジルアミン0.2部を加え、130℃でエポキシ当量370になるまで反応させた。
攪拌機、温度計、窒素導入管および還流冷却器を取りつけたフラスコに、jER828EL(商品名、ジャパンエポキシレジン社製エポキシ樹脂、エポキシ当量190、数平均分子量350)608部に、ビスフェノールA 137部及びジメチルベンジルアミン0.2部を加え、130℃でエポキシ当量370になるまで反応させた。
実施例1
製造例6で得たブロック化ポリイソシアネート化合物No.1 42.9部(固形分30部)及び製造例12で得たカチオン性乳化剤No.1 15部(固形分7.5部)を配合し、均一に攪拌した後、強く攪拌しながら脱イオン水を徐々に滴下し、固形分32.0%のブロック化ポリイソシアネート化合物の水分散体(B)を得た。
次いで、上記水分散体に製造例2で得たアミノ基含有エポキシ樹脂の水分散体218.8部(固形分70部)、製造例3で得た固形分55%の顔料分散ペーストNo.1 52.4部(固形分28.8部)、及び純水を撹拌しながら徐々に添加して固形分20%のカチオン電着塗料組成物X-1を得た。
実施例1のカチオン電着塗料組成物X-1の配合を、下記表1とした以外は、実施例1と同様にして、カチオン電着塗料組成物X-2~X-14を製造した。
尚、下記表1中の配合量は、有効成分または固形分の値である。
製造例1で得たアミノ基含有エポキシ樹脂 87.5部(固形分70部)及び製造例6で得たブロック化ポリイソシアネート化合物No.1 42.9部(固形分30部)を混合し、さらに10%酢酸13部を配合して均一に攪拌した後、強く攪拌しながら脱イオン水を徐々に滴下して固形分34%のエマルションを得た。
次に、上記エマルション294部(固形分100部)、製造例3で得た55%の顔料分散ペーストNo.1 52.4部(固形分28.8部)、脱イオン水350部を加え、固形分20%のカチオン電着塗料組成物X-15を製造した。
(注1)ノイゲンEA-167:商品名、第一工業製薬社製、ノニオン性乳化剤(ポリオキシエチレンアルキルスチレン化エーテル)。
(注2)ポリイソシアネート化合物(b-1)のイソシアネート基含有量を基準とした時の乳化剤の活性水素基含有量(mol%)。
<ゲル分率>
実施例及び比較例で得たカチオン電着塗料を用い、硬化膜厚が20μmとなるように、金属板に電着塗装した。続いて120℃の温度で30分間加熱した後、塗膜質量(Wa)を測定した。上記金属板をセパレート型丸底フラスコの中に設置し、塗膜1gに対してアセトン100gを加え5時間加熱還流した。取り出した塗膜を110℃×1時間で乾燥後、塗膜重量(Wb)を測定し、以下の式によりゲル分率を算出した。
ゲル分率(%)=(Wb/Wa)×100
以下の基準で評価を行なった。A~Cが合格であり、Dが不合格である。
A:ゲル分率が、90%以上である。
B:ゲル分率が、80%以上、且つ90%未満である。
C:ゲル分率が、70%以上、且つ80%未満である。
D:ゲル分率が、70%未満である。
化成処理(商品名、パルボンド#3020、日本パーカライジング社製、リン酸亜鉛処理剤)を施した冷延鋼板(150mm(縦)×70mm(横)×0.8mm(厚))を施した冷延鋼板(0.8mm×150mm×70mm)を被塗物として、実施例及び比較例で得たカチオン電着塗料を用いて乾燥膜厚17μmとなるように電着塗装し、120℃で30分間焼付け乾燥して試験板(貯蔵試験前)を得た。
次いで、図1に示す円筒形の密封容器(直径20cm×高さ15cm)に、実施例及び比較例で得た各々のカチオン電着塗料3500gを入れ、30℃の温度で30日間撹拌(幅8cm×高さ3cmの撹拌翼で回転速度700rpm)しながら貯蔵した。
上記貯蔵試験後のカチオン電着塗料を用いて乾燥膜厚17μmとなるように電着塗装し、120℃で30分間焼付け乾燥して試験板(貯蔵試験後)を得た。
試験板の塗面をサーフテスト301(商品名、株式会社ミツトヨ製、表面粗度計)を用いて、表面粗度値(Ra)をカットオフ0.8mmにて測定し、以下の基準で評価した。評価は、A~Cが合格であり、Dが不合格である。
A:表面粗度値(Ra)が、0.2未満である。
B:表面粗度値(Ra)が、0.2以上、且つ0.25未満である。
C:表面粗度値(Ra)が、0.25以上、且つ0.3未満である。
D:表面粗度値(Ra)が、0.3以上である。
試験板の素地に達するように塗膜にカッターナイフでクロスカット傷を入れ、これをJIS Z-2371に準じて、35℃ソルトスプレー試験を840時間行い、カット部からの片側での錆、フクレ幅によって以下の基準で評価した。
評価は、A~Cが合格であり、Dが不合格である。
Aは、錆及びフクレの最大幅がカット部より片側で、2.0mm以下である。
Bは、錆及びフクレの最大幅がカット部より片側で、2.0mmを超え、且つ2.8mm以下である。
Cは、錆及びフクレの最大幅がカット部より片側で、2.8mmを超え、且つ3.5mm以下である。
Dは、錆及びフクレの最大幅がカット部より片側で、3.5mmを超える。
Claims (8)
- アミノ基含有エポキシ樹脂の水分散体(A)、ブロック化ポリイソシアネート化合物の水分散体(B)、及び顔料分散ペースト(C)の3成分を混合して得られることを特徴とするカチオン電着塗料組成物の製造方法。
