WO2004059036A2 - Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques - Google Patents

Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques Download PDF

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Publication number
WO2004059036A2
WO2004059036A2 PCT/EP2003/014582 EP0314582W WO2004059036A2 WO 2004059036 A2 WO2004059036 A2 WO 2004059036A2 EP 0314582 W EP0314582 W EP 0314582W WO 2004059036 A2 WO2004059036 A2 WO 2004059036A2
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Prior art keywords
group
compounds according
compounds
layer
hydrophilic
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PCT/EP2003/014582
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German (de)
English (en)
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WO2004059036A3 (fr
Inventor
Ralf NÖRENBERG
Christian Wulff
Monica Fernandez Gonzalez
Helmut Witteler
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Basf Aktiengesellschaft
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Priority claimed from DE2002161559 external-priority patent/DE10261559A1/de
Priority claimed from DE2003118981 external-priority patent/DE10318981A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to MXPA05006936A priority Critical patent/MXPA05006936A/es
Priority to BR0317287-2A priority patent/BR0317287A/pt
Priority to EP03785889A priority patent/EP1579032A2/fr
Priority to JP2005509705A priority patent/JP2006513264A/ja
Priority to US10/540,466 priority patent/US20060113509A1/en
Priority to AU2003294913A priority patent/AU2003294913A1/en
Publication of WO2004059036A2 publication Critical patent/WO2004059036A2/fr
Publication of WO2004059036A3 publication Critical patent/WO2004059036A3/fr

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    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • C09D5/12—Wash primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1673—Esters of phosphoric or thiophosphoric acids
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
    • 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
    • B05D2202/00—Metallic substrate

Definitions

  • the present invention relates to compounds of the general formula XYL- (WZ) ⁇ , in which a hydrophobic and a hydrophilic part of the molecule are linked to one another, and X is an end group which can form strong chemical and / or physical interactions with metal surfaces , Y is an aliphatic hydrocarbon group, L is a linking group, W is a hydrophilic group and Z is another end group.
  • the invention further relates to preparations containing these compounds and the use of the compounds for treating metal surfaces.
  • Protective films and / or corrosion inhibitors are used to slow down or prevent corrosion. While a protective film is permanently applied to the metal, a corrosion inhibitor is usually added to substances, such as liquid mixtures, which would cause or accelerate corrosion when in contact with the metal.
  • a corrosion inhibitor is usually added to substances, such as liquid mixtures, which would cause or accelerate corrosion when in contact with the metal.
  • Technically well-suited systems have to meet a number of other requirements in addition to the corrosion-inhibiting effect. For example, they should be able to be applied evenly to a metal surface and have a good barrier effect against corrosion-stimulating gases and liquids.
  • the components of the protective films or the corrosion inhibitors should be easy, accessible in sufficient quantities and, moreover, should be as inexpensive as possible.
  • corrosion-inhibiting compounds have to meet a number of other requirements.
  • Protective films applied to prevent corrosion often form only one layer in a layer composite.
  • a simple example is a metallic surface which is first coated with a suitable agent for corrosion protection, and then a further coating, such as a varnish, is applied to this layer.
  • Connections used for this purpose must on the one hand have a good anti-corrosion effect. However, they still have to have very good adhesion to both the metallic surface and the additional layer in order to give the composite sufficient strength.
  • Modern automobile bodies or materials for household appliances with a high resistance to rusting through are usually produced in multi-stage processes and have many different layers. They typically consist of a steel sheet which is initially electrochemically or hot-dip galvanized. The galvanized sheet is usually phosphated to improve corrosion protection and to improve the adhesion of other layers. Thereafter, Cr (VI) solutions or other solvents are usually used. solutions treated. Finally, a primer layer made of organic materials is applied. The sheet treated in this way is then coated with one or, more usually, several different layers of lacquer. It would be highly desirable to replace this complicated layer structure with a simpler layer structure with fewer layers, but at least equally good or, preferably, better corrosion protection. It would be particularly desirable to be able to avoid phosphating and aftertreatment and instead to use a single primer layer which also takes over the functions of these layers.
  • EP-A 441 765 and JP-A 06-136014 disclose linear compounds in which a hydrophobic and a hydrophilic part of the molecule are directly linked to one another. They have a COOH group at the hydrophobic end and an R-O group at the hydrophilic end. Applications of these compounds in corrosion protection and other end groups are not disclosed.
  • WO 99/52574 discloses coatings that repel biopolymers, for example for coating reaction vessels.
  • compounds are used in which a hydrophobic part of the molecule, for example a hydrocarbon radical and a hydrophilic part of the molecule, for example a polyoxyalkylene radical, are linked directly to one another.
  • the hydrophobic residue has an end group such as -COOH, -PO (OH) 2 or -SiCl 3 , while the end group on the hydrophilic residue is, for example, a small alkyl group or -OH.
