CN115702224A - Electrodeposition coating composition - Google Patents
Electrodeposition coating composition Download PDFInfo
- Publication number
- CN115702224A CN115702224A CN202180029788.7A CN202180029788A CN115702224A CN 115702224 A CN115702224 A CN 115702224A CN 202180029788 A CN202180029788 A CN 202180029788A CN 115702224 A CN115702224 A CN 115702224A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- epoxy
- electrodeposition coating
- weight
- resin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 37
- 239000008199 coating composition Substances 0.000 title claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 67
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 67
- 239000000654 additive Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 125000002091 cationic group Chemical group 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- -1 alicyclic isocyanate Chemical class 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 22
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 239000012948 isocyanate Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 54
- 239000011248 coating agent Substances 0.000 description 53
- 239000000047 product Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 5
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to an electrodeposition coating composition comprising a resin, a curing agent, and a cationic water-dispersing additive prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amino group-containing alkoxysilane, and comprising the first and second epoxy resins in a weight ratio of 1 to 5.
Description
Technical Field
The present invention relates to an electrodeposition coating composition which is excellent in storage stability and filterability and can form a coating film excellent in weather resistance and also excellent in edge (edge) rust prevention.
Background
Generally, after the body of an automobile is finished, multi-layer coating is generally performed to prevent corrosion of the surface of the body and improve the sound insulation function and to make the appearance beautiful. Generally, the multilayer coating is formed by subjecting a vehicle body having undergone a pretreatment step to electrodeposition coating, intermediate coating, top coating, and clear coating.
The electrodeposition coating is a coating method in which a substrate is immersed in an electrodeposition coating liquid and a current is applied between the substrate and a counter electrode to electrically deposit a coating film on the surface of the substrate, and is also called electrophoretic coating, or ED coating. As the paint used for such electrodeposition coating, epoxy type and acrylic type are mainly used, and the epoxy type paint is mainly used in the coating specification where high corrosion resistance is required, and the acrylic type paint is mainly used in the coating specification where weather resistance and appearance characteristics are required.
As an example, a cathode electrocoating composition comprising: a polyoxyalkylene amine; glycidoxyalkylalkoxysilane; and a sealing agent as an additive comprising a reaction product of the glycidyl compound. However, the composition of patent document 1 is excellent in edge (edge) coverage but insufficient in storage stability and insufficient in filterability.
Therefore, it is a real situation that research and development of an electrodeposition coating composition excellent in storage stability and filterability, which is capable of forming a coating film excellent in weather resistance and also excellent in rust prevention of edges (edge) is required.
The prior art documents: korean granted patent No. 713732 (published: 2002, 4/26).
Disclosure of Invention
(problems to be solved by the invention)
The present invention aims to provide an electrodeposition coating composition which is excellent in storage stability and filterability and is capable of forming a coating film excellent in weather resistance and also excellent in edge (edge) rust prevention.
(measures taken to solve the problems)
The invention provides an electrodeposition coating composition comprising a resin, a curing agent and a cationic water-dispersing additive,
the cationic water-dispersing additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amino-containing alkoxysilane,
and the above first epoxy resin and second epoxy resin are contained in a weight ratio of 1.
(Effect of the invention)
According to the electrodeposition coating composition of the present invention, it is excellent in storage stability and filterability and capable of forming a coating film excellent in weather resistance and excellent in rust prevention of edge (edge).
Detailed Description
The present invention is described in detail below.
In the present invention, the valence of the acting group such as 'unreacted NCO content (NCO%)' can be measured by a method known in the art, and for example, it can be a value measured by a titration method (titration) or the like.
The electrodeposition coating composition according to the present invention comprises a resin, a curing agent, and a cationic water-dispersing additive.
Resin composition
The resin is a main agent of the electrodeposition coating composition, and plays a role of adjusting the characteristics of the prepared coating film.