- ブロック化ポリイソシアネート化合物の水分散体(B)が、ブロック化ポリイソシアネート化合物(b)及び乳化剤を含有し、該乳化剤の含有量が、水分散体(B)の樹脂固形分を基準として、0.01~40質量%であることを特徴とする請求項1に記載のカチオン電着塗料組成物の製造方法。
- 乳化剤が、カチオン性乳化剤であることを特徴とする請求項2に記載のカチオン電着塗料組成物の製造方法。
- ブロック化ポリイソシアネート化合物の水分散体(B)が、イソシアネート化合物(b-1)とブロック剤(b-2)とを反応して得られるブロック化ポリイソシアネート化合物(b)、及び乳化剤を含有し、該ポリイソシアネート化合物(b-1)のイソシアネート基含有量を基準として、乳化剤の活性水素基含有量が、50mol%以下であることを特徴とする請求項2又は3に記載のカチオン電着塗料組成物の製造方法。
- ブロック化ポリイソシアネート化合物の水分散体(B)が、イソシアネート化合物(b-1)とブロック剤(b-2)とを反応して得られるブロック化ポリイソシアネート化合物(b)を含有し、該ブロック剤(b-2)が、ピラゾール系化合物、活性メチレン系化合物、オキシム系化合物、フェノール系化合物、ラクタム系化合物及びアルコール系化合物からなる群より選ばれる少なくとも1種であることを特徴とする請求項1~4のいずれか1項に記載のカチオン電着塗料組成物の製造方法。
- 請求項1~5のいずれか1項に記載のカチオン電着塗料組成物の製造方法であって、当該製造方法で得られたカチオン電着塗料組成物を用い、下記条件により測定したゲル分率が、90%以上である事を特徴とするカチオン電着塗料組成物の製造方法。
〔ゲル分率の測定条件〕
カチオン電着塗料組成物を硬化塗膜が20μmの膜厚となるように金属板に電着塗装し、120℃で30分間加熱する。得られた硬化塗膜の塗膜質量(Wa)を測定し、アセトンに浸漬して5時間加熱還流させた。次いで、アセトンに浸漬した塗膜を110℃で1時間乾燥した後の塗膜質量(Wb)を測定し、下記式に従って得られる不溶塗膜残存率(%)をゲル分率とする。
ゲル分率(%)=(Wb/Wa)×100 - 請求項1~6のいずれか1項に記載の製造方法で得られたカチオン電着塗料組成物を用いて、金属被塗物に電着塗装して、160℃以下の温度で焼付けをする事を特徴とする塗膜形成方法。
- 請求項1~6のいずれか1項に記載の製造方法で得られたカチオン電着塗料組成物を用いて、金属被塗物に電着塗装して、80~130℃の温度で焼付けをする事を特徴とする塗膜形成方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17750169.9A EP3415574B1 (en) | 2016-02-08 | 2017-02-03 | Method for producing cationic electrodeposition coating composition |
JP2017566914A JP6608463B2 (ja) | 2016-02-08 | 2017-02-03 | カチオン電着塗料組成物の製造方法 |
CN201780009370.3A CN108603070B (zh) | 2016-02-08 | 2017-02-03 | 阳离子电沉积涂料组合物的制备方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-021879 | 2016-02-08 | ||
JP2016021879 | 2016-02-08 | ||
US201662295764P | 2016-02-16 | 2016-02-16 | |
US62/295,764 | 2016-02-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017138445A1 true WO2017138445A1 (ja) | 2017-08-17 |
Family
ID=59496206
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/003905 WO2017138445A1 (ja) | 2016-02-08 | 2017-02-03 | カチオン電着塗料組成物の製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10316200B2 (ja) |
EP (1) | EP3415574B1 (ja) |
JP (1) | JP6608463B2 (ja) |
CN (1) | CN108603070B (ja) |
WO (1) | WO2017138445A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020111717A (ja) * | 2019-01-08 | 2020-07-27 | 株式会社ウェルグリーン | 2液常温硬化型樹脂組成物及び硬化型樹脂の製造法 |