  • the use of the compounds for corrosion protection is not mentioned.
  • JP-A 60-226 117 discloses monoesters of aliphatic dicarboxylic acids with polyglycols and their use for producing electrolytic solutions for capacitors.
  • the connections should continue to be used especially in composite systems. be suitable and can mediate good adhesion between different layers. They should continue to be able to be adapted to various applications in the simplest possible way.
  • X an end group which can form strong chemical and / or physical interactions with metal surfaces, comprising at least one acidic group X 1 or salts thereof or at least one hydrolyzable, Si-containing group X 2 ,
  • Y a hydrocarbon group with 5 to 60 carbon atoms, which comprises essentially identical, linearly linked units
  • L 1 a linear linking group which connects a hydrophobic group Y with a hydrophilic group W, selected from the group of S, -SS-, -CO- O-, -O-CO-, -CO-NR 1 -, -NR 1 -CO-, -O-CO-NR 1 -, -NR 1 -CO-0-, -NR 1 -CO-NR 1 - or -
  • L 2 a branching group which connects a hydrophobic group Y with two hydrophilic groups W, selected from the group of -N ⁇ , -NR 1 -CR 1 ⁇ , -CO- N ⁇ , -NR 1 -CO-N ⁇ , -CO-NR 1 -CR ⁇ ,
  • L 3 a branching group, which is a hydrophobic group Y with three hydrophilic
  • Groups W connects selected from the group of -NR 1 -Cs, -NR 1 -CH 2 -Cs, -0-C--, -O-CHz-C ⁇ , -CO-NR 1 -CH 2 -C- -, -CO-NR 1 -C ⁇ , -CO-NR 1 -CH 2 -Cs, -CO-OC ⁇ or -CO-O-CH 2 -C--,
  • R 1 and R 1 ' each independently represent H or C 1 to C 4 alkyl
  • W a hydrophilic group
  • Z an end group which is a reactive end group Z 1 or a non-reactive end group Z 2 ,
  • the linking group L connects a hydrophobic group Y with n hydrophilic groups W, where n can be 1, 2 or 3.
  • Y is connected to the end group X and W to the end group Z.
  • Group X is an end group that can form strong chemical and / or physical interactions with metal surfaces.
  • the group comprises at least one acidic group X 1 or salts thereof or at least one hydrolyzable, Si-containing group X 2 .
  • the acidic group X 1 is preferably a group selected from the group of -COOH, -S0 3 H, -OSO 3 H, -PO (OH) 2 , -PO (OH) (OR 2 ), -OPO (OH) 2 , -OPO (OH) (OR 2 ) or -CR 3 (NH 2 ) (COOH).
  • the acidic group X 1 is particularly preferably - COOH, -PO (OH) 2 or -OPO (OH) 2 . PO (OH) 2 or -OPO (OH) 2 are very particularly preferred.
  • the radical R 2 is any group which is suitable as an ester group in phosphorus or phosphonic acid esters. It is preferably an unbranched or branched C 1 to C 8 alkyl group which can also have further substituents, in particular OH groups. Examples of suitable R 2 radicals include ethyl, butyl, hexyl, octyl, 2-ethylhexyl or 2-hydroxyethyl groups.
  • R 3 is preferably H or C 1 to C 6 alkyl, particularly preferably H or a methyl group. It can also be the residues that are typical of naturally occurring ⁇ -amino acids. Examples include the residues characteristic of lysine (- (CH 2 ) 4 -NH 2 ), serine (-CH 2 -OH), cysteine (-CH 2 -SH) or tyrosine (-CH 2 -C 6 H 4 -OH) ,
  • the acidic group X 1 can be present as an acid group. However, it can also be completely or partially neutralized and accordingly be present as a salt.
  • Particularly suitable counterions are alkali metal ions, alkaline earth metal ions, ammonium or tetraalkylammonium ions, without the invention being intended to be restricted thereto.
  • the Si-containing groups X 2 have hydrolyzable bonds which can react with OH groups on the surface of metals.
  • the groups X 2 can first hydrolyze wholly or partly with water to give -Si (OH) 3 groups, which then react with the surface. The reaction with the surface can of course also take place without such an intermediate stage or via other intermediate stages.
  • the silicon-containing group X 2 is an -SiR 3 group which has Si-R 4 bonds which can be split by water.
  • R 4 can in particular be halogen residues or alkoxy residues act.
  • R 4 is preferably Cl or an -OR 5 radical, R 5 preferably being an unbranched or branched C 1 to C 6 alkyl radical.
  • the end group X is preferably only a group X 1 or a group X 2 , which is in each case directly connected to the aliphatic hydrocarbon group Y. However, it can also be a larger end group which comprises one or more groups X 1 or X 2 . If several groups X 1 or X 2 are present, the end group X preferably comprises either only X 1 or only X 2 groups. However, it is also not excluded for special applications that both X 1 and X 2 are present in an end group. 1 to 3 groups X 1 or X 2 are preferably present in an end group.