The resin is not particularly limited as long as it is a resin that can be generally used as a main agent of an electrodeposition paint, and for example, an epoxy resin may be included. The resin may be a bisphenol type epoxy resin, and the bisphenol type epoxy resin may be, for example, a bisphenol a type epoxy resin.
The above resin may be included in the composition at a content of 5 to 30 parts by weight or 10 to 25 parts by weight for 5 to 30 parts by weight of the curing agent. When the content of the resin is less than the above-mentioned content, the rust inhibitive performance of the composition is insufficient, and when the content exceeds the above-mentioned content, the impact resistance of the resulting coating film is insufficient.
Curing agent
The curing agent and the resin are crosslinked to thereby effect curing of the composition.
The curing agent may be an isocyanate resin, and the isocyanate resin is not particularly limited as long as it is a curing agent generally used for a coating material. For example, the isocyanate resin may be an aromatic isocyanate and an alicyclic isocyanate, and the aromatic isocyanate may be preferably an alicyclic isocyanate because the aromatic ring may be decomposed by a double bond when exposed to UV, and thus weather resistance may be reduced.
The above alicyclic isocyanate may include, for example, one selected from the group consisting of 1-isocyanato (isocyanato) -3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4-diisocyanato-3, 5-trimethylcyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclohexane, 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4' -or 4,4' -diisocyanatodicyclohexylmethane, 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane, 4' -diisocyanato 3,3' -dimethyldicyclohexylmethane, 4' -diisocyanato-3, 3',3 ',5,5' -tetramethyldicyclohexylmethane, 4' -diisocyanato-1, 1' -bicyclohexyl (bicyclohexyl), 4' -diisocyanato-3, 3' -dimethyl-1, 1' -bicyclohexyl and 4,4' -diisocyanato-2, 2', 5' -tetramethyl-1, 1' -bicyclohexyl.
The isocyanate resin may be one whose ends are blocked with a blocking agent. The blocking agent stabilizes the terminal isocyanate group to a specific temperature, and when the temperature is higher than the specific temperature, the blocking agent dissociates from the isocyanate group to exert an action of adjusting reactivity. The blocking agent may be, for example, an oxime compound such as diethyl malonate, dimethylpyrazole, cyclohexanone oxime or methyl ethyl ketoxime, a lactam compound such as epsilon-caprolactam or gamma-butyrolactam, an alcohol compound such as methanol or ethanol, or the like.
The above curing agent may be included in the composition in a content of 5 to 30 parts by weight or 10 to 20 parts by weight with respect to 5 to 30 parts by weight of the resin. When the content of the curing agent is less than the above content, the curability of the composition is poor, and when the content exceeds the above content, the rust prevention of the coating film to be produced is poor.
Cationic water-dispersing additives
The cationic water-dispersing additive controls the fluidity of the composition at the edge (edge) when forming a coating film, and plays a role in improving the edge coverage and the thickening property of the coating film.
The cationic water-dispersible additive described above is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amino-containing alkoxysilane. The above additive composition may contain the first epoxy resin and the second epoxy resin in a weight ratio of 1 to 5. When the weight ratio of the first epoxy resin to the second epoxy resin is less than 1, that is, the content of the first epoxy resin is less than that of the second epoxy resin, the edge (edge) coating film thickening property of the composition is insufficient, and when it exceeds 5, that is, when the first epoxy resin is contained in excess based on the second epoxy resin, the resin synthesis stability is insufficient.
The above epoxy resin (total amount of the first epoxy resin and the second epoxy resin) and the amino group-containing alkoxysilane may be contained in a weight ratio of 5 to 1. In the case where the weight ratio of the epoxy resin to the amino group-containing alkoxysilane is less than the above range, that is, the content of the epoxy resin is less than the amino group-containing alkoxysilane, there is a problem in that the electrodeposition coating film is redissolved due to an excess of unreacted amine, and in the case where the cationic water-dispersing additive is contained in excess of the above range, the storage stability of the additive is insufficient due to an increase in the molecular weight of the prepared cationic water-dispersing additive.