JP2020180213A (ja) * | 2019-04-25 | 2020-11-05 | 関西ペイント株式会社 | カチオン電着塗料組成物 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11459665B2 (en) * | 2017-12-20 | 2022-10-04 | Basf Se | Composition for tin or tin alloy electroplating comprising suppressing agent |
US20210246319A1 (en) * | 2018-05-07 | 2021-08-12 | Basf Polyurethanes Gmbh | Epoxy resin-based cathodic electrodeposition (ced) of metal components as an adhesion promoter for pu systems |
WO2020175065A1 (ja) * | 2019-02-27 | 2020-09-03 | 関西ペイント株式会社 | 熱硬化性塗料組成物及び塗装物品 |
EP3950149A4 (en) * | 2019-03-29 | 2022-12-07 | Kansai Paint Co., Ltd | COMPOSITION OF CATIONIC ELECTRODEPOSITION COATING MATERIAL |
WO2023078670A1 (en) | 2021-11-04 | 2023-05-11 | Basf Coatings Gmbh | Self-emulsifying blocked polyisocyanate dispersion and process for preparing the same |
WO2023078664A1 (en) | 2021-11-04 | 2023-05-11 | Basf Coatings Gmbh | Electrodeposition coating composition and its preparation |
CN115975469A (zh) * | 2022-12-27 | 2023-04-18 | 安徽朗凯奇建材有限公司 | 一种装饰用保温防水涂料及其制备方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984299A (en) | 1970-06-19 | 1976-10-05 | Ppg Industries, Inc. | Process for electrodepositing cationic compositions |
US4017438A (en) | 1974-12-16 | 1977-04-12 | Ppg Industries, Inc. | Ketimine-blocked primary amine group-containing cationic electrodepositable resins |
JPS56120758A (en) * | 1980-01-28 | 1981-09-22 | Basf Farben & Fasern | Aqueous dispersion* manufacture of baking coat and method of depositing cationic synthetic resin together with fine nonionic synthetic resin from aqueous dispertion electrophoretically |
JPH02502291A (ja) * | 1987-07-29 | 1990-07-26 | ビーエーエスエフ ラツケ ウント フアルベン アクチエンゲゼルシヤフト | 陰極で析出可能な合成樹脂を含有する水性電気浸漬ラツカー浴及び電気伝導性基材の被覆法 |
JPH0439322A (ja) | 1990-06-04 | 1992-02-10 | Kansai Paint Co Ltd | 自己硬化性樹脂の製造方法 |
JPH07300698A (ja) | 1994-04-27 | 1995-11-14 | Kansai Paint Co Ltd | 電着塗膜形成方法 |
JPH0881644A (ja) * | 1994-07-15 | 1996-03-26 | Kansai Paint Co Ltd | カチオン電着塗料の製造方法 |
JPH10120947A (ja) | 1996-10-15 | 1998-05-12 | Nippon Paint Co Ltd | カチオン電着塗料組成物およびそれを用いたワキ防止方法 |
JP2002126616A (ja) * | 2000-10-26 | 2002-05-08 | Nippon Paint Co Ltd | 塗膜形成方法及び積層塗膜 |
JP2004027255A (ja) | 2002-06-21 | 2004-01-29 | Kansai Paint Co Ltd | 塗膜形成方法 |