  • Suitable end groups X which have a plurality of groups X 1 or X 2 include, in particular, groups which are derived from polyvalent carboxylic acids or polyhydric alcohols. For example, it can be residues derived from malonic acid, citric acid, malic acid, maleic acid or fumaric acid.
  • polyhydric alcohols include glycol, glycerin or pentaerythrol. The alcohols can also be phosphated and thus groups X with several phosphoric acid or phosphonic acid residues can be obtained.
  • the end group X is connected to the hydrophobic group Y.
  • Y is a hydrocarbon group with 5 to 60 carbon atoms, which comprises essentially similar units which are linked linearly to one another.
  • the group Y is preferably aliphatic and saturated, but it can also comprise aromatic units. Essentially of the same type should mean that at least 90% of the same type of units are generally used to build up the group.
  • the group is preferably formed from exclusively identical units.
  • the units can be unbranched or have branches. If branches are present, they are preferably CH 3 groups.
  • the linearly linked units which form the group Y are preferably methylene units -CH 2 -, propylene units -CH 2 -CH (CH 3 ) - or isobutylene units -CH 2 -C (CH 3 ) 2 -.
  • Y is particularly preferably a linear alkyl chain having 8 to 20 C atoms, very particularly preferably having 9 to 15 C atoms.
  • group Y is a polyisobutylene group, it preferably has an average molar mass M n of 150 to 750 g / mol, particularly preferably 400 to 600 g / mol.
  • Polyisobutylene units can in particular also comprise an aromatic unit.
  • the linking group L connects the hydrophobic group Y with the one or more hydrophilic groups W.
  • L 1 is a linear linking group selected from the group of S, -SS-, -CO-O-, -O-CO-, -CO-NR 1 -, -NR 1 -CO-, - O-CO-NR 1 -, -NR 1 -CO-0-, -NR 1 -CO-NR 1 - or - NR 1 -.
  • the linking group is preferably -CO-O-, -O-CO-, -CO-NR 1 -, -NR 1 -CO-, -O-CO-NR 1 -, -NR 1 -CO- 0- or -NR 1 -CO-NR 1 ' - and very particularly preferably around - CO-NR 1 -.
  • L 1 is -CO-O-, -COOH is excluded as end group X.
  • R 1 and R 1 ' are, independently of one another, H or a straight-chain or branched alkyl group, which can optionally also comprise further substituents.
  • R 1 is preferably H or Ci to C alkyl and. very particularly preferably around H or methyl.
  • the group L 2 has a branch. It is used to link a hydrophobic group Y with two hydrophilic groups W.
  • the actual branching is preferably an N atom which binds 2 hydrophilic groups W, while the third bond is connected directly or indirectly to Y.
  • the branching group L 2 is preferably a group selected from the group of -N ⁇ , -NR 1 -CR 1 ⁇ , -CO-N ⁇ , -NR 1 -CO-N ⁇ or - CO-NR 1 -CR 1 ' ⁇ , where R and R 1' have the meaning given above.
  • L 2 is particularly preferably -CO-N ⁇ or CO-NR 1 -CR 1 ' ⁇ .
  • Group L 3 is also branching. It is used to link a hydrophobic group Y with three hydrophilic groups W.
  • the actual branching is preferably a C atom which binds 3 hydrophilic group W, while the fourth bond is directly or indirectly connected to a heteroatom, in particular O or N, which in turn is connected to Y.
  • the branching group L 3 is preferably a group selected from the group of -NR -C--, -NR 1 -CH 2 -C ⁇ , -OC ⁇ , -0-CH 2 -C ⁇ , -CO -NR 1 -CH 2 -C--, -CO-NR 1 -C ⁇ , -CO-NR 1 -CH 2 -C--, -CO-OC ⁇ or -CO-0-CH 2 -C ⁇ .
  • the hydrophilic group W is selected by the person skilled in the art depending on the degree of hydrophilicity desired. These are in particular groups which, in addition to carbon atoms, comprise O and / or N atoms, for example as alcohol, ether or amino groups.
  • the group W is preferably a group comprising C 2 to C alkoxylate units. By selecting the type and number of alkoxylate units, the properties of the group W desired in each case depending on the intended use can be determined by the person skilled in the art.
  • the compounds according to the invention preferably comprise 1 to 10 alkoxylate units, particularly preferably 1 to 5 alkoxylate units. It is known to the person skilled in the art that such alkoxy groups can be obtained, for example, by oxalkylation or starting from technical polyglycols. The values given therefore represent the average number of units ten, whereby the average value does not of course have to be a natural number, but can also be any rational number.
  • the hydrophilic groups W are preferably groups predominantly comprising ethoxylate units. It is known to the person skilled in the art that small amounts of propoxylate or butoxylate units can be used to fine-tune the properties of such groups.