< first epoxy resin >
The first Epoxy resin has a low Epoxy Group Content (Epoxy Group Content) and a high viscosity at 25 ℃ as compared with the second Epoxy resin. For example, the epoxy group content may be as low as 300 to 2,000mmol/kg or 500 to 1,100mmol/kg and the viscosity at 25 ℃ may be as high as 40 to 75 mPas or 50 to 70 mPas for the above-described first epoxy resin as compared to the second epoxy resin.
The epoxy group content of the above-mentioned first epoxy resin may be 2,500 to 3,500mmol/kg or 2,900 to 3,300mmol/kg. When the epoxy group content of the first epoxy resin is less than the above range, the gloss of the coating film may be reduced, and when the epoxy group content exceeds the above range, the edge coverage of the composition may be insufficient.
The viscosity of the above first epoxy resin at 25 ℃ may be 50 to 80mPa · s or 55 to 70mPa · s. When the viscosity of the first epoxy resin at 25 ℃ is less than the above range, the edge coverage of the composition may be reduced, and when it exceeds the above range, the gloss of the coating film may be reduced.
The epoxy equivalent of the first epoxy resin may be 250 to 400g/eq or 300 to 350g/eq. When the epoxy equivalent of the first epoxy resin is less than the above range, the gloss of the coating film may be reduced, and when the epoxy equivalent exceeds the above range, the edge coverage of the composition may be reduced.
< second epoxy resin >
The epoxy group content of the above second epoxy resin may be 3,800 to 4,500mmol/kg or 4,000 to 4,300mmol/kg. In the case where the epoxy group content of the second epoxy resin is less than the above range, the synthetic stability of the additive may be problematic, and in the case where it exceeds the above range, the edge coverage of the composition may be reduced.
The viscosity of the above second epoxy resin at 25 ℃ may be 3 to 15mPa · s or 5 to 10mPa · s. In the case where the viscosity of the second epoxy resin at 25 ℃ is less than the above range, the gloss of the prepared coating film may be reduced, and in the case where it exceeds the above range, the edge coverage of the electrodeposition coating composition may be reduced.
The epoxy equivalent of the second epoxy resin may be 200 to 280g/eq or 220 to 260g/eq. When the epoxy equivalent of the second epoxy resin is less than the above range, the reaction rate of the composition increases, and the workability of the composition becomes insufficient, and when the epoxy equivalent exceeds the above range, the purity decreases.
< alkoxysilane containing amino group >
The amino group-containing alkoxysilane reacts with an epoxy group of the epoxy resin to form a cationic resin and silanol is formed in the resin, and the viscosity of the composition is increased by a siloxane reaction when the viscosity is reduced by drying after electrodeposition coating, thereby playing a role in controlling the fluidity of the edge portion.
The amino group-containing alkoxysilane may be represented by the following chemical formula 1.
[ chemical formula 1]
In the above-described chemical formula 1,
R 1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
For example, R 1 May be a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, R 2 It may be a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms.
The above alkylene and alkoxy groups may be linear or branched. The above-mentioned alkylene group means a branched or straight chain or cyclic divalent radical derived by removing 1 hydrogen atom from a carbon atom of an alkyl group. For example, the alkylene group may be methylene (-CH) 2 -), 1-ethylene (-CH (CH) 3 ) -), 1, 2-ethylene (-CH) 2 CH 2 -), 1-propylene (-CH (CH) 2 CH 3 ) -), 1, 2-propylene (-CH) 2 CH(CH 3 ) -), 1, 3-propylene (-CH) 2 CH 2 CH 2 -) 1, 4-butylene (-CH 2 CH 2 CH 2 CH 2 -) 2, 4-butylene (-CH 2 (CH 3 )CH 2 CH 2 -) and the like, but are not limited thereto.
The cationic water-dispersible additive may be a silanol group-containing silane-modified epoxy resin. For example, in the case of the above cationic water-dispersing additive, the solids content may be from 20 to 30% or from 23 to 27% by weight, the degree of neutralisation may be from 10 to 40mmol/100g or from 15 to 35mmol/100g and the viscosity at 25 ℃ may be from 10 to 100cps or from 30 to 80cps.