JP2006002003A (ja) * | 2004-06-16 | 2006-01-05 | Nippon Paint Co Ltd | カチオン電着塗料組成物 |
JP2015187194A (ja) * | 2014-03-26 | 2015-10-29 | 日本ペイント・オートモーティブコーティングス株式会社 | カチオン電着塗料用エマルションの乳化現場での製造方法およびアミン化樹脂の運搬方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2180996T3 (es) * | 1996-06-12 | 2003-02-16 | Du Pont | Procedimiento para la aplicacion de pinturas multicapa sobre substratos conductores de la electricidad. |
JP2008202122A (ja) * | 2007-02-22 | 2008-09-04 | Nippon Paint Co Ltd | 硬化電着塗膜形成方法および複層塗膜形成方法 |
JP6076187B2 (ja) * | 2012-04-26 | 2017-02-08 | 関西ペイント株式会社 | カチオン電着塗料組成物 |
-
2017
- 2017-02-03 JP JP2017566914A patent/JP6608463B2/ja active Active
- 2017-02-03 CN CN201780009370.3A patent/CN108603070B/zh active Active
- 2017-02-03 EP EP17750169.9A patent/EP3415574B1/en active Active
- 2017-02-03 WO PCT/JP2017/003905 patent/WO2017138445A1/ja active Application Filing
- 2017-02-07 US US15/426,128 patent/US10316200B2/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984299A (en) | 1970-06-19 | 1976-10-05 | Ppg Industries, Inc. | Process for electrodepositing cationic compositions |
US4017438A (en) | 1974-12-16 | 1977-04-12 | Ppg Industries, Inc. | Ketimine-blocked primary amine group-containing cationic electrodepositable resins |
JPS56120758A (en) * | 1980-01-28 | 1981-09-22 | Basf Farben & Fasern | Aqueous dispersion* manufacture of baking coat and method of depositing cationic synthetic resin together with fine nonionic synthetic resin from aqueous dispertion electrophoretically |
JPH02502291A (ja) * | 1987-07-29 | 1990-07-26 | ビーエーエスエフ ラツケ ウント フアルベン アクチエンゲゼルシヤフト | 陰極で析出可能な合成樹脂を含有する水性電気浸漬ラツカー浴及び電気伝導性基材の被覆法 |
JPH0439322A (ja) | 1990-06-04 | 1992-02-10 | Kansai Paint Co Ltd | 自己硬化性樹脂の製造方法 |
JPH07300698A (ja) | 1994-04-27 | 1995-11-14 | Kansai Paint Co Ltd | 電着塗膜形成方法 |
JPH0881644A (ja) * | 1994-07-15 | 1996-03-26 | Kansai Paint Co Ltd | カチオン電着塗料の製造方法 |
JPH10120947A (ja) | 1996-10-15 | 1998-05-12 | Nippon Paint Co Ltd | カチオン電着塗料組成物およびそれを用いたワキ防止方法 |
JP2002126616A (ja) * | 2000-10-26 | 2002-05-08 | Nippon Paint Co Ltd | 塗膜形成方法及び積層塗膜 |
JP2004027255A (ja) | 2002-06-21 | 2004-01-29 | Kansai Paint Co Ltd | 塗膜形成方法 |
JP2006002003A (ja) * | 2004-06-16 | 2006-01-05 | Nippon Paint Co Ltd | カチオン電着塗料組成物 |