  • the end group Z connected to W can be a reactive end group Z 1 or a non-reactive end group Z 2 .
  • reactive means that the group Z 1 can form bonds with those reactants which are typically used in coatings or lacquers.
  • a group Z 1 can optionally also include several of these groups.
  • R 6 is usually H or a straight-chain or branched Ci to C 6 alkyl group and R 7 is H or CH 3 .
  • Non-reactive groups Z 2 are, in particular, groups which have neither acidic H atoms nor ethylenically unsaturated groups or groups capable of addition.
  • Non-reactive groups are in particular H atoms, alkyl groups or groups in which acidic H atoms are substituted by alkyl groups, such as, for example, ether groups, carboxylic acid ester groups, tertiary amino groups or alkylated carboxamides.
  • the non-reactive group Z 2 is preferably a group selected from the group of -H, -OR 8 , -NR 8 R 9 , -COOR 8 or -CONR 8 R 9 .
  • R 8 and R 9 are, independently of one another, straight-chain or branched C 1 -C 6 -alkyl radicals, preferably methyl or ethyl groups.
  • Compounds which are particularly suitable for treating metal surfaces have phosphate or phosphonate groups as the end group X 1 , a linear C 8 - to C 2 o -alkyl group as the group Y, a carboxamide group -CO-NH- or a carboxylic acid ester group -CO-O- as the linking group Group L 1 , a hydrophilic group W comprising 1 to 5 ethoxy groups, and H or OCH 3 as end group Z 2 .
  • Suitable starting materials for the compounds according to the invention are ⁇ , ⁇ -bifunctional compounds of the general formula ⁇ -Y- ⁇ .
  • the two functional groups are connected by the hydrocarbon group Y, where Y is the above has defined meaning.
  • the two functional groups can be the same or different.
  • One of the two functional groups forms the end group X or can be used to form the end group.
  • the other functional group forms the linking group L or can be used to form the linking group.
  • the bifunctional compounds can be, for example, co-carboxyalkyl-1-enes, ⁇ -hydroxyalkyl-1-enes or ⁇ -hydroxycarboxylic acids or their cyclic esters.
  • Suitable starting compounds include ⁇ -dec-1-enoic acid or ⁇ -undec-1-enoic acid, 9-hydroxynonanoic acid or ⁇ -caprolactone.
  • ⁇ -Hydroxycarboxylic acids (1) or their cyclic esters (1 ') can be reacted, for example, with methyl-poly-ethylene glycol amines (2) according to the following scheme.
  • a carboxylic acid amide (3) is formed by reacting the hydroxycarboxylic acid (1) with methyl-poly-ethylene glycol amines (2).
  • the hydroxyl group of the carboxylic acid amide can, for example, be reacted with polyphosphoric acid (4).
  • the OH group can also be used to bind other acidic groups X 1 or Si-containing groups X 2 .
  • Compounds with branching groups L 2 or L 3 can be obtained by using other compounds (2 ') which have branches instead of methyl-poly-ethylene glycol amines (2) in the above synthesis scheme.
  • Examples include amines of the general formula HN [(CH 2 -CH 2 -0-) k R 8 ] 2 or H 2 NC- [CH 2 0- (CH 2 -CH 2 -0-) k R 8 ] 3 , where R 8 has the meaning mentioned above.
  • the arms of the connections mentioned can be the same or different. If alcohols (2 ") are used instead of the polyethylene glycol amines (2), compounds are obtained which have an ester group as a linking group.
  • Suitable alcohols are in particular oligo- or polyethylene glycol or derivatives thereof, such as monoethers, or compounds which have more than one oligo - or polyethylene glycol group or derivatives, for example compounds of the general formula HO-CH- [CH 2 0- (CH 2 -CH 2 -0-) k R 8 ] 2 or HO-C- [CH 2 0- (CH 2 -CH 2 -0-) k R 8 ] 3 .
  • Bifunctional compounds ⁇ -Y- ⁇ which have an olefinic group can preferably be used for the synthesis of compounds having phosphonic acid end groups.
  • Examples include ⁇ -carboxyalkyl-1-enes or ⁇ -hydroxyalkyl-1-enes.
  • Dialkyl phosphites can be attached to such olefinic groups by a radical mechanism, as described, for example, by Nifant'ev et al. Russian Journal of General Chemistry, 63, 8, Part 1, 1993, 1201-1205.
  • the phosphonic acid ester group can then be hydrolyzed with suitable acids. This is exemplified in the following synthesis scheme:
  • ⁇ -carboxyalkyl-1-ene (6) is first reacted with a dialkyphosphonic acid ester (7) to give the ⁇ -carboxyalkyl-1-phosphonic acid ester (8), which is hydrolyzed to give the ⁇ -carboxyalkyl-1-phosphonic acid (9).