When the solid content of the cationic water-dispersing additive is less than the above range, the edge coverage of the composition may be reduced, and when the solid content exceeds the above range, the viscosity of the composition may be increased and the storability may be reduced. In addition, when the neutralization degree of the cationic water-dispersing additive is less than the above range, the storage property of the composition may be insufficient, and when it exceeds the above range, the storage property of the composition may be insufficient. In addition, when the viscosity of the cationic water-dispersing additive is less than the above range, the edge coverage of the composition may be reduced, and when the viscosity exceeds the above range, the storage property of the composition may be insufficient.
The cationic water-dispersing additive may be included in the composition in an amount of 3 to 15 parts by weight or 5 to 10 parts by weight, relative to 5 to 30 parts by weight of the resin. In the case where the content of the cationic water-dispersing additive is less than the above content, the edge coverage of the composition may be reduced, and in the case where the content exceeds the above content, the appearance characteristics and gloss of the resulting coating film may be reduced.
Additive agent
The electrodeposition coating composition may further include 1 or more additives selected from the group consisting of amine compounds, solvents, neutralizing agents, antifoaming agents, oil-removing agents, and fluidity modifiers.
The additives are not particularly limited as long as they can be generally used in an electrodeposition coating composition.
With the electrodeposition coating composition according to the present invention as described above, it is excellent in storage stability and filterability and is capable of forming a coating film excellent in weather resistance and excellent in rust inhibitability of edge (edge).
The present invention will be described in more detail with reference to examples. However, these examples are only for the purpose of facilitating understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
Modes for carrying out the invention
Synthesis example 1: curing agent-1 (blocked cycloaliphatic isocyanate)
To a four-necked flask equipped with a thermometer and a cooler, 40 parts by weight of methyl isobutyl ketone, 400 parts by weight of isophorone diisocyanate, and 0.27 part by weight of dibutyltin laurate were added, and the temperature was raised to 30 ℃ under a nitrogen atmosphere. Thereafter, the temperature was adjusted to not more than 60 ℃ while adding 360 parts by weight of 2- (2-butoxyethoxy) ethanol, and the mixture was left at 60 ℃ for 90 minutes. Thereafter, 120 parts by weight of methyl ethyl ketoxime was added, the temperature was raised to 80 ℃ and the reaction was continued for 3 hours until the unreacted NCO% became 0.02% by weight or less, and then methyl isobutyl ketone was added to adjust the solid content to 80% by weight, thereby preparing a blocked alicyclic isocyanate.
Synthesis example 2: curing agent-2 (blocked aromatic isocyanate)
To a four-necked flask equipped with a thermometer and a cooler, 1,800 parts by weight of 2- (2-butoxyethoxy) ethanol, 106.6 parts by weight of methyl isobutyl ketone, and 0.2 part by weight of dibutyltin laurate were charged and heated to 30 ℃ under a nitrogen atmosphere. Thereafter, 2,028.6 parts by weight of an aromatic isocyanate (manufacturer: dow CHEMICAL COMPANY, product name: PAPI PB 7519) was added while adjusting the temperature to 60 ℃ or less, and left at 60 ℃ for 90 minutes. Thereafter, 0.1 part by weight of dibutyltin laurate and 200 parts by weight of trimethylolpropane were added, and then the mixture was heated to 80 ℃ and kept at the temperature for 3 hours until the unreacted NCO% became 0.02% by weight or less, and then methyl isobutyl ketone was added to adjust the solid content to 80% by weight, thereby preparing a blocked aromatic isocyanate.
