JP2008545827A - 塗料層を形成する腐食保護剤およびその無電流塗装のための方法 - Google Patents
塗料層を形成する腐食保護剤およびその無電流塗装のための方法 Download PDFInfo
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- JP2008545827A JP2008545827A JP2008512709A JP2008512709A JP2008545827A JP 2008545827 A JP2008545827 A JP 2008545827A JP 2008512709 A JP2008512709 A JP 2008512709A JP 2008512709 A JP2008512709 A JP 2008512709A JP 2008545827 A JP2008545827 A JP 2008545827A
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- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- CPEKAXYCDKETEN-UHFFFAOYSA-N benzoyl isothiocyanate Chemical compound S=C=NC(=O)C1=CC=CC=C1 CPEKAXYCDKETEN-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013861 fat-free Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical group [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
Abstract
Description
前記の技術水準を考慮して、本発明の課題は、技術的に簡単に実施できる方法を使用して保護される基板に被覆することができる、生態的に広い範囲で問題のない腐食保護剤を見出すことである。特に前記腐食保護剤は基板から形成される金属イオンの移動が広い範囲で抑制され、基板の縁部および空間に良好に堆積すべきである。更に異種金属イオンの影響をできる限り少なく維持し、かなり少ない材料の使用を有して有効な腐食保護を達成するべきである。更に腐食保護剤はできるだけ多くの異なる金属基板で有効な保護を発揮し、被覆される基板のレドックス電位に広い範囲で依存しないべきである。
本発明による被覆剤の水分散可能なおよび/または水溶性ポリマーPは、基板の腐食の際に遊離した金属イオンとキレートを形成するリガンドAおよびそれ自体で、および/または他の官能基Cと架橋剤V上で共有結合を形成できる架橋する官能基Bを有する。
場合により官能化された尿素および/またはチオ尿素、特にアシルチオ尿素、例えばベンゾイルチオ尿素、
場合により官能化されたアミンおよび/またはポリアミン、例えば特にEDTA、
場合により官能化されたアミド、特にカルボン酸アミド、
イミンおよびイミド、例えば特にイミン官能化ピリジン、
オキシム、有利に1,2−ジオキシム、例えば官能化ジアセチルジオキシム、
有機硫黄化合物、例えば特に場合により官能化されたチオール、例えばチオエタノール、チオカルボン酸、チオアルデヒド、チオケトン、ジチオカルバメート、スルホンアミド、チオアミド、特に有利にスルホネート、
有機燐化合物、例えば特にホスフェート、特に(メタ)アクリレートの燐酸エステル、およびホスホネート、特にビニルホスホン酸、およびヒドロキシ官能化、アミノ官能化およびアミド官能化ホスホネート、
場合により官能化されたポリアルコール、例えば特に炭水化物およびその誘導体およびキトサン、
場合により官能化された酸、例えば特に二官能性および/またはオリゴ官能性酸、または場合により官能化された(ポリ)カルボン酸、例えば特にイオン結合および/または配位結合により金属中心に結合できるカルボン酸、有利に酸基および/または二官能性またはオリゴ官能性酸を有する(ポリ)メタクリレート、
場合により官能化されたカルベン、
アセチルアセトネート、
場合により官能化されたアセチレン、および
フィチン酸およびその誘導体である。
特に有利に(メタ)アクリレート基、
エチルアクリレート基
ビニルエーテル基およびビニルエステル基
クロトネート基およびシンナメート基
アリル基
ジシクロペンタジエニル基
ノルボルニル基およびイソプレニル基
イソプロペニル基またはブテニル基である。
特に有利にヒドロキシル基、
メルカプト基およびアミノ基、
アルデヒド基、
アジド基、
酸基、特にカルボン酸基、
酸無水物基、特にカルボン酸無水物基、
酸エステル基、特にカルボン酸エステル基、
エーテル基、
特に有利にカルバメート基、
尿素基、
エポキシ基、
特に有利に本発明の被覆剤の焼き付け温度でブロックが分解するおよび/またはブロックを分解せずに形成されるネットワークに導入するブロック剤と特に有利に反応したイソシアネート基である。
熱により架橋する基Bおよび相補的基B´からなる特に有利な組み合わせは
ヒドロキシル基とイソシアネート基および/またはカルバメート基、
アミノ基とイソシアネート基および/またはカルバメート基、
カルボン酸基とエポキシ基である。
架橋剤Vは有利に酸性pH範囲、特にpH5未満、特に有利にpH3未満で加水分解安定である。
特にヒドロキシル基、
特にアルデヒド基、
アジド基、
酸無水物基、特にカルボン酸無水物基、
カルバメート基、
尿素基、