  • the hydrophilic group W and the end group Z can then be appended to the carboxylic acid function, for example by reaction with ethylene glycol, diethylene glycol, oligo- / polyethylene glycols, alkyl-poly-ethylene glycols, polyethylene glycol amines or alkyl-poly-ethylene glycol amines, and also the branching agents mentioned above Alcohols and amines.
  • compounds are formed with a carboxamide group (10) or a carboxylic ester group (11) as a linking group.
  • the compounds according to the invention are particularly suitable for use as corrosion inhibitors.
  • they can be added to products, such as liquid mixtures, which cause or accelerate corrosion in contact with metals. would. Examples include paints, varnishes or cleaning agents.
  • they can also be used in special anti-corrosion formulations.
  • the two end groups X and Z can be adapted for good adhesion, each with one of the materials, in order to obtain a good bond.
  • composites can be obtained from metal foils and plastic foils. Such composites are used in particular for the production of packaging materials.
  • the compounds according to the invention can furthermore be used very particularly advantageously for the production of monomolecular layers on metallic surfaces.
  • compounds are preferably used which have a linearly linking group L.
  • the compounds according to the invention can be used in particular for treating metals or metal surfaces.
  • Treatment is to be understood to mean both operations after the execution of which the compounds according to the invention remain temporarily or permanently on the surface and those in which no compounds remain on the surface. Examples include use as an adhesion promoter, corrosion inhibitor, primer, passivating agent or conversion layer former.
  • the compounds according to the invention can be used as such in the treatment of metals as such. For example, they can be sprayed or poured onto a metallic surface.
  • preparations which comprise at least one of the compounds according to the invention are preferably used for the treatment of metal surfaces.
  • the preparations according to the invention comprise one or more of the compounds according to the invention, a suitable solvent and optionally further components.
  • Suitable solvents are those solvents or solvent mixtures which are capable of dissolving, dispersing, suspending or emulsifying the compounds according to the invention. It can be organic solvents or water. Mixtures of various organic solvents or mixtures of organic solvents with water can of course also be used. The person skilled in the art makes a suitable selection from the solvents which are possible in principle, depending on the intended use and the type of compound used according to the invention. It is for the professional of course, in the case of compounds which have an end group X 2 , only use solvent mixtures which do not cause premature hydrolysis of the end group.
  • organic solvents examples include hydrocarbons such as toluene, xylene or mixtures such as are obtained, for example, from the refining of crude oil and are commercially available, for example, as petroleum ether, kerosene, Solvesso® or Risella®, ethers such as THF or polyethers such as polyethylene glycol, ether alcohols such as butyl glycol, Hexyl glycol, ether glycol acetates such as butyl glycol acetate, ketones such as acetone, alcohols such as methanol, ethanol or propanol. It is also possible to use ethoxylated monohydric or polyhydric alcohols, in particular products derived from C to C 8 alcohols.
  • Preparations which comprise water or a predominantly aqueous solvent mixture are preferred. This should be understood to mean mixtures which comprise at least 50% by weight, preferably at least 65% by weight and particularly preferably at least 80% by weight of water.
  • Other components are water-miscible solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butyl glycol or methoxypropanol or ethoxylated C 4 - C s t-alcohols.
  • Preparations which comprise water as solvent are particularly preferred.
  • the pH of an aqueous solution is determined by the person skilled in the art depending on the type of application desired. Of course, buffer systems can also be used to fix the pH to a certain value.
  • the amount of the compounds according to the invention dissolved, dispersed, suspended or emulsified in the solvent is determined by the person skilled in the art depending on the type of derivative and on the desired application. As a rule, however, the amount is between 0.1 to 100 g / l, preferably 0.5 to 50 g / l and particularly preferably 1 to 20 g / l, without the invention being intended to be restricted thereto. This information refers to a ready-to-use preparation. Of course, concentrates can also be produced that are only diluted to the desired concentration on site before they are actually used.
  • the preparations according to the invention can also comprise further components.
  • the type and amount of the compounds XYL- (WZ) n according to the invention in the preparation are chosen by the person skilled in the art depending on the desired application. Only one of the connections can be selected or two or more different connections can be selected.
  • the properties desired for the desired application can be determined in particular by the type of the end groups X and Z, the type and length of the hydrocarbon group Y and the type and
  • Length of the hydrophilic group W can be determined. Desired properties can be found adjust this way almost continuously. Furthermore, the properties can of course be controlled by using a mixture of several compounds according to the invention and further components.
  • binder can be any suitable polymeric binders.
  • the type and amount of binder depend on the desired application.
  • Formulations containing polymers are particularly suitable for overcoating.
  • Dispersing aids, emulsifiers or surface-active compounds can also be used.
  • examples include cationic, anionic, zwitterionic or nonionic surfactants, such as, for example, alkyl alkoxylates with ethylene and / or propylene oxide units.
  • the preparations can also comprise further corrosion inhibitors, such as, for example, 1- butynediol, benzotriazole, aldehydes, amine carboxylates or suitable phosphoric acid esters.