Synthesis example 3: preparation of cationic Water-dispersing additive-1
To the reaction vessel were charged 112 parts by weight of a first epoxy resin (manufacturer: dow chemical company, product name: DER 732, epoxy group content: 3,130mmol/kg, viscosity at 25 ℃ C.: 65. + -.5 mPa. Multidot.s, epoxy equivalent: 320 g/eq), 36 parts by weight of a second epoxy resin (manufacturer: hexion, product name: cardura E-10P, epoxy group content: 4,170mmol/kg, viscosity at 25 ℃ C.: 7 mPa. Multidot.s, epoxy equivalent: 240 g/eq), 110 parts by weight of an amino group-containing alkoxysilane (manufacturer: momentive, product name: silquest A-1100, gamma-aminopropyltriethoxysilane), and 120 parts by weight of isopropanol. Thereafter, the reaction was carried out by heating to 110 ℃ under an anhydrous nitrogen atmosphere until the Gardner-Holdt viscosity became T to W. Thereafter, 600 parts by weight of deionized water and 22 parts by weight of lactic acid (50 vol% aqueous solution) were additionally added and dispersed in an aqueous medium to prepare a cationic water-dispersing additive-1 having a solid content of 25 wt%, a neutralization degree of 25mmol/100g, and a viscosity of 45cps at 25 ℃.
Synthesis examples 4 to 8: preparation of cationic Water-dispersing additives-2 to-6
A cationic water-dispersible additive was prepared in the same manner as in synthesis example 3, except that the contents of the respective ingredients were adjusted as in table 1 below.
Synthesis example 9: preparation of cationic Water-dispersing additive-7
A reaction vessel was charged with 24 parts by weight of a third epoxy resin (manufacturer: national chemical, product name: YD-011, epoxy equivalent: 450 to 490 g/eq) and 52 parts by weight of BUTYL CELLOSOLVE (BUTYL CELLOSOLVE) followed by heating and melting. Thereafter, 276 parts by weight of polyoxypropylene diamine (manufacturer: huntsman, product name: jeffamine D2000, number average molecular weight: 2,000mol/g, amine equivalent: 996.5 g/eq), 29 parts by weight of a second epoxy resin (manufacturer: hexion, product name: cardura E-10P, epoxy group content: 4,170mmol/kg, viscosity at 25 ℃:7 mPas, epoxy equivalent: 240 g/eq) were added to conduct a reaction. When the epoxy equivalent reached 1,000g/eq or more, 24 parts by weight of a fourth epoxy resin (manufacturer: national chemical, product name: YD-128, epoxy equivalent: 180 to 190 g/eq) was added to react the epoxy resin, 19 parts by weight of lactic acid (50 vol% aqueous solution) was added to neutralize the epoxy resin, and 576 parts by weight of ionized water was slowly added dropwise to disperse the mixture in water to prepare a cationic water-dispersion additive-7 having a solid content of 35 wt% and a neutralization degree (MEQACID) of 25mmol/100 g.
[ Table 1]
Synthesis example 10: preparation of silane-modified epoxy amine compound
1,000 parts by weight of polyoxypropylene diamine (manufacturer: huntsman, product name: jeffamine D2000, number average molecular weight: 2,000mol/g, amine equivalent: 996.5 g/eq), 100 parts by weight of a second epoxy resin (manufacturer: hexion, product name: cardura E-10P, epoxy group content: 4,170mmol/kg, viscosity at 25 ℃:7 mPa. Multidot.s, epoxy equivalent: 240 g/eq), 141.6 parts by weight of glycidoxypropyltrimethoxysilane (manufacturer: momentive, product name: silquest A-187), and 130 parts by weight of 2-ethylhexanol were charged into a reaction vessel. Thereafter, the reaction was heated to 110 ℃ under an anhydrous nitrogen atmosphere until the Gardner-Holdt viscosity became S-T. Thereafter, 4049.6 parts by weight of deionized water and 66.3 parts by weight of lactic acid (50 vol% aqueous solution) were added and dispersed in an aqueous medium to prepare a silane-modified epoxy amine compound having a solid content of 22 wt%.