特に本発明の被覆剤の焼き付け温度でブロックが分解するおよび/またはブロックを分解せずに形成されるネットワークに導入するブロック剤と特に由利に反応したイソシアネート基、
(メタ)アクリレート基
ビニル基
またはこれらの組み合わせである。
本発明の被覆剤を被覆する前に、本発明の有利な実施態様において、基板を特に油状および脂肪残留物から浄化し、その際有利に洗剤および/またはアルカリ洗浄剤を使用する。本発明の他の有利な実施態様において、洗剤および/またはアルカリ洗浄剤で浄化した後に、本発明の被覆剤を被覆する前に、もう一度水で後洗浄する。基板表面上の堆積物および/または化学的に形成された、特に酸化された層を除去するために、本発明の他の有利な実施態様において、後洗浄工程の前に、例えば研磨剤を使用する表面の機械的洗浄および/または例えば脱酸化洗浄剤を使用する表面層の科学的除去をなお行う。
例1:腐食保護剤Kを有する第1の水槽の製造
水1リットルにモリブデン酸アンモニウム四水和物1.77g(0.01モル)を溶解する。溶液を硝酸を使用してpH2.5に調節する。場合により前記pH値の調節のためにアンモニア水溶液を加えて緩衝する。
平均分子量Mw=800g/モルを有するポリエチレンイミン(LupasolFG、BASF社、第一級アミノ基;第二級アミノ基;第三級アミノ基の比1:0.9:0.5)5g(6.25×10−3モル)を窒素雰囲気下にエタノール100gに予め入れ、75℃で45分以内で、エタノール86gに溶解したベンゾイルイソチオシアネート10.7g(0.066モル)と混合する。この温度でなお4時間攪拌し、生成物を更に精製せずに使用する。
塩化セリウム(III)七水和物3.1g(0.008モル)を水50mlに予め入れる。水50ml中の4−ヒドロキシ桂皮酸4.1g(0.025モル)および苛性ソーダ1g(0.025モル)からなる溶液を製造し、塩酸でpH=7.9にする。この溶液を徐々にセリウム溶液に、セリウム溶液のpH値が6を上回らないように添加する。沈殿物をエタノールおよび水で洗浄する。このセリウム錯体1.7g(0.003モル)を、酢酸エチル80.1g中のジメチルピラゾールで75%ブロックされた分枝状ポリイソシアネート(BayhydurVPLS2319、Bayer社)9.1g(NCO含量2.5%)およびOH官能性ジプロピレントリアミン(Jeffcat−ZR50、Huntsmann)0.7gと一緒に40℃で5時間反応させる。生成物は更に精製せずに使用する。
水1リットルに、例2aによるポリマー成分P3gおよび例2bによる架橋剤V2gを溶解する。溶液を硝酸を使用してpH=2.5に調節する。場合により前記pH値の調節のために、アンモニア水溶液を加えて緩衝する。
基板(亜鉛メッキ鋼からなる板片)を洗浄溶液(RidolineC72、Henkel)中55℃で5分間洗浄し、その後蒸留水で洗浄する。
完全脱塩水中の3%塩化ナトリウムの溶液を使用する。基板としてここで鋼、亜鉛メッキした鋼または亜鉛合金を使用できる。アルミニウムおよびその合金に関して塩化ナトリウム溶液を付加的に酢酸と一緒にpH=3に調節する。試料(3×3cm)をこの溶液170mlに浸漬し、デシケーター中でほぼ100%の水分で保存する。湿った雰囲気を脂肪不含圧縮空気により製造し、圧縮空気が完全脱塩水を有する2つの洗浄容器を通過し、引き続きデシケーターを貫流する。この構造により一定の空気湿度および一定の二酸化炭素含量が保証され、その際25℃に温度を維持する。試料を浸漬の前に分析用天秤で計量する。未処理の参考板片(鋼、亜鉛メッキ鋼)をエタノール中で超音波浴中で5分洗浄する。24時間保存後、板片を溶液から取り出し、計量ピペットを使用してビーカー上で負荷された3%塩化ナトリウム溶液で洗浄する(試料側で塩化ナトリウム溶液約10ml)、引き続き板片を窒素で乾式吹き付けし、50℃で15分乾燥し、計量する。板片を引き続き再び同じ濃度の新鮮な塩化ナトリウム溶液中に懸垂する。使用した塩化ナトリウム溶液を32%塩酸1mlと混合し、場合により存在する沈殿物を溶解する。得られた透明な溶液をICP−OES(高周波誘導結合プラズマ、発光分光分析)により基板金属(Zn、Fe、Al、Mg)の含量を測定する。
a)浸漬溶液のICP−OESデータ
ICP−OESデータは試料の面積に規格化される。このデータは線状の経過が得られる。腐食動力学の線形性により種々の被覆をグラフの上昇により比較できる。ICP−OESデータは面積および時間あたりの基板の分解を表し、それぞれの被覆で可能な腐食速度の直接的尺度である。
b)試料の計量
計量は更に被覆が表面の不活性化をどれだけ可能にするかまたはしないかの可能性に関する情報を与える。このためにモル濃度で質量損失を換算し、試料の面積に規格化する。アルカリのみで洗浄したそれぞれの基板を腐食動力学の比較に使用する。零参考値(純粋基板)およびほかの参考値と比べてICP−OESデータからの上昇が示される。
基板 ICP−OESデータ(10 −4 ・モル/l・h・cm 2 )
亜鉛メッキ鋼板(被覆せず) 8.136
亜鉛メッキ鋼板
例3により被覆 4.580
Gardbond95854(参考) 6.171
腐食試験の結果は従来の腐食保護(参考)に比較して本発明の被覆剤の卓越性を明らかに示す。
Claims (10)
- 金属基板のための水性被覆剤であり、前記被覆剤が水分散可能なおよび/または水溶性ポリマーPを含有し、前記ポリマーが、基板の腐食の際に遊離した金属イオンおよび/または基板表面とキレートを形成する共有結合したリガンドAおよびそれ自体で、ポリマーPの他の相補的官能基B´および/または他の官能基Bおよび/またはB´と架橋剤V上で共有結合を形成できる架橋する官能基Bを有する金属基板のための水性被覆剤。