  • Fine metal particles can also be used in preparations.
  • Lamels made of Al and / or Zn are particularly preferred as metal particles.
  • Preparations containing such lamellas can also be used as corrosion-preventing coatings.
  • a compound which has only a single ethoxy group as the hydrophilic group W and an OCH 3 group as the end group Z 2 can, for example, also be used to make an aluminum surface hydrophobic. If the hydrophilic group W is extended by further ethoxy groups, the hydrophilic character of the surface increases more and more.
  • a compound which differs from the above only in that it has three ethoxy groups instead of one can already be used for the hydrophilization of aluminum surfaces.
  • Preparations which comprise at least one compound with a reactive end group Z 1 in a mixture with at least one compound with a non-reactive end group Z 2 can be used with particular advantage. Depending on the ratio of Z 1 and Z 2 , for example, the adhesive strength of composites can be specifically adjusted.
  • compositions which comprise both compounds according to the invention and the compounds XYZ described in WO 98/29580, in which two end groups X and Z, which are separated from one another by a single hydrophobic group Y, as additional components.
  • the properties of the coating can be varied particularly elegantly by mixing with the compounds according to the invention.
  • the compounds according to the invention can ensure the desired hydrophilization of the surface, while the compounds XYZ ensure the attachment of a second lacquer layer.
  • the compounds and / or the preparations of the compounds can be used for the surface treatment of metals of all kinds. Of course, these can also be alloys of different metals.
  • the surface can be largely flat surfaces, for example the surface of sheets, foils, coils and the like. But it can also be the surface of any shaped body. This also includes the surfaces of very fine particles, for example metal powders, metal platelets or metal pigments. It can also be the surface of materials coated with metallic layers.
  • the compounds and / or preparations according to the invention can of course also be used for the treatment of the inner surfaces of hollow bodies. Examples include use as a coolant, in heat exchanger circuits or in heaters.
  • the metal to be treated is preferably one or more selected from the group of zinc, aluminum, magnesium, chromium, iron, nickel, tin or alloys of these metals with one another or with other metals.
  • the compounds or formulations according to the invention are particularly suitable for the treatment of Zn and / or aluminum and of steels or stainless steels.
  • a metal surface is brought into contact with the preparation according to the invention, for example by spraying, dipping, painting or rolling on.
  • the workpiece can be drained to remove excess treatment solution; in the case of sheets, metal foils or the like, however, excess treatment solution can also be squeezed off, for example.
  • the solvent is then removed, for example by increasing the temperature.
  • no-rinse processes in which the treatment solution is dried directly in a drying oven without rinsing immediately after application.
  • the treatment can also include rinsing steps before the removal of the solvent, rinsing steps afterwards and further post-treatment steps ,
  • the compounds according to the invention are furthermore particularly suitable for producing composites which comprise at least one metallic layer, a layer (A) which comprises at least one of the compounds according to the invention and at least one second layer (B).
  • Compounds which have a reactive group Z 1 are preferably used, so that further layers can also be reactively coupled.
  • Layer (A) is arranged between the metal layer and layer (B).
  • layer (A) is a monomolecular layer.
  • the second layer (B) can be, for example, a lacquer layer.
  • the composite can of course also comprise further layers.
  • the metal layer can still be action layer.
  • the metallic layer can also be coated on both sides with a layer (A).
  • the composites according to the invention have excellent adhesion between the metal layer and layer (B).
  • 9-hydroxynonanoic acid was obtained as described by W. Youchu, L. Fuchu, Synthetic Communications 1994, 24 (9), 1265-1269 by ozonating unsaturated fatty acids and working up the reaction mixture. Since the composition of a natural product such as oleic acid is not uniform, mixtures (depending on the starting material used) are often obtained as the product.
  • Methyldiglycolamine 200 g of diethylene glycol monomethyl ether (Fluka) were placed in a 2.5 l stirred autoclave with 700 ml of THF and 100 g of catalyst H1 / 88 (BASF). The mixture is then rendered inert twice with 5 bar nitrogen and then 500 ml of ammonia are added at room temperature. Is then hydrogen is continued at room temperature up to a pressure of 50 bar and heated with stirring to about 200 C C. Upon reaching 200 ° C, the pressure is by hydrogen were to admit increased to 270 bar.
  • Fluka diethylene glycol monomethyl ether
  • Example 1 Amidation of 9-hydroxynonanoic acid with methyl monoglycolamine
  • Example 3 Amidation of 9-hydroxynonanoic acid with methyltriglycolamine The procedure was as in Example 1, except that 16.2 g (0.1 mol) of methyltriglycolamine were used instead of methylmonoglycolamine as starting material.
  • Example 6 Amidation of ⁇ -caprolactone with methyltriglycolamine The procedure was as in Example 4, except that 32.5 g (0.2 mol) of methyltriglycolamine were used as the starting material instead of methylmonoglycolamine.