Examples 1 to 5 and comparative examples 1 to 6: preparation of electrodeposition coating composition
The raw materials of parts (part) 1 to part 4 described in tables 2 and 3 were charged into a separate type reactor equipped with a stirrer, a cooler, a heater and a thermometer and heated to 125 ℃, and then part 5 was charged and the epoxy equivalent was measured while maintaining the temperature at 145 ℃ until 1,110g/eq was reached. Thereafter, the temperature was adjusted to 110 ℃, part 6 and part 7 were added in sequence and the reaction was carried out at 125 ℃ for 90 minutes. Thereafter, the temperature was adjusted to 100 ℃ and after adding part 8 to part 10, cooled to 70 ℃. Thereafter, portion 11 was added followed by portion 12 and the reaction was carried out at 100 ℃ for 1 hour. Thereafter, the solvent was recovered in a vacuum in an amount corresponding to the content of the fraction 13 to obtain a resin reactant. Thereafter, the above resin reactant was added to the dispersion tank containing the parts 14 to 16 while performing water dispersion 1 time, and after stirring for 1 hour, the part 17 was added to adjust the viscosity. Thereafter, the temperature was adjusted to 45 ℃ or lower and part 18 was added to prepare an electrodeposition coating composition.
[ Table 2]
[ Table 3]
The product names of the respective ingredients used in the comparative examples and examples are shown in table 4 below.
[ Table 4]
Composition (A) | Name of product |
Resin-1 | KOREMUL-BSA-60A (manufacturer: korean Nonghuacheng) |
Resin-2 | BISPHENOL A (manufacturer: brocade lake P)&B chemistry) |
Resin-3 | EPOXY YD-128 (manufacturer: country chemical) |
Organic solvent | DOWANOL PM (manufacturer: the Dow chemical Co., ltd.) |
Crosslinking agent | AMICURE KT-22 (manufacturer: winning wound) |
Defoaming agent | SN DEFAOMER-180 (manufacturer: SAN NOPCO) |
Test examples: evaluation of physical Properties
The electrodeposition coating compositions prepared in the above examples and comparative examples were subjected to electrodeposition coating using a rectifier at 240V for 3 minutes on a test piece (chromate-treated aluminum test piece, horizontal width × vertical length × thickness =150mm × 70mm × 0.8 mm) pretreated with zinc phosphate to form a coating film. The physical properties of the resulting coating films were measured by the following methods and the results are shown in tables 5 and 6.
(1) Gloss of
The 60 ° gloss of the coating film was measured vertically and horizontally. In this case, it is determined that the higher the gloss value, the higher the gloss value.
(2) Curing Properties
Cotton, which was sufficiently wetted with a Methyl isobutyl ketone (MIBK) solvent, was moved on the coating film, and the number of movements until the coating film was flawed was measured at 170 ℃ and 175 ℃.
(3) Impact resistance
When a 1kg drop weight was dropped onto the final coating film while changing the drop height of the drop weight from 20cm to 50cm, the appearance of the coating film was observed and the maximum drop height at which cracks and peeling phenomena did not occur in the coating film was measured to evaluate the impact resistance.
(4) Hardness of
The hardness was measured according to MS652-05 and ISO15184 on a coated film using Mitsubishi pencil.
Specifically, the maximum hardness without damaging the final coating film was measured using pencils of 3B, 2B, HB, F, H, 2H and 3H (3B, 2B, HB, F, H, 2H, 3H: inferior/inferiorExcellent).
(5) Weather resistance-1: Q-UVA
Gloss changes were confirmed on a Q-UVA Type 21 day basis according to ISO 11507. The initial coating film before the weather resistance test was evaluated as follows on the basis of 60 ° gloss: the gloss change rate is excellent when less than 10%; the gloss change rate is generally 10% or more and less than 30%; when the gloss change rate is 30% or more, it is not preferable.
(6) Weather resistance-2: outdoor exposure
Test pieces were prepared and exposed to the open air for 21 days, and changes in gloss were confirmed on the basis of the 60 ° gloss of the initial coating film before the test. The evaluation was as follows: the gloss change rate is excellent when less than 10%; the gloss change rate is generally 10% or more and less than 30%; when the gloss change rate is 30% or more, it is not preferable.