JP2015187194A (ja) * | 2014-03-26 | 2015-10-29 | 日本ペイント・オートモーティブコーティングス株式会社 | カチオン電着塗料用エマルションの乳化現場での製造方法およびアミン化樹脂の運搬方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020111717A (ja) * | 2019-01-08 | 2020-07-27 | 株式会社ウェルグリーン | 2液常温硬化型樹脂組成物及び硬化型樹脂の製造法 |
JP2020180213A (ja) * | 2019-04-25 | 2020-11-05 | 関西ペイント株式会社 | カチオン電着塗料組成物 |
Also Published As
Publication number | Publication date |
---|---|
EP3415574A4 (en) | 2019-10-30 |
US10316200B2 (en) | 2019-06-11 |
JPWO2017138445A1 (ja) | 2018-12-06 |
JP6608463B2 (ja) | 2019-11-20 |
EP3415574A1 (en) | 2018-12-19 |
US20170226354A1 (en) | 2017-08-10 |
CN108603070B (zh) | 2021-03-05 |
CN108603070A (zh) | 2018-09-28 |
EP3415574B1 (en) | 2020-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6608463B2 (ja) | カチオン電着塗料組成物の製造方法 | |
US8026320B2 (en) | Cationic electrodeposition coating composition | |
JP6058113B2 (ja) | カチオン電着塗料組成物 | |
US8293820B2 (en) | Cationic electrodeposition coating composition and articles coated with the electrodeposition coating | |
US20120222962A1 (en) | Cationic electrodeposition coating composition | |
WO2020262549A1 (ja) | カチオン電着塗料組成物 | |
US20120024703A1 (en) | Compositions useful for electrocoating metal substrates and electrodeposition processes using the coatings | |
CN107109105B (zh) | 热固性涂料组合物 | |
JP6796229B1 (ja) | カチオン電着塗料の塗装方法 | |
WO2022014277A1 (ja) | カチオン電着塗料組成物 | |
JP6714752B1 (ja) | カチオン電着塗料組成物 | |
JP2022183490A (ja) | カチオン電着塗料組成物、電着塗装物および電着塗装物の製造方法 | |
JP2022129794A (ja) | カチオン電着塗料組成物 | |
JP4460699B2 (ja) | 可塑剤を含むカチオン電着塗料組成物 | |
JP2006045560A (ja) | 重付加体及び該重付加体を含有するカチオン電着塗料 | |
JP6997279B2 (ja) | エポキシ系樹脂及び電着塗料 | |
JP4417046B2 (ja) | カチオン電着塗料組成物 | |
JP2011202047A (ja) | カチオン性電着塗料組成物 | |
JP6976281B2 (ja) | カチオン電着塗料組成物 | |
WO2016167147A1 (ja) | 電着塗料組成物、電着塗料組成物用触媒 | |
WO2022092288A1 (ja) | カチオン電着塗料組成物 | |
JP2022129736A (ja) | 顔料分散ペースト、塗料組成物およびカチオン電着塗料組成物 | |
JPWO2004090055A1 (ja) | 重付加体及び該重付加体を含有するカチオン電着塗料 | |
JP5334133B2 (ja) | カチオン性電着塗料組成物の塗装方法 | |
JP2022088769A (ja) | カチオン電着塗料組成物、電着塗装方法及びカチオン電着塗膜 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17750169 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017566914 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017750169 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2017750169 Country of ref document: EP Effective date: 20180910 |