  • Example 7 Phosphating of the Amide from 9-Hydroxynonanoic Acid and Methyl Monoglycolamine
  • the product from Example 1 (20 g, 0.0671 mol) and 0.1 g hypophosphorous acid (50%) were placed in a reaction flask under a nitrogen atmosphere. 9.7 g (0.0839 mol) of polyphosphoric acid (85%) were added within 15 minutes.
  • the reaction mixture warmed to 50 ° C during the addition. After the addition had ended, the mixture was heated further to 75 ° C. and stirred at this temperature for 20 h.
  • the reaction was followed by 1 P NMR analysis
  • Example 8 Phosphating of the amide from 9-hydroxynonanoic acid and methyldiglycolamine
  • Example 7 The procedure was as in Example 7, except that the product from Example 2 (30 g, 0.0836 mol) and 12.0 g (0.1045 mol) polyphosphoric acid (85%) were used.
  • Example 9 Phosphating of the amide from 9-hydroxynonanoic acid and methyltriglycolamine
  • Example 7 The procedure was as in Example 7, except that the product from Example 3 (30 g, 0.078 mol) and 11.2 g (0.1045 mol) of polyphosphoric acid (85%) were used.
  • Example 10 Phosphating of the amide from ⁇ -caprolactone and methyl monoglycolamine The procedure was as in Example 7, except that the product from Example 4 (30 g, 0.1586 mol) and 22.9 g (0.1983 mol) of polyphosphoric acid (85%) were used.
  • Example 11 Phosphating the amide from ⁇ -caprolactone and methyldiglycolamine The procedure was as in Example 7, except that the product from Example 5 (30 g, 0.1085 mol) and 15.6 g (0.1983 mol) of polyphosphoric acid (85%) were used.
  • Example 12 Phosphating of the amide from ⁇ -caprolactone and methyltriglycolamine
  • Example 7 The procedure was as in Example 7, except that the product from Example 6 (30 g, 0.12 mol) and 17.3 g (0.15 mol) of polyphosphoric acid (85%) was used.
  • Example 13 Hydrophobicization of Aluminum A punched, not further surface-treated aluminum plate is immersed in an aqueous solution which contains 0.1% of a 9-methylmonoglycolamido-nonylphosphate and 5% cumene sulfonate. After 20 h, the plate is removed and the contact angle of water is determined using methods known from the literature. One finds a contact angle of 75 °. An untreated metal surface has a contact angle of approx. 60 °.
  • a punched, not further surface-treated aluminum plate is immersed in an aqueous solution which contains 0.1% of a 9-methyltriglycolamido-nonylphosphate and 5% Emulan® HE50 (solubilizer, BASF AG, Ludwigshafen). After 20 h, the plate is removed and the contact angle of water is determined using methods known from the literature. One finds a contact angle of 10 °. An untreated metal surface has a contact angle of approx. 60 °.
  • Example 15 Use for corrosion protection An electrochemically galvanized steel sheet was treated according to the procedure of Example 13 with 6-methyldiglykolamido-hexylphosphate (without cumene sulfonate) (contact angle ⁇ 20 °) and was characterized electrochemically. Static and cyclic electrovolammetry was carried out. A selection of the measured characteristic data is shown in Table 1.
  • the steel sheet was also examined for corrosion resistance using a salt spray test in accordance with DIN 10289.
  • the test was carried out on three samples and two untreated sheets for comparison.
  • the corrosion resistance was rated on a scale from 10 (no corrosion) to 1 (severe corrosion).
  • the evaluations were each carried out after a test period of at least 1 h to 6 h and are summarized in Table 2.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Combustion & Propulsion (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Chemically Coating (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne des composés de la formule générale X-Y-L-(W-Z)n où une partie molécule hydrophobe est liée à une partie molécule hydrophile, X représente un groupe terminal permettant de créer de fortes interactions chimiques et/ou physiques sur les surfaces métalliques; Y représente un groupe hydrocarbure aliphatique ; L représente un groupe lié ; W représente un groupe hydrophile et Z représente un autre groupe terminal. L'invention concerne les préparations contenant ces composés et l'utilisation des composés destinée au traitement des surfaces métalliques.
PCT/EP2003/014582 2002-12-23 2003-12-19 Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques WO2004059036A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MXPA05006936A MXPA05006936A (es) 2002-12-23 2003-12-19 Compuestos hidrofobicos-hidrofilicos para el tratamiento de superficies metalicas.