- 架橋剤Vが共有結合したリガンドAを有する請求項1記載の水性被覆剤。
- リガンドAが、尿素、アミン、アミド、イミン、イミド、ピリジン、有機硫黄化合物、有機燐化合物、有機ホウ素化合物、オキシム、アセチルアセトネート、ポリアルコール、酸、フィチン酸、アセチレンおよび/またはカルベンの群から選択される請求項1または2記載の水性被覆剤。
- ポリマーPおよび架橋剤Vが、熱および/または放射線により架橋可能である架橋する基Bおよび/またはB´を含有する請求項1から3までのいずれか1項記載の水性被覆剤。
- ポリマーPが、ポリマー骨格としてポリエステル、ポリアクリレート、ポリウレタン、ポリオレフィン、ポリアルコール、ポリビニルエーテル、ポリビニルアミン、およびポリアルキレンイミンから選択される1種以上の成分を含有する請求項1から4までのいずれか1項記載の水性被覆剤。
- 金属基板を腐食保護仕上げする方法において、基板を、20〜90℃の温度で1秒〜15分の時間の間、請求項1から5までのいずれか1項記載の被覆剤の浴に浸漬することを特徴とする金属基板を腐食保護仕上げする方法。
- 金属基板を腐食保護仕上げする二工程の方法において、
(a)第1工程において、基板を、基板上で変換を生じる腐食保護剤Kの浴に浸漬し、
(b)第2工程において、工程(a)により処理した基板を、20〜90℃の温度で1秒〜15分の時間の間、請求項1から5までのいずれか1項記載の被覆剤の浴に浸漬する
ことを特徴とする、金属基板を腐食保護仕上げする二工程の方法。 - 第1工程(a)において、カチオンとしてランタニド金属および/またはカチオンとしてクロムを除くd−元素金属および/またはアニオンとしてクロム含有メタラートを除くd−元素メタラートを有する少なくとも1種の化合物ならびに燐含有酸および/またはクロム含有酸を除く少なくとも1種の酸化可能な酸を含有する水性腐食保護剤を使用する請求項7記載の方法。
- 基板を、被覆剤の堆積後に50〜200℃の温度で熱によりおよび/または照射により後処理する請求項6から8までのいずれか1項記載の方法。
- 基板がFe、Alおよび/またはZnから選択される少なくとも20質量%の金属を含有する請求項6から10までのいずれか1項記載の方法。
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PCT/EP2006/003545 WO2006125498A1 (de) | 2005-05-23 | 2006-04-19 | Lackschichtbildendes korrosionsschutzmittel und verfahren zu dessen stromfreier applikation |
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2006
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JP2010509470A (ja) * | 2006-11-13 | 2010-03-25 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | 良好な接着性を有するコーティング膜を形成する防食剤およびその非ガルバニック塗布のための方法 |
JP2012516916A (ja) * | 2009-02-05 | 2012-07-26 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | 耐蝕性の複層塗装及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
MX2007013290A (es) | 2008-01-15 |
ES2354451T3 (es) | 2011-03-15 |
JP5388571B2 (ja) | 2014-01-15 |
BRPI0611636B1 (pt) | 2017-05-09 |
ZA200709672B (en) | 2008-11-26 |
CA2609277C (en) | 2012-07-24 |
WO2006125498A1 (de) | 2006-11-30 |
RU2411272C2 (ru) | 2011-02-10 |
US8475883B2 (en) | 2013-07-02 |
KR20080010440A (ko) | 2008-01-30 |
DE502006008086D1 (de) | 2010-11-25 |
RU2007147411A (ru) | 2009-06-27 |
PL1883679T3 (pl) | 2011-04-29 |
EP1883679B1 (de) | 2010-10-13 |
DE102005023728A1 (de) | 2006-11-30 |
EP1883679A1 (de) | 2008-02-06 |
CA2609277A1 (en) | 2006-11-30 |
CN101258203A (zh) | 2008-09-03 |
CN101258203B (zh) | 2011-10-05 |
BRPI0611636A2 (pt) | 2010-09-28 |
US20080193662A1 (en) | 2008-08-14 |
ATE484553T1 (de) | 2010-10-15 |
KR101261517B1 (ko) | 2013-05-06 |
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