(7) Coating film thickening property-1: blade
The electrodeposition coating composition was applied to the edge portion of the blade (blade edge) as described above, and the thickness of the coating film at the edge portion of the blade (blade edge) was measured by an electron microscope.
(8) Coating film thickening property-2: punching hole
The electrodeposition coating composition was applied to a punched-out test piece (manufacturer: ever Steel) at 240V for 3 minutes, and the thickness of the coating film at the edge portion of the punched-out test piece was measured by an electron microscope.
(9) Filterability
The extent to which the electrodeposition coating compositions prepared in examples and comparative examples passed was grasped by using a nylon mesh screen (sieve) of 100 mesh, and filterability was evaluated as O (good), delta (normal), and X (bad).
In addition, after the composition at 40 ℃ storage for 7 days, with the method of evaluation of filterability.
(10) Sifting wastes (sieve residue)
500g of the electrodeposition coating compositions prepared in examples and comparative examples was filtered through a 100 mesh nylon mesh screen (sieve) and then the residual amount remaining on the screen was measured.
In addition, after the above composition was stored at 40 ℃ for 7 days, the screen residue was measured in the same manner as the above method.
[ Table 5]
[ Table 6]
As shown in table 5, the compositions of examples 1 to 5 were excellent in filterability and small in the size of screen residue even after being stored at 40 ℃ for 7 days, and also excellent in thickening property of the coating film, and the coating films prepared therefrom were excellent in physical properties.
On the other hand, comparative example 6 using the cationic water-dispersing additive of comparative example 1 not containing the cationic water-dispersing additive and synthetic example 9 not containing the amino group-containing alkoxysilane had insufficient curability, insufficient thickening property of the coating film, and insufficient weather resistance. In addition, comparative example 2 using the cationic water-dispersing additive of synthesis example 6 not containing the second epoxy resin and comparative example 3 using the cationic water-dispersing additive of synthesis example 7 not containing the first epoxy resin had insufficient filterability after storage at 40 ℃ and also insufficient weather resistance. Further, comparative example 4 using the cationic water-dispersing additive of synthesis example 8 in which the weight ratio of the first epoxy resin to the second epoxy resin was 0.32.
On the other hand, comparative example 5 using the silane-modified epoxy amine compound instead of the cationic water-dispersing additive was insufficient in weather resistance.
(availability in industry)
The electrodeposition coating composition according to the present invention is excellent in storage stability and filterability, and can form a coating film excellent in weather resistance and also excellent in rust prevention of edges (edge).
Claims (6)
1. An electrodeposition coating composition comprising a resin, a curing agent, and a cationic water-dispersing additive,
the above cationic water-dispersing additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amino group-containing alkoxysilane, and comprises the above first epoxy resin and second epoxy resin in a weight ratio of 1.
2. The electrodeposition coating composition according to claim 1,
the first epoxy resin has a low epoxy group content and a high viscosity at 25 ℃ as compared with the second epoxy resin.
3. The electrodeposition coating composition according to claim 1,
the epoxy group content of the first epoxy resin is 2,500 to 3,500mmol/kg, the viscosity of the first epoxy resin at 25 ℃ is 50 to 80 mPas, and the epoxy equivalent is 250 to 400g/eq.
4. The electrodeposition coating composition according to claim 1, wherein,
the second epoxy resin has an epoxy group content of 3,800 to 4,500mmol/kg, a viscosity of 3 to 15mPa s at 25 ℃, and an epoxy equivalent of 200 to 280g/eq.
5. The electrodeposition coating composition according to claim 1, wherein,
the amino group-containing alkoxysilane is represented by the following chemical formula 1,
[ chemical formula 1]
In the above-described chemical formula 1,
R 1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
6. The electrodeposition coating composition according to claim 1, wherein,
the curing agent is an alicyclic isocyanate.
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