BR0317287-2A BR0317287A (pt) 2002-12-23 2003-12-19 Composto, uso do mesmo, preparação e processo para tratamento de superfìcies metálicas, e, compósito
EP03785889A EP1579032A2 (fr) 2002-12-23 2003-12-19 Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques
JP2005509705A JP2006513264A (ja) 2002-12-23 2003-12-19 金属表面処理用の疎水性−親水性化合物
US10/540,466 US20060113509A1 (en) 2002-12-23 2003-12-19 Hydrophobic-hydrophilic compounds for treating metallic surfaces
AU2003294913A AU2003294913A1 (en) 2002-12-23 2003-12-19 Hydrophobic-hydrophilic compounds for treating metallic surfaces

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10261559.4 2002-12-23
DE2002161559 DE10261559A1 (de) 2002-12-23 2002-12-23 Hydrophob-hydrophile Verbindungen zum Behandeln von metallischen Oberflächen
DE2003118981 DE10318981A1 (de) 2003-04-25 2003-04-25 Hydrophob-hydrophile Verbindungen zum Behandeln von metallischen Oberflächen
DE10318981.5 2003-04-25

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WO2004059036A2 true WO2004059036A2 (fr) 2004-07-15
WO2004059036A3 WO2004059036A3 (fr) 2005-03-17

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BR (1) BR0317287A (fr)
MX (1) MXPA05006936A (fr)
WO (1) WO2004059036A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138264A (ja) * 2005-11-21 2007-06-07 Noguchi Koki Kk 鉄鋼表面の防錆処理剤
WO2008088624A2 (fr) * 2007-01-12 2008-07-24 Dow Global Technologies Inc. Compositions de monomère réactif à terminaison acide carboxylique ou à terminaison hydroxyle
US8460445B2 (en) 2007-06-11 2013-06-11 Basf Se Corrosion protection coatings
CN103820801A (zh) * 2014-03-18 2014-05-28 天津安路浦环保科技发展有限公司 水基反应型铝材专用金属清洗剂及其制备方法

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WO2017150353A1 (fr) * 2016-03-03 2017-09-08 株式会社デンソー Échangeur de chaleur

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US4202706A (en) * 1979-03-12 1980-05-13 Minnesota Mining And Manufacturing Company Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof
EP0153973A1 (fr) * 1982-09-30 1985-09-11 Nihon Parkerizing Co., Ltd. Procédé de traitement de surfaces métalliques
US5059258A (en) * 1989-08-23 1991-10-22 Aluminum Company Of America Phosphonic/phosphinic acid bonded to aluminum hydroxide layer
WO1998029580A1 (fr) * 1996-12-28 1998-07-09 Metallgesellschaft Aktiengesellschaft Procede de traitement de surfaces metalliques
WO1999020682A1 (fr) * 1997-10-22 1999-04-29 N.V. Bekaert S.A. Systemes et procedes permettant d'accroitre l'adherence interfaciale entre une surface metallique et un milieu non metallique, et produits ainsi obtenus
WO2001058909A1 (fr) * 2000-02-10 2001-08-16 The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) Silanes imides contenant du phényléthynyle

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US4202706A (en) * 1979-03-12 1980-05-13 Minnesota Mining And Manufacturing Company Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof
EP0153973A1 (fr) * 1982-09-30 1985-09-11 Nihon Parkerizing Co., Ltd. Procédé de traitement de surfaces métalliques
US5059258A (en) * 1989-08-23 1991-10-22 Aluminum Company Of America Phosphonic/phosphinic acid bonded to aluminum hydroxide layer
WO1998029580A1 (fr) * 1996-12-28 1998-07-09 Metallgesellschaft Aktiengesellschaft Procede de traitement de surfaces metalliques
WO1999020682A1 (fr) * 1997-10-22 1999-04-29 N.V. Bekaert S.A. Systemes et procedes permettant d'accroitre l'adherence interfaciale entre une surface metallique et un milieu non metallique, et produits ainsi obtenus
WO2001058909A1 (fr) * 2000-02-10 2001-08-16 The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) Silanes imides contenant du phényléthynyle

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138264A (ja) * 2005-11-21 2007-06-07 Noguchi Koki Kk 鉄鋼表面の防錆処理剤
WO2008088624A2 (fr) * 2007-01-12 2008-07-24 Dow Global Technologies Inc. Compositions de monomère réactif à terminaison acide carboxylique ou à terminaison hydroxyle
WO2008088624A3 (fr) * 2007-01-12 2008-12-24 Dow Global Technologies Inc Compositions de monomère réactif à terminaison acide carboxylique ou à terminaison hydroxyle
US8460445B2 (en) 2007-06-11 2013-06-11 Basf Se Corrosion protection coatings
CN103820801A (zh) * 2014-03-18 2014-05-28 天津安路浦环保科技发展有限公司 水基反应型铝材专用金属清洗剂及其制备方法

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JP2006513264A (ja) 2006-04-20
BR0317287A (pt) 2005-11-08
KR20050089068A (ko) 2005-09-07
AU2003294913A8 (en) 2004-07-22
WO2004059036A3 (fr) 2005-03-17
EP1579032A2 (fr) 2005-09-28
MXPA05006936A (es) 2005-09-08

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